CN103920399A - Method for preparing methyl p-hydroxybenzoate molecularly-imprinted composite membrane at normal temperature - Google Patents
Method for preparing methyl p-hydroxybenzoate molecularly-imprinted composite membrane at normal temperature Download PDFInfo
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Abstract
The invention discloses a method for preparing a methyl p-hydroxybenzoate molecularly-imprinted composite membrane at normal temperature, belongs to the field of the material preparation technologies and separation technologies and in particular relates to a method for preparing a methyl p-hydroxybenzoate molecularly-imprinted composite membrane (MI CMMP) at normal temperature. The method takes a polyvinylidene fluoride microfiltration membrane as a substrate, takes the methyl p-hydroxybenzoate (MP) which is impurity in methyl salicylate as a template molecule, takes acrylamide (AM) as a functional monomer, takes N, N'-methylene bisacrylamide (MPAA) as a cross-linking agent and takes ammonium persulfate (APS) and N, N, N',N'-tetramethylethylenediamine (TEMED) as initiators. By adopting static adsorption experiments and selective permeation experiments, the selective recognition property of the prepared molecularly-imprinted membrane is researched. Results show that the methyl p-hydroxybenzoate molecularly-imprinted composite membrane prepared by the method is excellent in function of recognizing molecules of methyl p-hydroxybenzoate.
Description
Technical field
The present invention relates to a kind of method of Synthesis of Molecular Imprinting Polymers at normal temperatures, relate in particular to a kind of preparation method of methyl p-hydroxybenzoate molecularly imprinted composite membrane, and be applied to remove impurity--methyl p-hydroxybenzoate from wintergreen, belong to material preparation and separation technology field.
Background technology
Wintergreen, formal name used at school gaultherolin, has Chinese ilex fragrance, extracts the earliest in 1834 from Chinese ilex plant.Be mainly used in the spices of beverage, food, toothpaste and cosmetics, as joyous in tuberose, alloy etc. daily essence, the flavoring essence of strawberry, grape, also can be used for solvent and the intermediate of pesticide, bactericide, anodyne, benevolence photo etching and coating etc.Because natural gaultherolin is originated limited; therefore conventionally react and obtain with methanol esterification by salicylic acid; owing to often can producing accessory substance methyl p-hydroxybenzoate in this product; though it can do sterilization antiseptic; but there is data to show; if long-term a large amount of edible methyl p-hydroxybenzoate may cause digestive discomfort, skin, mucous membrane inflammation and generation estrogen.Therefore, the effectively separated impurity methyl p-hydroxybenzoate tool of removing in gaultherolin is of great significance.Wherein conventional separation method has extraction, recrystallization method, molecularly distilled and membrane separation process etc.These methods respectively have distinct advantages, but also respectively have its limitation.As solvent extraction technology in a large number with an organic solvent, easily produce secondary pollution; Recrystallization method experiment is consuming time, and yield is low, and requires high to the selection of solvent; Although molecularly distilled can be realized certain organic separation as a kind of novel distillating method, its device structure is complicated, and specification requirement is harsh, invests greatly and the serious waste energy; The membrane separation technique (Membrane Separation Technique, MST) of rising the sixties in 19th century is efficient, energy-conservation, easy to operate with it, molecular level filters, advantages of environment protection is widely used in enterprise production process.But conventional film isolation technics still exists some to limit the factor of its development, as current business sells that film (ultrafiltration, micro-filtration and reverse osmosis membrane) all can only be realized the separation of a certain class material and the separation that cannot realize single material, the organic compound to structural similarity particularly, conventional film cannot be carried out single, efficient Selective Separation to certain material.
Molecular imprinting (MIT) be in simulating nature circle as: the Molecular Recognization of enzyme-to-substrate, antibody and antigen etc., the target molecule of take has a kind of technology of the macromolecule imprinted polymer (Molecularly Imprinted Polymers, MIPs) of specific selectivity recognition function as template molecule preparation to this molecule.
The Application and Development of the molecular engram polymeric membrane (Molecular Imprinted Membrane, MIM) that produces that molecular imprinting is combined with membrane separation technique is one of the most attractive research.Molecular imprinted polymer membrane (MIM) has the advantage of molecular engram and membrane separation technique concurrently, and on the one hand, this technology is convenient to continued operation, is easy to amplify, and energy consumption is low, and capacity usage ratio is high, is the typical case of " Green Chemistry "; On the other hand, it has overcome current commercial membranes material cannot realize single material as ultrafiltration, micro-filtration and reverse osmosis membrane etc. and select separated shortcoming, for specific molecular is separated feasible effective solution route is provided from the similar mixture of structure.Consider that synthetic molecular engram film has the single-minded selective recognition function of predetermined substance, for the removal of impurities process of gaultherolin provides kind new method, and constantly in large industrial goods separation and purification field, bring into play irreplaceable effect.
