CN103304752A - Method for preparing silica gel bisphenol A molecularly imprinted polymer by half-covalent process by taking diamine A as template - Google Patents
Method for preparing silica gel bisphenol A molecularly imprinted polymer by half-covalent process by taking diamine A as template Download PDFInfo
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Abstract
The invention discloses a method for preparing a silica gel bisphenol A molecularly imprinted polymer by a half-covalent process by taking diamine A as a template, relating to a method for preparing a bisphenol A molecularly imprinted polymer. The method disclosed by the invention aims at solving the problems of low yield, amorphous particle, low efficiency and identification rate and low locus utilization rate caused by excessively deep embedding of a bisphenol A molecularly imprinted polymer prepared by the existing half-covalent process. The method comprises the following steps of: (I) performing silica gel activation to obtain activated silica gel; (II) connecting silica gel with double bonds to obtain grafted silica gel; (III) polymerizing to obtain a polymerization reaction product; (IV) performing hydrolysis and elution to obtain a silica gel bisphenol A molecularly imprinted polymer. The method disclosed by the invention is mainly used for preparing a silica gel bisphenol A molecularly imprinted polymer.
Description
Technical field
The present invention relates to a kind of method for preparing bisphenol A molecular engram polymer.
Background technology
Dihydroxyphenyl propane, also claim BPA, it is one of most widely used industrial raw material in the world, be mainly used in the high molecular polymers such as polycarbonate synthesis and Resins, epoxy, materials can be applicable to mineral water bottle, baby bottles, the manufacturing of the products such as the inwall of tinned pre-and beverage and care products additive.Dihydroxyphenyl propane is typical environment incretion interferent, and easily in vivo enrichment can be combined with estrogen receptor in body, thereby it is movable to affect normal endocrine metabolism.Correlative study confirmation dihydroxyphenyl propane can be simulated oestrogenic hormon, and the disturbance endocrine system reduces immunizing power, increases the ill probability of cancer, hinders brain development, impels obesity, and the risk of metabolism syndrome and diabetes increases.
At present, the main analysis test method of dihydroxyphenyl propane has high performance liquid chromatography, gas-chromatography, and capillary electrophoresis.(content is generally at ngL owing to bisphenol A concentration in the actual sample is low
-1Perhaps μ gL
-1Rank) and environmental matrices complicated, must carry out pre-treatment and enrichment to sample.Solid-Phase Extraction (solid-phaseextraction, SPE) be method the most frequently used in the dihydroxyphenyl propane sample pre-treatments, tradition SPE sorbent material (such as C18, bonded silica gel, PS-DVB and graphitized carbon black etc.) lacks the special adsorption selectivity to dihydroxyphenyl propane, in order to overcome this problem, we need to seek a kind of material with special adsorptivity.
Molecular imprinting is a kind of the preparation specific target molecules (template molecule) to be had the technology of the high molecular polymer of specific selectivity.The method of molecularly imprinted polymer mainly is covalent method, non-covalent method and half covalent method, and it is slower that covalent method prepares in molecularly imprinted polymer self-assembly or the recognition process combination and the speed of dissociating, and is difficult to reach thermodynamic(al)equilibrium, is unsuitable for quick identification; The standby molecularly imprinted polymer selective recognition of non-covalent legal system is low, and the hole profile is unintelligible.Based on such reason, impel us to explore and utilize half covalent method to prepare molecularly imprinted polymer.Half covalent method is a kind of method of the in recent years people such as Vulfson development, the method was actually molecular self-assembling and pre-assembled combining, first with the mode combination by covalent linkage of template molecule and function monomer, by the chemical process wash-out, when entering in the trace chamber again, template is combined in the mode of non covalent bond with function monomer residue wherein.It is clear that half covalent method combines the configuration of pre-assembled method, and the fast advantage of object release rate of the good and self-assembly method of special Selective adsorption has solved the shortcoming of the slower object bonding of covalency trace and release.
