CN104231303B - Preparation method and applications of molecular imprinting composite membrane - Google Patents
Preparation method and applications of molecular imprinting composite membrane Download PDFInfo
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- CN104231303B CN104231303B CN201410423960.9A CN201410423960A CN104231303B CN 104231303 B CN104231303 B CN 104231303B CN 201410423960 A CN201410423960 A CN 201410423960A CN 104231303 B CN104231303 B CN 104231303B
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Abstract
The invention relates to a preparation method and applications of a molecular imprinting composite membrane. The invention relates to a method for removing p-hydroxybenzoic acid from acetylsalicylic acid, and particularly relates to a method for synthesizing p-hydroxybenzoic acid composite imprint microfiltration membrane through taking commercial organic membrane polyvinylidene difluoride membrane (PVDF) as a substrate, 3-aminopropyltriethoxysilane (KH-550) and pyridine as membrane modifiers, impurity p-hydroxybenzoic acid (p-HB) in acetylsalicylic acid as a template molecule, 4-vinylpyridine (4-VP) as a functional monomer, N,N'-methylenebisacrylamide (MBAA) as a cross-linking agent, azodiisobutyronitrile (AIBN) as an initiator and methanol as a pore-forming agent. A static adsorption experiment is used for researching the adsorption balance, dynamics and selective recognition performances of the prepared composite imprinting microfiltration membrane. Results show that the p-hydroxybenzoic acid composite imprint microfiltration membrane obtained by adopting the method has excellent recognition performance on the p-hydroxybenzoic acid molecules.
Description
Technical field
The invention belongs to material preparation and separation technology field, especially a kind of preparation method of molecularly imprinted composite membrane and
The application of its P-hydroxybenzoic acid in separating acetyl salicylic acid.
Background technology
Aspirin, also known as aspirin, are conventional analgesic, can be used as antipyretic, analgesia, antiinflammatory, rheumatism
And suppression platelet aggregation medicine.For generating heat（Flu, influenza etc.）, pain（Headache, toothache, neuralgia, myalgia and dysmenorrhea
Deng）, rheumatism（Rheumatic arthritis, rheumatoid arthritiss）, and prevention temporal cerebral ischemia seizure, myocardial infarction or its
His postoperative thrombosiss.Impurity P-hydroxybenzoic acid is usually contained in aspirin production process.P-hydroxybenzoic acid
It is broad-spectrum organic synthesiss raw material.It is also widely used in the sides such as food, cosmetics, the anti-corrosion, antifungus agent of medicine and antibacterial
Face.Zoopery shows that P-hydroxybenzoic acid has a faint estrogen activity, about the naturally-produced estradiol of human body
100000/, some estrogen can stimulate the growth of tumor, and therefore P-hydroxybenzoic acid is probably a kind of recessive carcinogen.
So P-hydroxybenzoic acid has great importance in removal aspirin.Traditional separation method：As extraction, using big
The organic solvent of amount, is also easy to produce secondary pollution；Recrystallization method, time consumption and energy consumption.The membrane separation technique that the sixties in 19th century rises
(Membrane Separation Technique, MST) with its efficiently, energy-conservation, easy to operate, molecular level filters, environment friend
Good the advantages of, is widely used in enterprise production process.But traditional membrane separation technique yet suffer from some limit its development because
Element, such as current commercially film (ultrafiltration, microfiltration and reverse osmosis membrane) all can only be realized the separation of a certain class material and cannot realize list
The separation of individual material, particularly similar to structure organic compound, conventional film cannot carry out single, efficient to certain material
Selective Separation.
Molecular imprinting (MIT) is to simulate in nature such as：The molecular recognition of enzyme-to-substrate, antibody and antigen etc. is made
With having the macromolecule imprinted polymer of specific selectivity identification function to this molecule with target molecule for template molecule preparation
A kind of technology of (Molecularly Imprinted Polymers, MIPs).