Summary of the invention
The present invention be take polyvinylidene fluoride microporous filtering film (PVDF) as the synthetic trace composite membrane that methyl p-hydroxybenzoate molecule is had to single-minded evident characteristics of substrate, and for to the selective identification of gaultherolin methyl p-hydroxybenzoate with separated, this composite membrane has higher adsorptivity and selective to methyl p-hydroxybenzoate molecule.
Technical scheme of the present invention is:
A preparation method for methyl p-hydroxybenzoate molecularly imprinted composite membrane, carries out according to the following steps:
(1) Kynoar (PVDF) microfiltration membranes isopropyl alcohol, rear with distilled water cleaning, be then placed in sodium hydrate aqueous solution 55
ounder C, react 5 ~ 10 min, film surface becomes brown, and taking-up film is washed with distilled water to cleaning fluid and is neutral, and film is dried stand-by.
(2) get potassium dihydrogen phosphate and add in sodium hydrate aqueous solution, with distilled water diluting to 100 mL, obtain phosphate buffer solution.
(3) pvdf membrane of processing in step (1) is positioned in conical flask, the phosphate buffer solution that adds preparation in methanol solution and step (2), add again methyl p-hydroxybenzoate (MP), acrylamide (AM) and N, N '-methylene-bisacrylamide (MBAA), vibration makes its dissolving.
(4) in mixed solution, pass into nitrogen, continue 10 ~ 20 min, inject ammonium persulfate (APS) solution and TEMED (TEMED) solution simultaneously, sealing is placed on 25
o8 ~ 12 h vibrate in water bath chader under C.
(5) after reaction, film is taken out, first with distilled water, clean and remove unreacted methyl p-hydroxybenzoate template, acrylamide monomer, N, N'-methylene-bisacrylamide crosslinking agent and initator, with the mixed liquor of methyl alcohol and acetic acid, wash 48 ~ 72 h again, to remove template molecule methyl p-hydroxybenzoate, after oven dry, obtain methyl p-hydroxybenzoate trace composite membrane (MICM
mP).
Wherein, the concentration of the sodium hydrate aqueous solution described in step (1) is 4 ~ 6 mol L
-1, the concentration of described pvdf membrane in mixed solution is 6 ~ 10 g L
-1.
Wherein, the potassium dihydrogen phosphate quality described in step (2) is 0.136 ~ 0.68 g, and the concentration of sodium hydrate aqueous solution is 0.1 ~ 0.3 mol L
-1, the concentration of the phosphate buffer solution obtaining is 10 ~ 50 mmol L
-1.
Wherein, the volume ratio of the methyl alcohol described in step (3) and phosphate buffer is (0 ~ 10): (40 ~ 30), the concentration of MP and AM is respectively 6.25 ~ 12.5 mmol L
-1with 25 ~ 50 mmol L
-1, the concentration of MBAA is 50 ~ 200 mmol L
-1.
Wherein, (10% ~ 20%, w/v) (5% ~ 10%, v/v) volume used is respectively 120 μ L and 60 μ L to the APS solution described in step (4) with TEMED solution.
Wherein, the volume ratio of the methyl alcohol described in step (5) and acetic acid is (9 ~ 7): (1 ~ 3).
The preparation method of corresponding non-trace composite membrane (NICM) is same as described above, but does not add template molecule methyl p-hydroxybenzoate.
In above-mentioned technical scheme, with isopropyl alcohol pvdf membrane, be in order to prevent surperficial approach effect, pvdf membrane is immersed to reaction in sodium hydrate aqueous solution so that film surface forms carbon-carbon double bond.
Phosphate buffer solution described in technique scheme, it act as the hydrolysis that prevents ammonium persulfate.
Methyl p-hydroxybenzoate described in technique scheme, it act as template molecule.
Acrylamide described in technique scheme, it act as function monomer.
N described in technique scheme, N '-methylene-bisacrylamide, it act as crosslinking agent.
Ammonium persulfate solution described in technique scheme and TEMED solution, it act as initator.
Film described in technique scheme, it act as host material.