The preparation of the bisphenol A molecular engram polymer of reporting at present is most to be non-covalent method, and the polymer molecule type of this kind method preparation is unintelligible, and in conjunction with insecure, special adsorptive power is poor, has dihydroxyphenyl propane and overflow in actual sample is processed, and test result is inaccurate.All adopt the method for mass polymerization with the bisphenol A molecular engram polymer of half covalent method preparation, the method needs repeatedly to grind, and wastes time and energy, and productive rate is low, particulate amorphous, and efficient, resolving power are low, can destroy the part imprinted sites in process of lapping; Embedding is excessively dark, and the part target molecule can't wash-out, reduces the site utilization ratio.
Summary of the invention
The bisphenol A molecular engram polymer that the objective of the invention is to solve existing half covalent method preparation exists that productive rate is low, particulate amorphous, efficient and the rate of distinguishing is low and because embedding is excessively dark, cause the low problem of site utilization ratio, and a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method is provided.
A kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method, specifically finish according to the following steps:
One, silica gel activating: at first with the silica gel ultra-sonic dispersion in massfraction is 5%～10% hydrochloric acid soln, then be stirring and refluxing reaction 12h～24h under 20～25 ℃ of conditions in temperature, the solid reaction product that obtains utilizes distilled water to be washed till filtrate to be till the neutrality, solid after the washing is put into retort furnace, be 380 ℃～420 ℃ lower roasting 18h～30h in temperature, obtain activated silica gel; The quality of the silica gel described in the step 1 and massfraction are that the volume ratio of 5%～10% hydrochloric acid soln is 1g:(4mL～10mL);
Two, silica gel connects two keys: with the activated silica gel ultra-sonic dispersion in toluene, then under nitrogen protection, add vinyltrimethoxy silane, stirring at room 18h～30h separates the solid that obtains and adopts toluene ultrasonic cleaning 4～6 times, and the solid after the cleaning obtains grafting silica gel through suction filtration; The quality of the activated silica gel described in the step 2 and the volume ratio of toluene are (1g～4g): 20mL; The volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is (3～14): 4;
Three, polymerization: at first diamine A and methacrylic acid are added in the toluene, ultra-sonic dispersion is evenly rear to be heated to 50 ℃～100 ℃ from room temperature, and be 50 ℃～100 ℃ lower stirring reaction 2h～5h in temperature, then add grafting silica gel, and stirring reaction 5min～30min at room temperature, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, ultra-sonic dispersion is evenly rear to be 55 ℃～80 ℃ lower mechanical stirring reaction 18h～30h in nitrogen protection and temperature, obtains polymeric reaction product again; The quality of diamine A described in the step 3 and the volume ratio of toluene are (0.2g～0.4g): 15mL; The volume ratio of the methacrylic acid described in the step 3 and toluene is (150 μ L～350 μ L): 15mL; The quality of the grafting silica gel described in the step 3 and the volume ratio of toluene are (1g～4g): 15mL; The volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is (5～9): 15; The quality of the Diisopropyl azodicarboxylate described in the step 3 and the volume ratio of toluene are (0.07g～0.1g): 15mL;
Four, hydrolysis wash-out: adopt methyl alcohol that polymeric reaction product is carried out supersound washing 5～10 times, the solid that supersound washing obtains extracts as solvent carries out Soxhlet take the sodium hydrate methanol solution of 0.01mol/L～0.1mol/L, Soxhlet is extracted 2d～5d, the extract that obtains adopts first methanol wash, adopt again distilled water wash, adopt at last methanol wash, the product drying after the washing namely obtains the Silica Surface bisphenol A molecular engram polymer again.