Molecular imprinting is combined the molecular engram polymeric membrane (Molecular producing with membrane separation technique
Imprinted Membrane, MIM) development and application be most one of research of captivation.Molecular imprinted polymer membrane
(MIM) advantage having molecular engram and membrane separation technique concurrently, on the one hand, this technology is easy to continuous operation it is easy to amplify, energy consumption
Low, capacity usage ratio is high, is the typical case of " Green Chemistry "；On the other hand, it overcomes the such as ultrafiltration, micro- of current business membrane material
Filter and reverse osmosis membrane etc. cannot be realized single material and select detached shortcoming, be by specific molecular from the mixture that structure is similar to
Separate and provide feasible effective solution route.Molecular engram film in view of synthesis has the single-minded selection to predetermined substance
Property identification function, is that the dedoping step of P-hydroxybenzoic acid provides kind of a new method, and constantly isolates and purifies in large industrial goods
Field plays irreplaceable effect.
Content of the invention
Technical scheme refers to synthesize to para hydroxybenzene first with polyvinylidene fluoride microporous filter membrane (PVDF) for substrate
Acid molecule has the trace composite membrane of single-minded evident characteristics, and for the Selective recognition to P-hydroxybenzoic acid in aspirin
And separate.Result shows that this composite membrane has higher adsorptivity and selectivity to p-hydroxybenzoic acid.
The technical solution used in the present invention is：
A kind of preparation method of molecularly imprinted composite membrane, is carried out as follows：
（1）By polyvinylidene fluoride micro-filtration membrane（PVDF）It is placed in potassium hydroxide and potassium dichromate mixed aqueous solution, 50 ~
Take out after 60 DEG C of reaction 1.0 ~ 1.5 h, with distilled water wash, then film is soaked in aqueous solution of sodium bisulfite, film is pressed from both sides
Go out, be washed to neutrality with distillation, then with ethanol rinse post-drying；
（2）By step（1）The filter membrane processing is placed in APTES（KH-550）With toluene mixture liquid
In, add triethylamine, seal after being passed through nitrogen, water-bath is shaken, and soaks post-drying with ethanol after taking the film out；
（3）By step（2）The filter membrane processing is placed in pyridine, maleic anhydride and N,N-dimethylformamide mixed liquor
In, water-bath, soaks post-drying with ethanol after taking the film out；
（4）By P-hydroxybenzoic acid（p-HB）With 4-vinylpridine（4-VP）It is mixed to join in methanol, this is mixed
Liquid is placed in 3 h under dark condition；
（5）By step（3）The filter membrane processing is placed in step（4）Solution in, add N, N '-methylene-bisacrylamide
（MBAA）And azodiisobutyronitrile（AIBN）, seal after being passed through nitrogen, water-bath is shaken, take out, soaked with acetic acid mixture with methanol
Foam washing is washed, and obtains P-hydroxybenzoic acid trace composite membrane after drying（MIM p-HB）.
（6）Corresponding non-trace composite membrane（NIM p-HB）Preparation method remove step（4）In be not added with template molecule to hydroxyl
The outer above-mentioned steps of benzoic acid are identical.
In such scheme, step（1）In gather inclined difluoro second in potassium hydroxide described in every 1 L and mixed potassium dichromate
The addition of alkene micro-filtration membrane is 6 ~ 10 g, and in described mixed solution, the concentration of potassium hydroxide is 0.5 mmol/L, potassium dichromate
Mass fraction is 0.5 ~ 0.75%, and sodium sulfite solution mass fraction used is 1.2%, and soak time is 20 ~ 30 min.
In such scheme, step（2）Described in filter membrane, APTES, the usage ratio of toluene
For 0.12 ~ 0.2 g：1.5~1.8 mL ：20 ~ 25 mL, triethylamine consumption is 2 ~ 4, and Sealing period is 5 min, bath temperature
For 70 DEG C, the concussion time is 8 h, soaks 30 min in ethanol.
In such scheme, step（3）The amount ratio of middle filter membrane, pyridine, maleic anhydride and N,N-dimethylformamide
Example is 0.12 ~ 0.20 g：1~3 mL：1.5~4.5 g：20~30 mL；Bath temperature is 50 DEG C, and the response time is 3 h, in ethanol
Middle immersion 20 min.