Above-mentioned trace composite membrane is applied to the methyl p-hydroxybenzoate in adsorbing separation gaultherolin, and concrete grammar carries out according to following step:
(1) accurately take the MICM of equivalent
mPand NICM (g) joins in methyl p-hydroxybenzoate methanol/water (3:7, the v:v) mixed solution that contains variable concentrations, 25
ostanding in C insulating box, after 4 hours, investigate the adsorbance of trace and non-blotting membrane, if the mixed liquor volume adding is
v(L) initial concentration of, joining solution is
c 0(mg L
-1), after certain hour absorption, its concentration is
c 1(mg L
-1), by following equation, can calculate the adsorbance of membrane
q(mg g
-1) be:
Q=?(
C 0-?
C 1)*
V/
m
(2) get gaultherolin (MS) and methyl p-hydroxybenzoate (MP) preparation 10 mg L
-1methanol/water (3:7, V:V) mixed solution.Get the solution that 10 mL prepare and join in conical flask, the trace and the non-trace composite membrane that respectively add a slice to weigh, be placed on conical flask in the insulating box of 25 ℃ after standing 4 h; Take out trace and non-trace adsorbed film, the concentration of not adsorbing solute is measured with ultraviolet specrophotometer.
(3) two identical aquariums with ground arm of self-control, blotting membrane or blank film are fixed in the middle of two aquariums with clip, form H shape permeability device, guarantee that two ponds do not have seepage, in a pond, adding substrate is methanol/water (3:7, the v:v) mixed solution of gaultherolin and methyl p-hydroxybenzoate, in another pond, add methanol/water (3:7, v:v) solution, every certain hour sampling, measures the concentration of the substrate that sees through polymer film.
Technological merit of the present invention:
(1) trace process occurs in membrane material surface, avoided conventional template molecule because of embedding cross deeply cannot wash-out problem.
(2) film basification is made its surface form two keys, thereby make molecularly imprinted polymer by covalent bond, be connected on the surface of film, avoided coming off of in membrane cleaning process polymer.
(3) adopt ammonium persulfate solution and TEMED solution as initator, can make reaction can carry out at normal temperatures, avoided the consumption of heat.
(4) utilize the methyl p-hydroxybenzoate molecularly imprinted composite membrane that the present invention obtains to there is Heat stability is good, superior methyl p-hydroxybenzoate molecular recognition performance.
The specific embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1
(1) get 0.12 g Kynoar (PVDF) microfiltration membranes isopropyl alcohol, rear with distilled water cleaning, being then placed in 20 mL concentration is 4 mol L
-1sodium hydrate aqueous solution in 55
ounder C, react 10 min, film surface becomes brown, and taking-up film is washed with distilled water to cleaning fluid and is neutral, and film is dried stand-by.
(2) get potassium dihydrogen phosphate 0.136 g, adding 5.82 mL concentration is 0.1 mol L
-1sodium hydrate aqueous solution, with distilled water diluting to 100 mL, obtain 10 mmol L
-1phosphate buffer solution.
(3) pvdf membrane of processing in step (1) is positioned in conical flask, the phosphate buffer solution that adds preparation in 0 mL methanol solution and 40 mL steps (2), add again 0.0381 g methyl p-hydroxybenzoate (MP), 0.0711 g acrylamide (AM) and 0.3084 g N, N '-methylene-bisacrylamide (MBAA), vibration makes its dissolving.
(4) in mixed solution, pass into nitrogen, continue 10 min, inject 120 μ L ammonium persulfate (APS) solution (10% simultaneously, w/v) N of and 60 μ L, N, N ', (5%, v/v), sealing is placed on 25 to N '-tetramethylethylenediamine (TEMED) solution
o8 h vibrate in water bath chader under C.
(5) after reaction, film is taken out, first with distilled water, clean and remove unreacted methyl p-hydroxybenzoate template, acrylamide monomer, N, N'-methylene-bisacrylamide crosslinking agent and initator, use again the mixed liquor (9:1 of methyl alcohol and acetic acid, v:v) washing 48 h, to remove template molecule methyl p-hydroxybenzoate, after oven dry, obtain methyl p-hydroxybenzoate trace composite membrane (MICM
mP).The preparation method of corresponding non-trace composite membrane (NIM) is same as described above, but does not add template molecule methyl p-hydroxybenzoate.
(6) prepared blotting membrane is carried out to Staticadsorption experiment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate solution, solvent is methanol/water (3:7, v:v) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0224g and 0.0256g, puts into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, the content of measuring methyl p-hydroxybenzoate in solution with ultraviolet specrophotometer, the adsorbance that calculates trace polymeric membrane is 0.7144 mg g
-1adsorbance 0.3835 mg g apparently higher than non-trace polymeric membrane
-1.