Advantage of the present invention: one, the bisphenol A molecular engram polymer of the present invention's preparation uses the surface molecule print technology, thoroughly solved embedding than the bisphenol A molecular engram polymer of conventional art preparation excessively dark, the site utilization ratio is excessively low, the problem of particulate matter setting, and productive rate is high, and adsorption rate is high; Two, the bisphenol A molecular engram polymer of the present invention's preparation adopts the method for half covalency, the preparation clear-cut, and each intermolecular combination is firm, is the holey crosslinking structure, and this structure is so that this molecule imprinted polymer has higher resolving power and adsorption rate; Three, to adopt first diamine A be that template prepares bisphenol A molecular engram polymer by half covalent method at Silica Surface in the present invention, and the method has thoroughly solved template molecule leakage problems in the adsorption process; Four, the template molecule Bisphenol F molecule pattern more reported of the diamine A masterplate molecule that uses of the present invention is more near dihydroxyphenyl propane, and the hydroxyl in the amino specific activity Bisphenol F is strong among the diamine A, easily and function monomer react.
The Silica Surface bisphenol A molecular engram polymer of the present invention preparation has obvious selectivity recognition capability to dihydroxyphenyl propane, and the Silica Surface bisphenol A molecular engram polymer of the present invention's preparation is when being used for the absorption dihydroxyphenyl propane, and clearance can reach more than 80%.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the activated silica gel that obtains of test one step 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the grafting silica gel that obtains of test one step 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of the Silica Surface bisphenol A molecular engram polymer of test one preparation;
Fig. 4 is the red spectrogram of Fourier, A represents to test the red spectrogram of Fourier of the activated silica gel that a step 1 obtains among the figure, B represents to test the red spectrogram of Fourier of the grafting silica gel that a step 2 obtains among the figure, and C represents to test the red spectrogram of Fourier of the Silica Surface bisphenol A molecular engram polymer of a preparation among the figure;
Fig. 5 is curve of adsorption kinetics figure, and ■ represents to test the curve of adsorption kinetics figure of a Silica Surface bisphenol A molecular engram polymer for preparing among the figure, among the figure ● the curve of adsorption kinetics figure of the existing non-molecularly imprinted polymer of expression;
Fig. 6 is the clearance column diagram.
Embodiment
Embodiment one: present embodiment is a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method, specifically finishes according to the following steps:
One, silica gel activating: at first with the silica gel ultra-sonic dispersion in massfraction is 5%～10% hydrochloric acid soln, then be stirring and refluxing reaction 12h～24h under 20～25 ℃ of conditions in temperature, the solid reaction product that obtains utilizes distilled water to be washed till filtrate to be till the neutrality, solid after the washing is put into retort furnace, be 380 ℃～420 ℃ lower roasting 18h～30h in temperature, obtain activated silica gel; The quality of the silica gel described in the step 1 and massfraction are that the volume ratio of 5%～10% hydrochloric acid soln is 1g:(4mL～10mL);
Two, silica gel connects two keys: with the activated silica gel ultra-sonic dispersion in toluene, then under nitrogen protection, add vinyltrimethoxy silane, stirring at room 18h～30h separates the solid that obtains and adopts toluene ultrasonic cleaning 4～6 times, and the solid after the cleaning obtains grafting silica gel through suction filtration; The quality of the activated silica gel described in the step 2 and the volume ratio of toluene are (1g～4g): 20mL; The volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is (3～14): 4;
Three, polymerization: at first diamine A and methacrylic acid are added in the toluene, ultra-sonic dispersion is evenly rear to be heated to 50 ℃～100 ℃ from room temperature, and be 50 ℃～100 ℃ lower stirring reaction 2h～5h in temperature, then add grafting silica gel, and stirring reaction 5min～30min at room temperature, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, ultra-sonic dispersion is evenly rear to be 55 ℃～80 ℃ lower mechanical stirring reaction 18h～30h in nitrogen protection and temperature, obtains polymeric reaction product again; The quality of diamine A described in the step 3 and the volume ratio of toluene are (0.2g～0.4g): 15mL; The volume ratio of the methacrylic acid described in the step 3 and toluene is (150 μ L～350 μ L): 15mL; The quality of the grafting silica gel described in the step 3 and the volume ratio of toluene are (1g～4g): 15mL; The volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is (5～9): 15; The quality of the Diisopropyl azodicarboxylate described in the step 3 and the volume ratio of toluene are (0.07g～0.1g): 15mL;
Four, hydrolysis wash-out: adopt methyl alcohol that polymeric reaction product is carried out supersound washing 5～10 times, the solid that supersound washing obtains extracts as solvent carries out Soxhlet take the sodium hydrate methanol solution of 0.01mol/L～0.1mol/L, Soxhlet is extracted 2d～5d, the extract that obtains adopts first methanol wash, adopt again distilled water wash, adopt at last methanol wash, the product drying after the washing namely obtains the Silica Surface bisphenol A molecular engram polymer again.