In such scheme, step（4）Described in methanol in P-hydroxybenzoic acid concentration be 25 ~ 50 mmol/L, 4- second
The concentration of thiazolinyl pyridine is 100 ~ 200 mmol/L.
In such scheme, step（5）The concentration of middle N, N '-methylene-bisacrylamide is 100 ~ 400 mmol/L, azo
The concentration of bis-isobutyronitrile is 1.5 ~ 4.8 mmol/L.
In such scheme, step（5）Described in methanol and acetic acid mixture in, methanol is 9 with the volume ratio of acetic acid：
1, wash time is 48 ~ 72 h.
The molecularly imprinted composite membrane of above-mentioned preparation is applied to P-hydroxybenzoic acid in separating acetyl salicylic acid, specifically according to such as
Lower step is carried out：
（1）Respectively take a piece of MIM p-HBAnd NIM p-HBAdd to respectively in P-hydroxybenzoic acid methanol aqueous solution after weighing（First
Alcohol/water=3:7, V/V）, investigate the adsorbance of trace and non-blotting membrane after standing 4 h in 25 DEG C of calorstats, if liquor capacity isV(L), initial concentration isC 0(mg/L), after absorption, concentration isC 1(mg/L), then adsorbanceQ(mg/g) it is：
Q=(C 0-C 1)V/m
（2）Prepare aspirin and P-hydroxybenzoic acid methanol water mixed solution（Methanol/water=3:7, V/V）, the two
Concentration is 10 mg/L；Respectively take a piece of MIM p-HBAnd NIM p-HBAdd to respectively after weighing in above-mentioned solution, in 25 DEG C of constant temperature
Take out after standing 4 h in case, the concentration ultraviolet spectrophotometer of unadsorbed solute measures.
（3）Two identicals of self-control carry the aquarium of ground arm, add step in a pond（2）In mixed solution,
Methanol aqueous solution is added in another pond（Methanol/water=3:7, V/V）, use the fixed blotting membrane of clip or blank film between two ponds,
Composition H-shaped osmotic device, every certain time sampling, measures the concentration of substrate through film.
Advantages of the present invention：
(1) printing process occurs on membrane material surface, it is to avoid conventional template molecule because embed too deep and cannot eluting
Problem.
(2) add APTES, make molecularly imprinted polymer pass through covalently to be connected to the table of film
Face, it is to avoid polymer comes off in membrane cleaning process.
(3) using the p-hydroxybenzoic acid blotting membrane that the present invention obtains, there is superior p-hydroxybenzoic acid
Recognition performance.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Embodiment 1：
（1）Take 0.12 g polyvinylidene fluoride microporous filtering film（PVDF）It is placed in containing 0.56 g potassium hydroxide and 0.1 g dichromic acid
In 20 mL aqueous solutions of potassium, reaction at 55 DEG C was taken out after 1.5 hours, is cleaned repeatedly with distilled water, is then soaked in film and contains
20 min in 20 mL aqueous solutions of 0.24 g sodium sulfite, film is pressed from both sides out, is washed to neutrality with distillation, after ethanol rinse
Dry, obtain the pvdf membrane of surface hydroxylation.
（2）By step（1）The middle pvdf membrane processing is positioned in 100 mL conical flasks, adds 1.5 mL 3- aminopropans
Ethyl triethoxy silicane alkane（KH-550）And 20 mL toluene, and 2 triethylamines of Deca, seal after logical nitrogen 5 min, 70 DEG C of water-baths are shaken
Swing 8 h, after taking the film out, use ethanol soaking and washing 30 min, dry stand-by.
（3）By step（2）The middle pvdf membrane processing is positioned in 100 mL conical flasks, adds 1 mL pyridine, 1.5 g suitable
Anhydride maleique and 20 mL DMFs, 50 DEG C of water-bath 3 h, use ethanol soaking and washing after taking the film out
20 min, dry stand-by
（4）Take 0.069 g P-hydroxybenzoic acid（p-HB）With 0.2103 g 4-vinylpridine（4-VP）Add 20 mL
In the solution of methanol, after being completely dissolved, it is placed in 3 h under dark condition.
