CN103881018A - Method of preparing temperature-sensitive molecularly imprinted polymers through suspension polymerization - Google Patents
Method of preparing temperature-sensitive molecularly imprinted polymers through suspension polymerization Download PDFInfo
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- CN103881018A CN103881018A CN201410074504.8A CN201410074504A CN103881018A CN 103881018 A CN103881018 A CN 103881018A CN 201410074504 A CN201410074504 A CN 201410074504A CN 103881018 A CN103881018 A CN 103881018A
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Abstract
The invention relates to a method of preparing temperature-sensitive molecularly imprinted polymers through suspension polymerization, and belongs to the technical field of preparation of environment function materials. In particular, the temperature-sensitive molecularly imprinted polymers (MIPs) are prepared by adopting a suspension polymerization method by taking acrylamide as a functional monomer, N-isopropyl acrylamide as a temperature-sensitive monomer, phenol as template molecules, potassium persulfate as an initiator, methylbenzene as a pore-foaming agent, N, N-methylene bisacrylamide as a crosslinking agent and span-80 as a surfactant, and is applied in a water environment to selectively absorb and separate phenol. The prepared temperature-sensitive molecularly imprinted polymers are highly dispersed in regular spherical shapes. Holes in special shapes and sizes left by the template molecules are contained on the surfaces of the polymers. The holes have specially arranged binding site and the MIPs can highly selectively adsorb the target pollutant phenol.
Description
Technical field
The invention belongs to environment functional material preparing technical field, relate to a kind of method of preparing Temperature-sensitive Molecular Imprinted Polymers by suspension polymerization, and be applied to the chlorophenol pollutant in selective adsorption Separation of Water environment.
Background technology
Along with industrial technology, especially developing rapidly of organic synthesis industry, output and the kind of organic compound grow with each passing day, and its pollution range and degree to environment is also day by day serious.Have every year according to estimates 1000 kinds of novel organic compound to put goods on the market, wherein their great majority are chemical substances of suitable difficult for biological degradation.Chlorophenols organism can be by phenolic compound direct chlorination or Hydrolysis of Chlorobenzene, is the Persistent organic pollutants of a quasi-representative, and it is introduced into the result that environment is also human behavior.Be used as sterilant, sterilizing agent and sanitas and be widely used because chlorophenols organism has anti-, the sterilization of wide spectrum and disinsection efficiency, be mainly used in timber, vegetables, leather, the sanitas of coating etc. and sterilizing agent, meanwhile, or the synthetic intermediate product of much industry or use as starting material such as agricultural chemicals, sterilant, mycocide, pharmacy industries.Chlorophenol pollutant is difficult for being degraded by natural microorganisms, easily in environment, accumulates, and chlorophenol pollutant can cause a lot of human diseasess, even may produce carcinogenic, teratogenesis, mutagenic effect.Therefore, from the aqueous solution, effectively remove the important topic that chlorophenol is field of environment protection.
The control of P-Chlorophenol pollutant and control are the new challenges facing in water prevention and cure of pollution field.Various water technologies have been widely used in administering the chlorophenol pollutant in water surrounding, for example extraction process, absorption method, membrane separation technique, oxidation style etc.Absorption in water treatment refers to the porousness solid matter (sorbent material) with adsorptive power, a kind for the treatment of process of the impurity such as the oligodynamical organic matter in Adsorption water.Because sorbent material has huge specific surface area and good absorption property, it is to dissolved organic matter in water, comprises that biological process and oxidation style are difficult to the organic pollutant removed and have good removal effect as chlorophenol etc.At present, absorption method is to remove the common method of chlorophenol pollutant in water surrounding.
Recently, molecular imprinting has obtained everybody extensive concern.Molecular imprinting is preparation has single-minded recognition capability polymkeric substance process to a certain specific molecular, and the polymkeric substance of preparation is called molecularly imprinted polymer.In molecularly imprinted polymer, contain a lot of specified shapes and big or small hole, in hole, there is the binding site of particular arrangement, and the structure of template molecule is had to certain memory and recognition function.Molecularly imprinted polymer can be realized highly selective absorption to target contaminant.In recent years, attempted temperature sensitive type responsive materials to be incorporated into and in molecular imprinting, to prepare Temperature-sensitive Molecular Imprinted Polymers.Temperature-sensitive Molecular Imprinted Polymers can effectively be realized the controlled of separation/enrichment process by temperature " switch ", has avoided traditional Adsorption and desorption additive process loaded down with trivial details, uses the drawback of soda acid.
The method of preparing Temperature-sensitive Molecular Imprinted Polymers has a variety of, comprises suspension polymerization, letex polymerization and dispersion polymerization etc., and wherein suspension polymerization is to prepare one of effective ways of Temperature-sensitive Molecular Imprinted Polymers microballoon.The size of its polymer beads of preparing and size distribution can be controlled by adjusting reaction parameter.The Temperature-sensitive Molecular Imprinted Polymers microballoon of preparing by suspension polymerization has higher specific surface area and remarkable absorption property.