Diamine A and methacrylic acid reaction process are as follows in the present embodiment step 3:
The bisphenol A molecular engram polymer of present embodiment preparation uses the surface molecule print technology, thoroughly solved embedding than the bisphenol A molecular engram polymer of conventional art preparation excessively dark, the site utilization ratio is excessively low, the problem of particulate matter setting, and productive rate is high, and adsorption rate is high.
The bisphenol A molecular engram polymer of present embodiment preparation adopts the method for half covalency, the preparation clear-cut, and each intermolecular combination is firm, is the holey crosslinking structure, and this structure is so that this molecule imprinted polymer has higher resolving power and adsorption rate.
It is that template prepares bisphenol A molecular engram polymer by half covalent method at Silica Surface that present embodiment adopts diamine A first, and the method has thoroughly solved template molecule leakage problems in the adsorption process.
The template molecule Bisphenol F molecule pattern that the diamine A masterplate molecule that present embodiment is used has been reported more is more near dihydroxyphenyl propane, and the hydroxyl in the amino specific activity Bisphenol F is strong among the diamine A, easily and function monomer react.
Embodiment two: the difference of present embodiment and embodiment one is: the silica gel described in the step 1 is 60～100 order amorphous silica gels, 100～200 order amorphous silica gels, 200～300 order amorphous silica gels, 60～100 order spherical silica gels, 100～200 order spherical silica gels or 200～300 order spherical silica gels.Other are identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or twos' difference is: the quality of the silica gel described in the step 1 and massfraction are that the volume ratio of 5%～10% hydrochloric acid soln is 1g:(4.3mL～8.48mL).Other are identical with embodiment one or two.
Embodiment four: the difference of one of present embodiment and embodiment one to three is: the quality of the activated silica gel described in the step 2 and the volume ratio of toluene are (2g～3g): 20mL.Other are identical with embodiment one to three.
Embodiment five: the difference of one of present embodiment and embodiment one to four is: the volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is (4～6): 3.Other are identical with embodiment one to four.
Embodiment six: the difference of one of present embodiment and embodiment one to five is: the quality of the diamine A described in the step 3 and the volume ratio of toluene are (0.2g～0.3g): 15mL.Other are identical with embodiment one to five.
Embodiment seven: the difference of one of present embodiment and embodiment one to six is: the volume ratio of the methacrylic acid described in the step 3 and toluene is (170 μ L～300 μ L): 15mL.Other are identical with embodiment one to six.
Embodiment eight: the difference of one of present embodiment and embodiment one to seven is: the quality of the grafting silica gel described in the step 3 and the volume ratio of toluene are (2g～3g): 15mL.Other are identical with embodiment one to seven.
Embodiment nine: the difference of one of present embodiment and embodiment one to eight is: the volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is (6～8): 15.Other are identical with embodiment one to eight.