(5) by step（3）The middle pvdf membrane processing is positioned over（4）In mixed solution in, then in solution add
0.3084 g N, N '-methylene-bisacrylamide（MBAA）With 0.0048 g azodiisobutyronitrile（AIBN）, logical nitrogen 5 min is close
Envelope, 10 h are vibrated in 60 DEG C of water-baths.Take the film out after reaction, with methanol/acetic acid（9:1, V:V）Wash 48 h, divided with removing template
Sub- P-hydroxybenzoic acid, unreacted monomer, cross-linking agent and initiator, obtain P-hydroxybenzoic acid trace composite membrane after drying
（MIMp-HB）.Corresponding non-trace composite membrane（NIMp-HB）Preparation method same as described above, but be not added with template molecule pair
Hydroxy benzoic acid.
(6) obtained blotting membrane is carried out Staticadsorption experiment.
Prepare the P-hydroxybenzoic acid solution of 10 mg/L, solvent is methanol/water（3:7, V/V）Mixed solution, respectively take
A piece of blotting membrane and non-trace film quality are respectively 0.0245g and 0.0267g, are respectively put in the solution that 10 mL prepare, 25
DEG C calorstat in standing 4 hours after, with ultraviolet spectrophotometer measure solution in P-hydroxybenzoic acid content, be calculated
The adsorbance of trace polymerization film is adsorbance 0.4383 mg/L apparently higher than non-trace polymerization film for 0.6532 mg/L.
(7) obtained blotting membrane is carried out static Competitive adsorption assessment.
Prepare aspirin and the P-hydroxybenzoic acid solution of 10 mg/L, solvent is methanol/water（3:7, V/V）Mixed
Close solution, respectively take a piece of blotting membrane and non-trace film quality to be respectively 0.0214g and 0.0266g, be respectively put into what 10 mL prepared
In solution, after standing 4 hours in 25 DEG C of calorstat, with aspirin in ultraviolet spectrophotometer measurement solution with to hydroxyl
The content of yl benzoic acid, the separation factor being calculated trace polymerization film is 2.522 hence it is evident that being higher than the separation of non-trace polymerization film
The factor 1.254.
(8) obtained blotting membrane is carried out permeance property analysis test.
Two identical aquariums with ground arm of self-control, blotting membrane or blank film clip are fixed on two
In the middle of individual aquarium, composition H-shaped osmotic device, it is ensured that two ponds do not have seepage, adds concentration of substrate to be 50 mg/L in a pond
Aspirin and the methanol/water of P-hydroxybenzoic acid（3:7, V:V）Mixed solution, adds methanol/water in another pond（3:7,
V:V）Solution, sample interval is respectively 5,15,20,30,45,60,720 min, measures the substrate passing through polymeric film
Concentration.
Result shows, in the blank sample cell when blotting membrane is for permeable membrane during balance, acetysalicylic concentration is 18.15
The concentration of mg/L P-hydroxybenzoic acid is 12.01 mg/L, and when non-trace composite membrane is permeable membrane, second in blank sample pond
The salicylic concentration of acyl is 20.77 mg/L, and the concentration of P-hydroxybenzoic acid is 24.32 mg/L.
Embodiment 2：
(1) 0.12 g polyvinylidene fluoride micro-filtration membrane (PVDF) is taken to be placed in containing 0.56 g potassium hydroxide and 0.15 g weight
In 20 mL aqueous solutions of Neutral potassium chromate, reaction at 60 DEG C was taken out after 1 hour, is cleaned repeatedly with distilled water, is then soaked in film
20 min in the 20 mL aqueous solutions containing 0.24 g sodium sulfite, film is pressed from both sides out, is washed to neutrality with distillation, uses ethanol rinse
Post-drying, obtains the pvdf membrane of surface hydroxylation.
(2) by step（1）The middle pvdf membrane processing is positioned in 100 mL conical flasks, adds 1.8 mL 3- aminopropans
Ethyl triethoxy silicane alkane（KH-550）And 20 in mL toluene, and 4 triethylamines of Deca, seal after logical nitrogen 5 min, 70 DEG C of water-baths
Vibrate 8 h, after taking the film out, use ethanol soaking and washing 30 min, dry stand-by.
