CN102784616B - Methyl-p-hydroxy benzoate surface imprinting absorbent as well as preparation method and application thereof - Google Patents
Methyl-p-hydroxy benzoate surface imprinting absorbent as well as preparation method and application thereof Download PDFInfo
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- CN102784616B CN102784616B CN201210299333.XA CN201210299333A CN102784616B CN 102784616 B CN102784616 B CN 102784616B CN 201210299333 A CN201210299333 A CN 201210299333A CN 102784616 B CN102784616 B CN 102784616B
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Abstract
The invention discloses a methyl-p-hydroxy benzoate surface imprinting absorbent as well as a preparation method and an application of the methyl-p-hydroxy benzoate surface imprinting absorbent, which belongs to the technical field of environmental material preparation. The preparation method disclosed by the invention comprises the steps of: forming a preassembling system by using synthetic monodisperse silicon dioxide nano microballoons as a substrate, methyl-p-hydroxy benzoate as template molecules and 3-aminopropyltriethoxysilane as a functional monomer; then adding tetraethyl orthosilicate as a crosslinking agent and acetic acid as a catalyst to obtain a colloid absorbent body; and finally eluting the template molecules for the absorbent body and washing the absorbent body as neutral, and vacuumizing and drying to obtain the methyl-p-hydroxy benzoate surface imprinting absorbent. As imprinting occurs on the surface of the substrate material of silicon dioxide nano particles, the problem that part of the template molecules due to over-deep embedment cannot be eluted is solved. The imprinting absorbent obtained by the method has high mechanical strength, the identification point is not easy to damage, the non-special absorption is reduced, and the imprinting absorbent has the advantages of high selectivity to methyl-p-hydroxy benzoate, remarkable separation effect, and repeated use, and is expected to provide the novel methyl-p-hydroxy benzoate absorbent for purification of industrialized production of wintergreen oil.
Description
Technical field
The invention belongs to environmentally conscious materials preparing technical field, relate to a kind of preparation method who removes the new adsorbent of methyl hydroxybenzoate in wintergreen, relate in particular to surface imprinted adsorbent of a kind of methyl hydroxybenzoate and its preparation method and application.
Background technology
Molecular imprinting (MIT) be in simulating nature circle as: enzyme-to-substrate, the Molecular Recognization of antibody and antigen etc., take target molecule as template molecule, preparation has macromolecule imprinted polymer (the Molecularly Imprinted Polymers of specific selectivity recognition function to this molecule, MIPs) a kind of technology---select and can produce with template molecule the functional monomer of specific interaction, at template molecule, carry out polymerization with crosslinking agent around, form three-dimensional cross-linked polymer network, finally pass through physics, the methods such as chemistry are removed template molecule, just obtained and there is functional high-polymer template molecule to special compatibility and identity hole.Surface molecule print technology is by being based upon molecular recognition site on the surface of host material, thereby be conducive to removing and combination again of template molecule, preferably resolve some major defects that traditional molecular imprinting integral body also exists, as excessively dark in avtive spot embedding, the kinetic rate of mass transfer and charge transfer is slow, and the dynamic performance of adsorption-desorption is not good etc.Conventional host material has inorganic silicon, the titanium base materials such as silica, aluminium oxide or titanium oxide.
Silica (SiO
2) water insoluble and any solvent, nonpoisonous and tasteless, stable chemical nature does not react with any other material except highly basic, hydrofluoric acid, Heat stability is good, stable chemical nature, has higher mechanical strength etc.The present invention adopts monodisperse nano silicon dioxide microballoon prepared by sol-gel technique because its particle diameter is very little, so specific area is large, and adsorption power is strong, and surface can be large, so it has many other same type of material and is difficult to the feature replacing
Wintergreen is gaultherolin, conventional and cosmetics and production of flavor, and the odorant as pharmaceutical preparation lumen medicine and paint etc. as usual, other are as contained and also have application with medicine in the mouths such as chewing gum, mouthwash.In wintergreen production process often with impurity methyl hydroxybenzoate (methyl p-hydroxybenzoate), there is data to show that methyl hydroxybenzoate is as a kind of anticorrisive agent, if the long-term edible food that adds methyl hydroxybenzoate, may cause digestive discomfort, skin, mucous membrane inflammation; If be present in cosmetics, repeat for a long time accumulation use and can cause allergic, to add the DNA of intensive ultraviolet his-and-hers watches chrotoplast destruction, seriously can be carcinogenic.Therefore the impurity methyl hydroxybenzoate of effectively removing in wintergreen has important Research Significance, consider that synthetic imprinted polymer has the single-minded selective recognition function of predetermined substance methyl hydroxybenzoate (MP), thereby for the purifying of wintergreen production process provides a class new method, can bring into play irreplaceable effect in large industrial goods separation and purification field.