Embodiment ten: the difference of one of present embodiment and embodiment one to nine is: the quality of the Diisopropyl azodicarboxylate described in the step 3 and the volume ratio of toluene are (0.08g～0.09g): 15mL.Other are identical with embodiment one to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method, specifically finish according to the following steps:
One, silica gel activating: at first with 100～200 order spherical silica gel ultra-sonic dispersion in massfraction is 7% hydrochloric acid soln, then be stirring and refluxing reaction 18h under 23 ℃ of conditions in temperature, the solid reaction product that obtains utilizes distilled water to be washed till filtrate to be till the neutrality, solid after the washing is put into retort furnace, be 400 ℃ of lower roasting 24h in temperature, obtain activated silica gel; The quality of 100～200 order spherical silica gels described in the step 1 and massfraction are that the volume ratio of 7% hydrochloric acid soln is 1g:7mL;
Two, silica gel connects two keys: with the activated silica gel ultra-sonic dispersion in toluene, then under nitrogen protection, add vinyltrimethoxy silane, stirring at room 24h separates the solid that obtains and adopts toluene ultrasonic cleaning 5 times, and the solid after the cleaning obtains grafting silica gel through suction filtration; The quality of the activated silica gel described in the step 2 and the volume ratio of toluene are 2.5g:20mL; The volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is 2:1;
Three, polymerization: at first diamine A and methacrylic acid are added in the toluene, ultra-sonic dispersion is evenly rear to be heated to 90 ℃ from room temperature, and be 90 ℃ of lower stirring reaction 4h in temperature, then add grafting silica gel, and stirring reaction 20min at room temperature, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, ultra-sonic dispersion is evenly rear to be 65 ℃ of lower mechanical stirring reaction 24h in nitrogen protection and temperature, obtains polymeric reaction product again; The quality of diamine A described in the step 3 and the volume ratio of toluene are 0.3g:15mL; The volume ratio of the methacrylic acid described in the step 3 and toluene is 250 μ L:15mL; The quality of the grafting silica gel described in the step 3 and the volume ratio of toluene are 2.5g:15mL; The volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is 7:15; The quality of the Diisopropyl azodicarboxylate described in the step 3 and the volume ratio of toluene are 0.09g:15mL;
Four, hydrolysis wash-out: adopt methyl alcohol that polymeric reaction product is carried out supersound washing 8 times, the solid that supersound washing obtains extracts as solvent carries out Soxhlet take the sodium hydrate methanol solution of 0.06mol/L, Soxhlet is extracted 4d, the extract that obtains adopts first methanol wash, adopt again distilled water wash, adopt at last methanol wash, the product drying after the washing namely obtains the Silica Surface bisphenol A molecular engram polymer again.
Fig. 1 is 500 times of scanning electron microscope (SEM) photographs of the activated silica gel that obtains of test one step 1, and silica gel used in the present invention is spherical silica gel as shown in Figure 1, and there is a small amount of impurity on the surface.
Fig. 2 is 500 times of scanning electron microscope (SEM) photographs of the grafting silica gel that obtains of test one step 2, Silica Surface is relatively smooth as shown in Figure 2, this is because silane coupling agent generates due to the rete in Silica Surface reaction, in the simultaneous reactions process under violent stirring Silica Surface impurity reduce to some extent, this proof silane coupling agent successfully be grafted on the Silica Surface.
Fig. 3 is 40000 times of scanning electron microscope (SEM) photographs of the Silica Surface bisphenol A molecular engram polymer of test one preparation, as shown in Figure 3, the network that the spherical silica gel surface is comprised of the imprinted polymer microballoon and void structure and make its surface irregularity uneven, this explanation imprinted polymer successfully has been grafted to above the silica gel.
Fig. 4 is the red spectrogram of Fourier, A represents to test the red spectrogram of Fourier of the activated silica gel that a step 1 obtains among the figure, B represents to test the red spectrogram of Fourier of the grafting silica gel that a step 2 obtains among the figure, and C represents to test the red spectrogram of Fourier of the Silica Surface bisphenol A molecular engram polymer of a preparation among the figure; A compares with B as shown in Figure 4,920cm
-1The Si-OH absorption peak strength at place obviously weakens, thereby this is that the hydroxyl quantity that causes Silica Surface reduces 2792cm because the hydroxyl of silane coupling agent VTMO and Silica Surface reacts
-1Near the vibration absorption peak of C-H has appearred, this can prove that silane coupling agent VTMO successfully is grafted on the silica gel.Among the contrast C, 1500cm
-1Ester group peak, 2792cm have obviously appearred in the place
-1Near C-H vibration absorption peak obviously strengthens, and this is because in the imprinted polymer ethylene glycol dimethacrylate unit is arranged, simultaneously 3357cm
-1The place among the MAA-stretching vibration peak of OH group, and there is no the absorption vibration peak of diamine A in the infrared spectrum, therefore deducibility template molecule diamine A wash-out.By above contrast, analysis, illustrate that Silica Surface has successfully synthesized bisphenol A molecular engram polymer.