(7) prepared blotting membrane is carried out to static Competitive adsorption assessment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate and gaultherolin solution, solvent is methanol/water (3:7, v:v) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0211g and 0.0247g, put into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, content with methyl p-hydroxybenzoate and gaultherolin in ultraviolet specrophotometer measurement solution, the separation factor that calculates trace polymeric membrane is 3.021, apparently higher than the separation factor 1.114 of non-trace polymeric membrane.
(8) prepared blotting membrane is carried out to permeance property analytical test.
Make two identical aquariums with ground arm by oneself, blotting membrane or blank film are fixed in the middle of two aquariums with clip, form H shape permeability device, guarantee that two ponds do not have seepage, in a pond, adding concentration of substrate is 50 mg L
-1methyl p-hydroxybenzoate and the methanol/water (3:7 of gaultherolin, v:v) mixed solution, in another pond, add methanol/water (3:7, v:v) solution, sample interval is respectively 5,15,20,30,45,60,720 min, measures the concentration of the substrate that sees through polymer film.
Result demonstration, during balance, when blotting membrane is permeable membrane, in blank sample cell, the concentration of gaultherolin is 21.34 mg L
-1, the concentration of methyl p-hydroxybenzoate is 12.08 mg L
-1, and when non-trace composite membrane is permeable membrane, in blank sample pond, the concentration of gaultherolin is 20.78 mg L
-1, the concentration of methyl p-hydroxybenzoate is 19.98 mg L
-1.
embodiment 2
(1) get 0.16 g Kynoar (PVDF) microfiltration membranes isopropyl alcohol, rear with distilled water cleaning, being then placed in 20 mL concentration is 5 mol L
-1sodium hydrate aqueous solution in 55
ounder C, react 7.5 min, film surface becomes brown, and taking-up film is washed with distilled water to cleaning fluid and is neutral, and film is dried stand-by.
(2) get potassium dihydrogen phosphate 0.408 g, adding 8.73 mL concentration is 0.2 mol L
-1sodium hydrate aqueous solution, with distilled water diluting to 100 mL, obtain 25 mmol L
-1phosphate buffer solution.
(3) pvdf membrane of processing in step (1) is positioned in conical flask, the phosphate buffer solution that adds preparation in 5 mL methanol solutions and 35 mL steps (2), add again 0.0571 g methyl p-hydroxybenzoate (MP), 0.1067 g acrylamide (AM) and 0.6938 g N, N '-methylene-bisacrylamide (MBAA), vibration makes its dissolving.
(4) in mixed solution, pass into nitrogen, continue 15 min, inject 120 μ L ammonium persulfate (APS) solution (15% simultaneously, w/v) N of and 60 μ L, N, N ', (7.5%, v/v), sealing is placed on 25 to N '-tetramethylethylenediamine (TEMED) solution
o10 h vibrate in water bath chader under C.
(5) after reaction, film is taken out, first with distilled water, clean and remove unreacted methyl p-hydroxybenzoate template, acrylamide monomer, N, N'-methylene-bisacrylamide crosslinking agent and initator, use again the mixed liquor (8:2 of methyl alcohol and acetic acid, v:v) washing 64 h, to remove template molecule methyl p-hydroxybenzoate, after oven dry, obtain methyl p-hydroxybenzoate trace composite membrane (MICM
mP).The preparation method of corresponding non-trace composite membrane (NIM) is same as described above, but does not add template molecule methyl p-hydroxybenzoate.
(6) prepared blotting membrane is carried out to Staticadsorption experiment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate solution, solvent is methanol/water (3:7, V/V) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0231g and 0.0247g, puts into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, the content of measuring methyl p-hydroxybenzoate in solution with ultraviolet specrophotometer, the adsorbance that calculates trace polymeric membrane is 0.6516 mg g
-1adsorbance 0.3263 mg g apparently higher than non-trace polymeric membrane
-1.
(7) prepared blotting membrane is carried out to static Competitive adsorption assessment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate and gaultherolin solution, solvent is methanol/water (3:7, V/V) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0234g and 0.0241g, put into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, content with methyl p-hydroxybenzoate and gaultherolin in ultraviolet specrophotometer measurement solution, the separation factor that calculates trace polymeric membrane is 2.847, apparently higher than the separation factor 1.079 of non-trace polymeric membrane.
(8) prepared blotting membrane is carried out to permeance property analytical test.