Summary of the invention
The monodisperse silica Nano microsphere that technical scheme of the present invention refers to synthesize is substrate, methyl hydroxybenzoate (MP) is as template molecule, 3-aminopropyl triethoxysilane (APTES) is function monomer, tetraethyl orthosilicate (TEOS) is crosslinking agent, acetic acid (HAc) is catalyst, adopts sol-gel process to prepare the surface imprinted adsorbent (MIP of methyl hydroxybenzoate
mP) method.
The preparation method of the surface imprinted adsorbent of a kind of methyl hydroxybenzoate, be the monodisperse silica Nano microsphere synthesizing be substrate, methyl hydroxybenzoate is template molecule, 3-aminopropyl triethoxysilane is that function monomer forms pre-assembled system, adding tetraethyl orthosilicate is crosslinking agent again, acetic acid is that catalyst makes colloid adsorbent parent, finally will after adsorbent parent wash-out template molecule, be washed till neutrality, and vacuum drying forms.
Synthetic monodisperse silica Nano microsphere preparation process of the present invention is as follows:
Steps A, by tetraethyl orthosilicate, H
2o, ammoniacal liquor, absolute ethyl alcohol be mix and blend 4 ~ 5h at 25 ℃ of room temperatures,
Wherein, described tetraethyl orthosilicate volume is 4.05 ~ 4.45 mL,
Described ammonia concn is 7.0 mol/L, and volume is 48.95 mL,
Described absolute ethyl alcohol volume is 37.6 ~ 38 mL;
Step B, product is washed till to neutrality with distilled water, 60 ℃, vacuum is dry.
Pre-assembled system preparation process of the present invention is as follows:
Steps A, by synthetic monodisperse silica nano particle described in 200 ~ 400 mg steps 2, add ultrasonic dispersion 5min in 15 ~ 30 ml methanol solutions;
Step B, by methyl hydroxybenzoate and 3-aminopropyl triethoxysilane, according to mol ratio, be that 1:2 ~ 5 join in the methanol solution of above-mentioned silica, the concentration of methyl hydroxybenzoate is 66.67 mmol/L, and ultrasonic mixing 30 min form.
Colloid adsorbent parent preparation process of the present invention is as follows:
In steps A, the pre-assembled system that makes in step 3, add successively tetraethyl orthosilicate, acetic acid, 400 ~ 800 rpm magnetic agitation, 25 ℃ of reaction 18 ~ 24 h of room temperature,
Wherein, the volume of described tetraethyl orthosilicate is 2.0 ~ 4.0 mL,
Described acetate concentration is 1mol/L, and volume is 0.5 ~ 1.0 mL;
Step B, 60 ℃ of vacuum drying 12 h.
Wash-out template molecule of the present invention and vacuum drying step comprise:
Steps A, the methyl alcohol of take: the mixed liquor that the volume ratio of hydrochloric acid is 1:1 ~ 2 is washed three times as extract,
Wherein, the concentration of described hydrochloric acid is 6 mol/L;
Step B, with the NaOH solution of 0.05 mol/L, be washed till neutrality, distilled water washing three times;
Vacuum drying 12 h at 100 ℃ of step C, polymer.
Corresponding non-trace adsorbent (NIP) preparation method is identical with above-mentioned preparation method, but does not add template molecule methyl hydroxybenzoate.
The surface imprinted adsorbent of methyl hydroxybenzoate that preparation method of the present invention is synthetic.
The selective identification that the surface imprinted adsorbent of synthetic methyl hydroxybenzoate of the present invention is used for to wintergreen methyl hydroxybenzoate is with separated, absorption methyl hydroxybenzoate is had to selective height, separating effect is remarkable, reuse advantage often, being expected provides novel methyl hydroxybenzoate adsorbent for the purifying of the commercial process of wintergreen.