Adsorptive power detects
Test two: the Silica Surface bisphenol A molecular engram polymer and the existing non-molecularly imprinted polymer of 20mg that take by weighing 20mg test one preparation, add respectively in the plastic centrifuge tube of two parts of 0.1mmol/L dihydroxyphenyl propane solution that fill 10mL, different time vibrates respectively, centrifugal, the ultraviolet detection supernatant liquor, measure three times and average, by formula Q=(Co-Ct) * V/M calculates adsorptive capacity: wherein Q is the unit adsorptive capacity (mg/g) of concussion different time; Co is the starting point concentration (mg/L) of template molecule; Ct is the concentration (mg/L) of t template molecule during the moment; V is the volume (L) of solution upon adsorption; M is the quality (g) of imprinted polymer.
Fig. 5 is curve of adsorption kinetics figure, and ■ represents to test the curve of adsorption kinetics figure of a Silica Surface bisphenol A molecular engram polymer for preparing among the figure, among the figure ● the curve of adsorption kinetics figure of the existing non-molecularly imprinted polymer of expression; As seen in Figure 5, along with the increase of time, the Silica Surface bisphenol A molecular engram polymer of test one preparation and existing non-molecularly imprinted polymer increase gradually about 18 minutes the adsorptive capacity of dihydroxyphenyl propane and reach adsorption equilibrium.When reaching balance, the Silica Surface bisphenol A molecular engram polymer of test one preparation is 7.8mg/g to the adsorptive capacity of dihydroxyphenyl propane, and existing non-molecularly imprinted polymer only has 2.1mg/g to the adsorptive capacity of dihydroxyphenyl propane.The Silica Surface bisphenol A molecular engram polymer of above explanation test one preparation has special adsorption selectivity to dihydroxyphenyl propane, and adsorptive power is far above the adsorptive power of existing non-molecularly imprinted polymer.As can be seen from Figure 5, the time of equilibrium adsorption of the Silica Surface bisphenol A molecular engram polymer of test one preparation is about 18 minutes, time of equilibrium adsorption and molecular imprinting surface cross-linked network pattern have direct relation, good surface topography is conducive to accelerate the rate of mass transfer between recognition site and the template molecule, be that surface topography is better, the adsorption equilibrium required time is shorter.From Fig. 5, we also can find out, adsorb dynamic curve after 18 minutes straight, do not have the problem of dihydroxyphenyl propane seepage.
Test three: the Silica Surface bisphenol A molecular engram polymer and the existing non-molecularly imprinted polymer of 80mg that take by weighing 80mg test one preparation, add respectively in two parts of 0.1mmol/L dihydroxyphenyl propane acetonitrile solutions that fill 10mL, with at room temperature continuous oscillation of mixture 2 hours, the centrifuging and taking supernatant liquor, the absorbancy of dihydroxyphenyl propane solution when measuring adsorption equilibrium with ultraviolet spectrophotometer, calculate the concentration of the dihydroxyphenyl propane of supernatant liquor, calculate molecularly imprinted polymer to the clearance E (%) of dihydroxyphenyl propane according to change in concentration situation before and after the absorption again, with sample be eluted to detect without bis-phenol A till, carry out again adsorption experiment after the room temperature vacuum-drying, repeat 5 times according to above step, calculate according to formula E=(Co-Ce)/Co * 100% that molecularly imprinted polymer is to the clearance of dihydroxyphenyl propane each time, wherein E is adsorption efficiency (%); Co is the starting point concentration (mmol/L) of the front substrate of absorption; The concentration of substrate (mmol/L) when Cp is adsorption equilibrium.