Make two identical aquariums with ground arm by oneself, blotting membrane or blank film are fixed in the middle of two aquariums with clip, form H shape permeability device, guarantee that two ponds do not have seepage, in a pond, adding concentration of substrate is 50 mg L
-1methyl p-hydroxybenzoate and the methanol/water (3:7 of gaultherolin, V:V) mixed solution, in another pond, add methanol/water (3:7, V:V) solution, sample interval is respectively 5,15,20,30,45,60,720 min, measures the concentration of the substrate that sees through polymer film.
Result demonstration, during balance, when blotting membrane is permeable membrane, in blank sample cell, the concentration of gaultherolin is 19.95 mg L
-1, the concentration of methyl p-hydroxybenzoate is 11.16 mg L
-1, and when non-trace composite membrane is permeable membrane, in blank sample pond, the concentration of gaultherolin is 19.85 mg L
-1, the concentration of methyl p-hydroxybenzoate is 18.68 mg L
-1.
embodiment 3
(1) get 0.20 g Kynoar (PVDF) microfiltration membranes isopropyl alcohol, rear with distilled water cleaning, being then placed in 20 mL concentration is 5 mol L
-1sodium hydrate aqueous solution in 55
ounder C, react 5 min, film surface becomes brown, and taking-up film is washed with distilled water to cleaning fluid and is neutral, and film is dried stand-by.
(2) get potassium dihydrogen phosphate 0.68 g, adding 9.77 mL concentration is 0.3 mol L
-1sodium hydrate aqueous solution, with distilled water diluting to 100 mL, obtain 50 mmol L
-1phosphate buffer solution.
(3) pvdf membrane of processing in step (1) is positioned in conical flask, the phosphate buffer solution that adds preparation in 10 mL methanol solutions and 30 mL steps (2), add again 0.0761 g methyl p-hydroxybenzoate (MP), 0.1422 g acrylamide (AM) and 1.2334 g N, N '-methylene-bisacrylamide (MBAA), vibration makes its dissolving.
(4) in mixed solution, pass into nitrogen, continue 20 min, inject 120 μ L ammonium persulfate (APS) solution (20% simultaneously, w/v) N of and 60 μ L, N, N ', (10%, v/v), sealing is placed on 25 to N '-tetramethylethylenediamine (TEMED) solution
o12 h vibrate in water bath chader under C.
(5) after reaction, film is taken out, first with distilled water, clean and remove unreacted methyl p-hydroxybenzoate template, acrylamide monomer, N, N'-methylene-bisacrylamide crosslinking agent and initator, use again the mixed liquor (7:3 of methyl alcohol and acetic acid, v:v) washing 72 h, to remove template molecule methyl p-hydroxybenzoate, after oven dry, obtain methyl p-hydroxybenzoate trace composite membrane (MICM
mP).The preparation method of corresponding non-trace composite membrane (NIM) is same as described above, but does not add template molecule methyl p-hydroxybenzoate.
(6) prepared blotting membrane is carried out to Staticadsorption experiment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate solution, solvent is methanol/water (3:7, v:v) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0232g and 0.0253g, puts into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, the content of measuring methyl p-hydroxybenzoate in solution with ultraviolet specrophotometer, the adsorbance that calculates trace polymeric membrane is 0.7232 mg g
-1adsorbance 0.3568 mg g apparently higher than non-trace polymeric membrane
-1.
(7) prepared blotting membrane is carried out to static Competitive adsorption assessment.
Prepare 10 mg L
-1methyl p-hydroxybenzoate and gaultherolin solution, solvent is methanol/water (3:7, v:v) mixed solution, respectively get a slice blotting membrane and non-blotting membrane, quality is respectively 0.0237 g and 0.0240 g, put into respectively the solution of 10 mL preparations, in the insulating box of 25 ℃ after standing 4 hours, content with methyl p-hydroxybenzoate and gaultherolin in ultraviolet specrophotometer measurement solution, the separation factor that calculates trace polymeric membrane is 3.272, apparently higher than the separation factor 1.106 of non-trace polymeric membrane.
(8) prepared blotting membrane is carried out to permeance property analytical test.
Make two identical aquariums with ground arm by oneself, blotting membrane or blank film are fixed in the middle of two aquariums with clip, form H shape permeability device, guarantee that two ponds do not have seepage, in a pond, adding concentration of substrate is 50 mg L
-1methyl p-hydroxybenzoate and the methanol/water (3:7 of gaultherolin, v:v) mixed solution, in another pond, add methanol/water (3:7, v:v) solution, sample interval is respectively 5,15,20,30,45,60,720 min, measures the concentration of the substrate that sees through polymer film.