Absorption property analysis test method described in technical scheme is specially:
(1) Static Adsorption test
Take 20 mg methyl hydroxybenzoate trace adsorbent (MIP
mP) and non-trace adsorbent (NIP) add in corresponding test solution, standing in water bath with thermostatic control, initial concentration, time of repose and the analogue of investigating adsorbent solution disturb the impact on trace adsorbent identification Metagin ester molecule; After absorption, by centrifugation, collect and obtain test fluid clear liquid at the middle and upper levels, not absorption methyl hydroxybenzoate molecular concentration ultraviolet spectroscopy, and according to result calculate adsorption capacity (
q e, mg/g):
Q e=[(
C 0-
C e)
V ] /
W
Wherein
c 0(mg/L) and
c e(mg/L) be respectively the concentration of methyl hydroxybenzoate before and after absorption,
w(g) be adsorbent consumption,
v(mL) be test fluid volume.
(2) selective absorption test
Choose methyl hydroxybenzoate (MP), P-hydroxybenzoic acid (
p-HB), gaultherolin (MS) is competitive Adsorption substrate, is configured to respectively the methanol solution of three kinds of compounds, the concentration of every kind of substrate is all 25 mg/L; Get the solution that 9.0 mL configure and join in colorimetric cylinder, add respectively 20 mg trace adsorbent (MIP
mP) and non-trace adsorbent (NIP), test fluid is placed in the water-bath of 25 ℃ to standing 8.0 h respectively; After standing completing, centrifugation obtains supernatant, and the ultraviolet spectra for concentration (UV) of the various competitive Adsorption substrates of absorption is not measured.
beneficial effect
This product is because the host material that trace occurs in Nano particles of silicon dioxide is surperficial, avoided segment template molecule because of embedding cross deeply cannot wash-out problem, the trace adsorbent mechanical strength obtaining is high, and identification point is survivable, has reduced widely non-specific adsorption; The methyl hydroxybenzoate composite material surface trace adsorbent that utilizes the present invention to obtain, has Heat stability is good, higher adsorption capacity, fast Adsorption Kinetics, significantly methyl hydroxybenzoate molecular recognition performance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of Nano particles of silicon dioxide, trace and non-imprinted polymer in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of Nano particles of silicon dioxide in embodiment 1 (a), methyl hydroxybenzoate silica surface imprinted polymer (b).
The specific embodiment
Below in conjunction with embodiment, the present invention is described in detail, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
embodiment 1
(1) monodisperse silica nano particle is synthetic
The tetraethyl orthosilicate (TEOS) that adds 4.45 mL in 250 ml there-necked flasks, the H of 9.0 mL
2o and 48.95 mL concentration are the ammoniacal liquor of 7.0 mol/L, the absolute ethyl alcohol of 37.6 mL, and room temperature (25 ℃) stirs 4 ~ 5 hours; Product is washed till to neutrality with distilled water, and 60 ℃, vacuum is dry.
(2) methyl hydroxybenzoate imprinted polymer (MIP
mP) preparation
200 mg monodisperse silica nano particles are joined to ultrasonic dispersion 5 min in 15 mL methyl alcohol, subsequently by the methyl hydroxybenzoate of 1.0 mmol (MP), the 3-aminopropyl triethoxysilane (APTES) of 5 mmol, joining in above-mentioned suspension makes template molecule and function monomer effect form pre-assembled system, then in said mixture, add 2.0 mL tetraethyl orthosilicates (TEOS), 0.5 mL 1mol/L acetic acid is in suspension, and room temperature (25 ℃) stirs 24 h; Then centrifugal, 60 ℃ of vacuum drying 12 h; Hydrochloric acid (the 1:1 of 25 ml methyl alcohol and 6 mol/L for synthetic polymer; V/v) wash three times, then use 0.05 mol/L NaOH to be washed till neutrality, then wash with distilled water, last polymer is dry 12 h at 100 ℃.
Corresponding non-trace adsorbent (NIP) preparation method is same as described above, but does not add template molecule methyl hydroxybenzoate.
(3) Static Adsorption test
Getting the Metagin ester solution that 9 ml initial concentrations are respectively 20,40,60,100,150,200,250,300 and 350 mg/l joins in colorimetric cylinder, add respectively the above-mentioned trace making of 20 mg and non-trace adsorbent, test fluid is placed in the water-bath of 25 ℃ after standing 12 h, centrifugation obtains supernatant, the salicylic acid molecular concentration ultraviolet spectroscopy not adsorbing, and calculate adsorption capacity according to result.
Result shows, the saturated adsorption capacity of the surface imprinted adsorbent of methyl hydroxybenzoate is 35.14 mg/g, apparently higher than 17.08 mg/g of non-trace adsorbent.