Fig. 6 is the clearance column diagram, as can be seen from Figure 6, the Silica Surface bisphenol A molecular engram polymer of test one preparation is respectively 28.91% and 26.13% to the clearance of competition molecule phenol and nonyl phenol, the dihydroxyphenyl propane clearance is then up to 80.34%, this Silica Surface bisphenol A molecular engram polymer that this invention preparation is described has obvious selectivity recognition capability, special high adsorption capacity.And existing non-molecularly imprinted polymer is very low and close to the clearance of three kinds of materials, is respectively 25.97%, 24.36%, 22.91%, and the existing non-molecularly imprinted polymer of this explanation does not have the selectivity recognition capability to dihydroxyphenyl propane.
Claims (10)
1. method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method is characterized in that take diamine A as template the method for preparing the Silica Surface bisphenol A molecular engram polymer by half covalent method finishes according to the following steps:
One, silica gel activating: at first with the silica gel ultra-sonic dispersion in massfraction is 5%～10% hydrochloric acid soln, then be stirring and refluxing reaction 12h～24h under 20～25 ℃ of conditions in temperature, the solid reaction product that obtains utilizes distilled water to be washed till filtrate to be till the neutrality, solid after the washing is put into retort furnace, be 380 ℃～420 ℃ lower roasting 18h～30h in temperature, obtain activated silica gel; The quality of the silica gel described in the step 1 and massfraction are that the volume ratio of 5%～10% hydrochloric acid soln is 1g:(4mL～10mL);
Two, silica gel connects two keys: with the activated silica gel ultra-sonic dispersion in toluene, then under nitrogen protection, add vinyltrimethoxy silane, stirring at room 18h～30h separates the solid that obtains and adopts toluene ultrasonic cleaning 4～6 times, and the solid after the cleaning obtains grafting silica gel through suction filtration; The quality of the activated silica gel described in the step 2 and the volume ratio of toluene are (1g～4g): 20mL; The volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is (3～14): 4;
Three, polymerization: at first diamine A and methacrylic acid are added in the toluene, ultra-sonic dispersion is evenly rear to be heated to 50 ℃～100 ℃ from room temperature, and be 50 ℃～100 ℃ lower stirring reaction 2h～5h in temperature, then add grafting silica gel, and stirring reaction 5min～30min at room temperature, add Ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, ultra-sonic dispersion is evenly rear to be 55 ℃～80 ℃ lower mechanical stirring reaction 18h～30h in nitrogen protection and temperature, obtains polymeric reaction product again; The quality of diamine A described in the step 3 and the volume ratio of toluene are (0.2g～0.4g): 15mL; The volume ratio of the methacrylic acid described in the step 3 and toluene is (150 μ L～350 μ L): 15mL; The quality of the grafting silica gel described in the step 3 and the volume ratio of toluene are (1g～4g): 15mL; The volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is (5～9): 15; The quality of the Diisopropyl azodicarboxylate described in the step 3 and the volume ratio of toluene are (0.07g～0.1g): 15mL;
Four, hydrolysis wash-out: adopt methyl alcohol that polymeric reaction product is carried out supersound washing 5～10 times, the solid that supersound washing obtains extracts as solvent carries out Soxhlet take the sodium hydrate methanol solution of 0.01mol/L～0.1mol/L, Soxhlet is extracted 2d～5d, the extract that obtains adopts first methanol wash, adopt again distilled water wash, adopt at last methanol wash, the product drying after the washing namely obtains the Silica Surface bisphenol A molecular engram polymer again.
2. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1 is characterized in that the silica gel described in the step 1 is 60～100 order amorphous silica gels, 100～200 order amorphous silica gels, 200～300 order amorphous silica gels, 60～100 order spherical silica gels, 100～200 order spherical silica gels or 200～300 order spherical silica gels.
3. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1 is characterized in that the quality of the silica gel described in the step 1 and massfraction are that the volume ratio of 5%～10% hydrochloric acid soln is 1g:(4.3mL～8.48mL).
4. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1, the volume ratio that it is characterized in that the quality of the activated silica gel described in the step 2 and toluene is (2g～3g): 20mL.
5. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1 is characterized in that the volume ratio of the vinyltrimethoxy silane described in the step 2 and toluene is (4～6): 3.
6. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1, the volume ratio that it is characterized in that the quality of the diamine A described in the step 3 and toluene is (0.2g～0.3g): 15mL.
7. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1 is characterized in that the volume ratio of the methacrylic acid described in the step 3 and toluene is (170 μ L～300 μ L): 15mL.
8. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1, the volume ratio that it is characterized in that the quality of the grafting silica gel described in the step 3 and toluene is (2g～3g): 15mL.
9. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1 is characterized in that the volume ratio of the Ethylene glycol dimethacrylate described in the step 3 and toluene is (6～8): 15.
10. a kind of method for preparing the Silica Surface bisphenol A molecular engram polymer take diamine A as template by half covalent method according to claim 1, the volume ratio that it is characterized in that the quality of the Diisopropyl azodicarboxylate described in the step 3 and toluene is (0.08g～0.09g): 15mL.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480350A (en) * | 2013-09-23 | 2014-01-01 | 哈尔滨工程大学 | Method for preparing molecularly imprinted polymer through silica gel surface coating |
| CN103980443A (en) * | 2014-05-27 | 2014-08-13 | 黑龙江大学 | Method for preparing hydrophilic bisphenol A molecularly imprinted polymer by using semi-covalent method |
| CN104892868A (en) * | 2015-05-14 | 2015-09-09 | 江苏科技大学 | Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof |
| CN105566586A (en) * | 2016-03-04 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Preparation method of benzenearsonic acid molecular imprinting polymer |
| CN113318482A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic hybrid material and preparation method and application thereof |
| CN113929840A (en) * | 2021-10-11 | 2022-01-14 | 华中科技大学 | Hollow porous medium for separating and enriching taxane, preparation and application thereof |
-
2013
- 2013-06-18 CN CN201310241429.5A patent/CN103304752B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| JAE CHUN RYU ET AL: ""Molecularly Imprinted polymer for adsorption of Bisphenol A"", 《JOURNAL OF THE KOREAN CHEMICAL SOCIETY》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103480350A (en) * | 2013-09-23 | 2014-01-01 | 哈尔滨工程大学 | Method for preparing molecularly imprinted polymer through silica gel surface coating |
| CN103980443A (en) * | 2014-05-27 | 2014-08-13 | 黑龙江大学 | Method for preparing hydrophilic bisphenol A molecularly imprinted polymer by using semi-covalent method |
| CN103980443B (en) * | 2014-05-27 | 2016-06-01 | 黑龙江大学 | A kind of half covalent method prepares the method for wetting ability bisphenol A molecular engram polymer |
| CN104892868A (en) * | 2015-05-14 | 2015-09-09 | 江苏科技大学 | Silica gel surface molecularly imprinted polymer with specific adsorption of DEHP and preparation method and application thereof |
| CN104892868B (en) * | 2015-05-14 | 2017-09-12 | 江苏科技大学 | A kind of specific adsorption DEHP Silica Surface molecularly imprinted polymer and preparation method and application |
| CN105566586A (en) * | 2016-03-04 | 2016-05-11 | 中国科学院新疆理化技术研究所 | Preparation method of benzenearsonic acid molecular imprinting polymer |
| CN105566586B (en) * | 2016-03-04 | 2017-12-19 | 中国科学院新疆理化技术研究所 | A kind of preparation method of arsenobenzene acids molecularly imprinted polymer |
| CN113318482A (en) * | 2020-02-28 | 2021-08-31 | 北方民族大学 | Hydrophilic hybrid material and preparation method and application thereof |
| CN113318482B (en) * | 2020-02-28 | 2022-08-09 | 北方民族大学 | Hydrophilic hybrid material and preparation method and application thereof |
| CN113929840A (en) * | 2021-10-11 | 2022-01-14 | 华中科技大学 | Hollow porous medium for separating and enriching taxane, preparation and application thereof |
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