(3) by step（2）The middle pvdf membrane processing is positioned in 100 mL conical flasks, adds 3 mL pyridines, 4.5 g
Maleic anhydride and 20 mL DMFs, 50 DEG C of water-bath 3 h, use ethanol soaking and washing after taking the film out
20 min, dry stand-by.
(4) take 0.1382 g P-hydroxybenzoic acid（p-HB）With 0.4206 g 4-vinylpridine（4-VP）Add 20
In the solution of mL methanol, after being completely dissolved, it is placed in 3 h under dark condition.
(5) by step（3）The middle pvdf membrane processing is positioned over（4）In mixed solution in, then in solution add
1.2334 g N, N '-methylene-bisacrylamide（MBAA）With 0.0157 g azodiisobutyronitrile（AIBN）, logical nitrogen 5 min is close
Envelope, 10 h are vibrated in 60 DEG C of water-baths.Take the film out after reaction, with methanol/acetic acid (9:1, V:V) wash 72 h, divided with removing template
Sub- P-hydroxybenzoic acid, unreacted monomer, cross-linking agent and initiator, obtain P-hydroxybenzoic acid trace composite membrane after drying
（MIM p-HB）.Corresponding non-trace composite membrane（NIM p-HB）Preparation method same as described above, but be not added with template molecule pair
Hydroxy benzoic acid.
(6) obtained blotting membrane is carried out Staticadsorption experiment.
Prepare the P-hydroxybenzoic acid solution of 10 mg/L, solvent is methanol/water（3:7, V/V）Mixed solution, respectively take
A piece of blotting membrane and non-trace film quality are respectively 0.0226 g and 0.0235 g, are respectively put in the solution that 10 mL prepare, 25
DEG C calorstat in standing 4 hours after, with ultraviolet spectrophotometer measure solution in P-hydroxybenzoic acid content, be calculated
The adsorbance of trace polymerization film is adsorbance 0.3362 mg/g apparently higher than non-trace polymerization film for 0.5832 mg/g.
(7) obtained blotting membrane is carried out static Competitive adsorption assessment.
Prepare aspirin and the P-hydroxybenzoic acid solution of 10 mg/L, solvent is methanol/water（3:7, V/V）Mixed
Close solution, respectively take a piece of blotting membrane and non-trace film quality to be respectively 0.0232 g and 0.0243 g, be respectively put into 10 mL and prepare
Solution in, standing after 4 hours in 25 DEG C of calorstat, with aspirin and right in ultraviolet spectrophotometer measurement solution
The content of hydroxy benzoic acid, the separation factor being calculated trace polymerization film is 2.788 hence it is evident that being higher than dividing of non-trace polymerization film
From the factor 1.174.
(8) obtained blotting membrane is carried out permeance property analysis test.
Two identical aquariums with ground arm of self-control, blotting membrane or blank film clip are fixed on two
In the middle of individual aquarium, composition H-shaped osmotic device, it is ensured that two ponds do not have seepage, adds concentration of substrate to be 50 mg/L in a pond
Aspirin and the methanol/water of P-hydroxybenzoic acid（3:7, V:V）Mixed solution, adds methanol/water in another pond（3:7,
V:V）Solution, sample interval is respectively 5,15,20,30,45,60,720 min, measures the substrate passing through polymeric film
Concentration.
Result shows, in the blank sample cell when blotting membrane is for permeable membrane during balance, acetysalicylic concentration is 16.98
Mg/L, the concentration of P-hydroxybenzoic acid is 9.98 mg/L, and when non-trace composite membrane is permeable membrane, second in blank sample pond
The salicylic concentration of acyl is 18.65 mg/L, and the concentration of P-hydroxybenzoic acid is 22.69 mg/L.