Result demonstration, during balance, when blotting membrane is permeable membrane, in blank sample cell, the concentration of gaultherolin is 19.48 mg L
-1, the concentration of methyl p-hydroxybenzoate is 11.04 mg L
-1, and when non-trace composite membrane is permeable membrane, in blank sample pond, the concentration of gaultherolin is 20.43 mg L
-1, the concentration of methyl p-hydroxybenzoate is 18.81 mg L
-1.
Claims (6)
1. a preparation method for methyl p-hydroxybenzoate molecularly imprinted composite membrane, is characterized in that carrying out according to the following steps:
(1) by polyvinylidene fluoride microporous filtering film, pvdf membrane, is placed in sodium hydrate aqueous solution, then 55
oafter reacting 5 ~ 10 min under C, take out, taking-up film is washed with distilled water to cleaning fluid and is neutral, and film is dried stand-by;
(2) get potassium dihydrogen phosphate and add in sodium hydrate aqueous solution, with distilled water diluting to 100 mL, obtain phosphate buffer solution;
(3) pvdf membrane of processing in step (1) is positioned in conical flask, the phosphate buffer solution that adds preparation in methanol solution and step (2), add again methyl p-hydroxybenzoate (MP), acrylamide (AM) and N, N '-methylene-bisacrylamide (MBAA), vibration makes its dissolving;
(4) in mixed solution, pass into nitrogen, continue 10 ~ 20 min, inject ammonium persulfate (APS) solution and TEMED (TEMED) solution simultaneously, sealing is placed on 25
o8 ~ 12 h vibrate in water bath chader under C;
(5) after reaction, film is taken out, first with distilled water, clean and remove unreacted methyl p-hydroxybenzoate template, acrylamide monomer, N, N'-methylene-bisacrylamide crosslinking agent and initator, with the mixed liquor of methyl alcohol and acetic acid, wash 48 ~ 72 h again, to remove template molecule methyl p-hydroxybenzoate, after oven dry, obtain methyl p-hydroxybenzoate trace composite membrane (MICM
mP).
2. the preparation method of a kind of methyl p-hydroxybenzoate molecularly imprinted composite membrane according to claim 1, is characterized in that, in the mixed aqueous solution described in step (1), the concentration of NaOH is 4 ~ 6 mol L
-1, the concentration of described pvdf membrane in mixed aqueous solution is 6 ~ 10 g L
-1.
3. the preparation method of a kind of methyl p-hydroxybenzoate molecularly imprinted composite membrane according to claim 1, is characterized in that, the potassium dihydrogen phosphate quality described in step (2) is 0.136 ~ 0.68 g, and the concentration of sodium hydrate aqueous solution is 0.1 ~ 0.3 mol L
-1, the concentration of the phosphate buffer solution obtaining is 10 ~ 50 mmol L
-1.
4. the preparation method of a kind of methyl p-hydroxybenzoate molecularly imprinted composite membrane according to claim 1, it is characterized in that, the volume ratio of the methyl alcohol described in step (3) and phosphate buffer is (0 ~ 10): (40 ~ 30), the concentration of methyl p-hydroxybenzoate (MP) and acrylamide (AM) is respectively 6.25 ~ 12.5 mmol L
-1with 25 ~ 50 mmol L
-1, N, the concentration of N '-methylene-bisacrylamide (MBAA) is 50 ~ 200 mmol L
-1.
5. the preparation method of a kind of methyl p-hydroxybenzoate molecularly imprinted composite membrane according to claim 1, it is characterized in that, ammonium persulfate (APS) solution quality volume fraction described in step (4) is 10% ~ 20%(w/v) consumption is 120 μ L, N, N, N ', the volume fraction of N '-tetramethylethylenediamine (TEMED) solution is 5% ~ 10%(v/v) consumption is 60 μ L.
6. the preparation method of a kind of methyl p-hydroxybenzoate molecularly imprinted composite membrane according to claim 1, is characterized in that, the volume ratio of the methyl alcohol described in step (5) and acetic acid is (9 ~ 7): (1 ~ 3).
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| CN104231303A (en) * | 2014-08-27 | 2014-12-24 | 江苏大学 | Preparation method and applications of molecular imprinting composite membrane |
| CN104231303B (en) * | 2014-08-27 | 2017-02-22 | 江苏大学 | Preparation method and applications of molecular imprinting composite membrane |
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