(4) selective absorption test
Select methyl hydroxybenzoate (MP), P-hydroxybenzoic acid (
p-HB), gaultherolin (MS) is competitive Adsorption substrate, is configured to respectively the methanol solution of three kinds of compounds, the concentration of every kind of substrate is all 20mg/l; Get the solution that 10 ml configure and join in colorimetric cylinder, add respectively the above-mentioned trace making of 20 mg and non-trace adsorbent, test fluid is placed in the water-bath of 25 ℃ to standing 8.0 h respectively; After time of repose completes, centrifugation obtains supernatant, not the concentration ultraviolet spectroscopy of the various competitive Adsorption substrates of absorption; Result shows, the surface imprinted adsorbent pair of methyl hydroxybenzoate
pthe separation factor of-HB and MS is 6.129 and 5.664 to be all obviously greater than but not the corresponding separation factor of imprinted polymer is 1.511 and 1.217, shows that the surface imprinted adsorbent of this methyl hydroxybenzoate has good selective recognition performance to Metagin ester molecule.
embodiment 2:
(1) Nano particles of silicon dioxide is synthetic
The tetraethyl orthosilicate (TEOS) that adds 4.05 mL in 250 ml there-necked flasks, 9.0 mL H
2o and 48.95 mL concentration are the ammoniacal liquor of 7.0 mol/L, the absolute ethyl alcohol of 38.0 mL, and room temperature (25 ℃) stirs 4 ~ 5 hours; Product is washed till to neutrality with distilled water, and 60 ℃, vacuum is dry.
(2) methyl hydroxybenzoate imprinted polymer (MIP
mP) preparation
400 mg monodisperse silica nano particles are joined to ultrasonic dispersion 5 min in 30 mL methyl alcohol, subsequently by the methyl hydroxybenzoate of 2.0 mmol (MP), the 3-aminopropyl triethoxysilane (APTES) of 10 mmol, joining in above-mentioned suspension makes template molecule and function monomer effect form pre-assembled system, then in said mixture, add 4 mL tetraethyl orthosilicates (TEOS), 1 mL 1mol/L acetic acid in suspension, stirring at room 18 h; Then centrifugal, 60 ℃ of vacuum drying 16 h; Hydrochloric acid (the 1:2 of 50 ml methyl alcohol and 6 mol/L for synthetic polymer; V/v) wash three times, then be washed till neutrality with 0.05 mol/L NaOH, then wash with distilled water, last polymer is dry 12 h at 100 ℃.
Corresponding non-trace adsorbent (NIP) preparation method is same as described above, but does not add template molecule methyl hydroxybenzoate.
(3) Static Adsorption test
Getting the Metagin ester solution that 9 ml initial concentrations are respectively 20,40,60,100,150,200,250,300 and 350 mg/l joins in colorimetric cylinder, add respectively the above-mentioned trace making of 20 mg and non-trace adsorbent, test fluid is placed in the water-bath of 25 ℃ after standing 12 h, centrifugation obtains supernatant, the methyl hydroxybenzoate molecular concentration ultraviolet spectroscopy not adsorbing, and calculate adsorption capacity according to result.
Result shows, the saturated adsorption capacity of the surface imprinted adsorbent of methyl hydroxybenzoate is 32.68 mg/g, apparently higher than 19.46 mg/g of non-trace adsorbent.
(4) selective absorption test
Select methyl hydroxybenzoate (MP), P-hydroxybenzoic acid (
p-HB), gaultherolin (MS) is competitive Adsorption substrate, is configured to respectively the methanol solution of three kinds of compounds, the concentration of every kind of substrate is all 20 mg/L; Get the solution that 9 mL configure and join in colorimetric cylinder, add respectively the above-mentioned trace making of 20 mg and non-trace adsorbent, test fluid is placed in the water-bath of 25 ℃ to standing 8.0 h respectively; After standing completing, centrifugation obtains supernatant, not the concentration ultraviolet spectroscopy of the various competitive Adsorption substrates of absorption; Result shows, the surface imprinted adsorbent pair of methyl hydroxybenzoate
pthe separation factor of-HB and MS is 6.017 and 5.031 to be all obviously greater than but not the corresponding separation factor of imprinted polymer is 1.412 and 1.115, shows that the surface imprinted adsorbent of this methyl hydroxybenzoate has good selective recognition performance to Metagin ester molecule.