Described embodiment be the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment, not
In the case of deviating from the flesh and blood of the present invention, any conspicuously improved, replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (7)
1. a kind of preparation method of molecularly imprinted composite membrane is it is characterised in that carry out as follows：
(1) polyvinylidene fluoride micro-filtration membrane is placed in potassium hydroxide and potassium dichromate mixed aqueous solution, reacts at 50～60 DEG C
Take out after 1.0～1.5h, with distilled water wash, then film is soaked in aqueous solution of sodium bisulfite, with steaming after taking the film out
Distilled water is washed till neutrality, then with ethanol rinse post-drying；
(2) filter membrane processing step (1) is placed in APTES and toluene mixture liquid, adds three second
Amine, seals after being passed through nitrogen, water-bath is shaken, and soaks post-drying with ethanol after taking the film out；
(3) filter membrane processing step (2) is placed in pyridine, maleic anhydride and DMF mixed liquor, and 50
DEG C water-bath 3h, soaks post-drying with ethanol after taking the film out；
(4) P-hydroxybenzoic acid and 4-vinylpridine are mixed to join in methanol, this mixed liquor is placed under dark condition
3h；
(5) filter membrane processing step (3) is placed in the mixed liquor of step (4), adds N, N '-methylene-bisacrylamide and idol
Nitrogen bis-isobutyronitrile, seals after being passed through nitrogen, water-bath is shaken, uses methanol and acetic acid mixture washing by soaking after taking-up, after drying
To P-hydroxybenzoic acid trace composite membrane.
2. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that described in every 1L in step (1)
Potassium hydroxide and mixed potassium dichromate in polyvinylidene fluoride micro-filtration membrane addition be 6～10g, described mixed solution
The concentration of middle potassium hydroxide is 0.5mmol/L, and the mass fraction of potassium dichromate is 0.5～0.75%, and sodium sulfite used is molten
Liquid mass fraction is 1.2%, and soak time is 20～30min.
3. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that the filter described in step (2)
Film, APTES, the usage ratio of toluene are 0.12～0.2g：1.5～1.8mL：20～25mL, three second
Amine consumption is 2～4, and Sealing period is 5min, and bath temperature is 70 DEG C, and the concussion time is 8h, soaks 30min in ethanol.
4. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that filter membrane, pyrrole in step (3)
The usage ratio of pyridine, maleic anhydride and N,N-dimethylformamide is 0.12～0.20g：1～3mL：1.5～4.5g：20
～30mL；Soak 20min in ethanol.
5. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that the first described in step (4)
In alcohol, the concentration of P-hydroxybenzoic acid is 25～50mmol/L, and the concentration of 4-vinylpridine is 100～200mmol/L.
6. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that the step described in step (5)
Suddenly the filter membrane consumption that (3) are processed is：6～10g filter membrane, N, N is added in the mixed liquor of every 1L step (4) '-methylene bisacrylamide acyl
The concentration of amine is 100～400mmol/L, and the concentration of azodiisobutyronitrile is 1.5～4.8mmol/L.
7. the preparation method of molecularly imprinted composite membrane as claimed in claim 1 is it is characterised in that the first described in step (5)
In alcohol and acetic acid mixture, methanol is 9 with the volume ratio of acetic acid：1, wash time is 48～72h.
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| CN104741009B (en) * | 2015-03-20 | 2017-03-29 | 江苏大学 | The preparation method and applications of salicylic acid molecular engram acetyl cellulose blend film |
| CN108201795B (en) * | 2017-12-22 | 2019-12-03 | 江苏大学 | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material |
| CN109351348A (en) * | 2018-09-28 | 2019-02-19 | 昆明理工大学 | It is a kind of using 4-vinylpridine as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
| CN110776596B (en) * | 2019-10-28 | 2022-01-28 | 东南大学 | Para-hydroxybenzoic acid selective resin and preparation method thereof |
| CN113019337A (en) * | 2021-02-01 | 2021-06-25 | 江苏大学 | Preparation method of polytetrafluoroethylene boron affinity imprinted membrane and application of polytetrafluoroethylene boron affinity imprinted membrane in selective separation of shikimic acid |
| CN115212855B (en) * | 2022-07-04 | 2024-04-12 | 广东食品药品职业学院 | Molecularly imprinted membrane and preparation method and application thereof |
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