Fig. 1 is the infrared spectrogram of Nano particles of silicon dioxide, trace and non-imprinted polymer in embodiment 1; As can be seen from Figure 1 at 3438 cm
-1wide and strong peak is owing to the stretching vibration of O-H.At approximately 1103 cm
-1the feature that place observes shows the antisymmetric stretching vibration of Si-O-Si key.At 1506 cm
-1with 2933 cm
-1the characteristic peak at place, left and right is respectively the stretching vibration of N-H and C-H.Comparison by Nano particles of silicon dioxide, trace and non-imprinted polymer at above two characteristic peaks, has shown the surface of successful grafting of APTES to nano particle.
Fig. 2 is the scanning electron microscope (SEM) photograph of Nano particles of silicon dioxide in embodiment 1 (a), methyl hydroxybenzoate silica surface imprinted polymer (b); As can be seen from Figure 2 synthetic monodisperse silica microspheres particle diameter distribution homogeneous, smooth surface, and coarse bulk at the synthetic imprinted polymer layer of silica surface, show trace success.
Claims (7)
1. the preparation method of the surface imprinted adsorbent of methyl hydroxybenzoate, be the monodisperse silica Nano microsphere synthesizing be substrate, methyl hydroxybenzoate is template molecule, 3-aminopropyl triethoxysilane is that function monomer forms pre-assembled system, adding tetraethyl orthosilicate is crosslinking agent again, acetic acid is that catalyst makes colloid adsorbent parent, finally will after adsorbent parent wash-out template molecule, be washed till neutrality, and vacuum drying forms.
2. the preparation method of the surface imprinted adsorbent of a kind of methyl hydroxybenzoate according to claim 1, is characterized in that, described synthetic monodisperse silica Nano microsphere preparation process is as follows:
Steps A, by tetraethyl orthosilicate, H
2o, ammoniacal liquor, absolute ethyl alcohol be mix and blend 4 ~ 5h at 25 ℃ of room temperatures,
Wherein, described tetraethyl orthosilicate volume is 4.05 ~ 4.45 mL,
Described ammonia concn is 7.0 mol/L, and volume is 48.95 mL,
Described absolute ethyl alcohol volume is 37.6 ~ 38 mL;
Step B, product is washed till to neutrality with distilled water, 60 ℃, vacuum is dry.
3. the preparation method of the surface imprinted adsorbent of a kind of methyl hydroxybenzoate according to claim 1, is characterized in that, described pre-assembled system preparation process is as follows:
Steps A, by monodisperse silica Nano microsphere synthetic described in 200 ~ 400 mg, add ultrasonic dispersion 5min in 15 ~ 30 ml methanol solutions;
Step B, by methyl hydroxybenzoate and 3-aminopropyl triethoxysilane, according to mol ratio, be that 1:2 ~ 5 join in the methanol solution of above-mentioned silica, the concentration of methyl hydroxybenzoate is 66.67 mmol/L, and ultrasonic mixing 30 min form.
4. the preparation method of the surface imprinted adsorbent of a kind of methyl hydroxybenzoate according to claim 1, is characterized in that, described colloid adsorbent parent preparation process is as follows:
Steps A, in the described pre-assembled system making, add successively tetraethyl orthosilicate, acetic acid, 400 ~ 800 rpm magnetic agitation, 25 ℃ of room temperatures reaction, 18 ~ 24 h,
Wherein, the volume of described tetraethyl orthosilicate is 2.0 ~ 4.0 mL,
Described acetate concentration is 1mol/L, and volume is 0.5 ~ 1.0 mL;
Step B, 60 ℃ of vacuum drying 12 h.
5. the preparation method of the surface imprinted adsorbent of a kind of methyl hydroxybenzoate according to claim 1, is characterized in that, described wash-out template molecule and vacuum drying step comprise:
Steps A, the methyl alcohol of take: the mixed liquor that the volume ratio of hydrochloric acid is 1:1 ~ 2 is washed three times as extract,
Wherein, the concentration of described hydrochloric acid is 6 mol/L;
Step B, with the NaOH solution of 0.05 mol/L, be washed till neutrality, distilled water washing three times;
Vacuum drying 12 h at 100 ℃ of step C, polymer.
6. the synthetic surface imprinted adsorbent of methyl hydroxybenzoate of preparation method according to claim 1.
7. the surface imprinted adsorbent of methyl hydroxybenzoate according to claim 6, is characterized in that, uses it for the selective identification of methyl hydroxybenzoate in wintergreen with separated.
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