Summary of the invention
Technical scheme of the present invention refers to suspension polymerization prepares Temperature-sensitive Molecular Imprinted Polymers, taking acrylamide as function monomer, taking NIPA as temperature sensitive monomer, taking phenol as template molecule, taking Potassium Persulphate as initiator, taking toluene as pore-creating agent, with N, N-methylene-bisacrylamide is linking agent, taking span-80 as tensio-active agent, adopt the method preparation of suspension polymerization to generate Temperature-sensitive Molecular Imprinted Polymers (MIPs), and be applied to selective adsorption separating phenol in water surrounding.
technical scheme
Utilize suspension polymerization to prepare the method for Temperature-sensitive Molecular Imprinted Polymers, carry out according to the following steps:
(1) prepare oil phase
By toluene, span-80 joins in the there-necked flask that hexanaphthene is housed and forms oil phase under the protection of nitrogen, wherein gate ring hexane, the ratio of toluene and span-80 is (130-140): (3-4): (0.5-0.6) (mL/mL/g), this oil phase is under nitrogen protection, and temperature of reaction is 35 DEG C, and stirring velocity is 400 rpm/min, fully stir 1-2 h, until dissolve completely;
(2) prepare water
By phenol, acrylamide, NIPA, Potassium Persulphate, N, N-methylene-bisacrylamide is soluble in water, wherein controls phenol, acrylamide, NIPA, Potassium Persulphate, the ratio of N,N methylene bis acrylamide and water is: (0.3-0.4): (1-1.2): (4-4.5): (0.4-0.5): (1-1.2): (30-40) (g/g/g/g/g/mL).This water is under nitrogen protection, and stirring velocity is 400 rpm/min, fully stirs 10-20 min, until dissolve completely;
(3) Temperature-sensitive Molecular Imprinted Polymers is prepared in suspension polymerization
By the water of preparation in step (2), within 60 min, join dropwise in the oil phase of preparation in step (1), the volume ratio of oil phase and water is (133-144): (30-40), stirring velocity is controlled at 400 rpm/min, temperature is controlled at 70 DEG C, and the reaction times is 4 h.
The Temperature-sensitive Molecular Imprinted Polymers obtaining cleans 3 times with ethanol, then uses washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of methyl alcohol and acetic acid eluent, wherein methyl alcohol: the ratio of acetic acid is 90:10 (V/V), and the Temperature-sensitive Molecular Imprinted Polymers preparing in step (3) is cleaned to 7-10 days in apparatus,Soxhlet's, then be washed till neutrality, natural air drying with deionized water.
What pay special attention to is, the preparation method of the non-imprinted polymer of temperature sensitive type (MNIPs) is identical with the preparation method of above-mentioned Temperature-sensitive Molecular Imprinted Polymers, just in the water preparation process of step (2), do not add template molecule phenol, and do not have step (4).
The polymerization process adopting in above-mentioned technical scheme is suspension polymerization.
Phenol described in above-mentioned technical scheme, it act as template molecule.
Acrylamide described in above-mentioned technical scheme, it act as function monomer.
Potassium Persulphate described in above-mentioned technical scheme, it act as initiator.
Toluene described in above-mentioned technical scheme, it act as pore-creating agent.
NIPA described in above-mentioned technical scheme, it act as temperature sensitive monomer.
N,N methylene bis acrylamide described in above-mentioned technical scheme, it act as linking agent.
Span-80 described in above-mentioned technical scheme, it makes promising tensio-active agent.
Technological merit of the present invention: this product is Temperature-sensitive Molecular Imprinted Polymers, prepare by suspension polymerization, contain specified shape that multiple template molecules stay and big or small hole at polymer surfaces, in hole, have the binding site of particular arrangement, molecularly imprinted polymer can be realized highly selective absorption to target contaminant.Temperature sensitive type sorbing material has responsiveness to temperature, and when temperature is during lower than critical temperature, microsphere volume shrinks, and polymkeric substance hole dwindles; When temperature is during higher than critical temperature, polymkeric substance hole increases.
Brief description of the drawings
Fig. 1 is the pattern of Temperature-sensitive Molecular Imprinted Polymers of preparation in embodiment 1 under powerful microscope.As can be seen from the figure, Temperature-sensitive Molecular Imprinted Polymers is high dispersive, presents the spherical of rule.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Temperature-sensitive Molecular Imprinted Polymers configuration of surface of preparation in embodiment 1.As can be seen from the figure, there are a lot of holes in polymer surfaces, and this will be conducive to the absorption of polymkeric substance P-Chlorophenol pollutant.
Fig. 3 is nitrogen adsorption desorption thermoisopleth and the pore size distribution curve of embodiment 2.The specific surface area of Temperature-sensitive Molecular Imprinted Polymers is 397 m
2/ g, according to BDDT sorting technique, this thermoisopleth can be classified as Second Type, from a figure, can find out, and there is hysteretic phenomenon in this thermoisopleth, and this has confirmed the existence in porous cave.In b figure, shown pore size distribution curve, as can be seen from the figure, the mean pore size of Temperature-sensitive Molecular Imprinted Polymers is 6 nm.
Embodiment
Absorption property analysis test method described in technique scheme is specially:
(1) Static Adsorption test
The phenol solution that 10 mL different concns are housed is joined in colorimetric cylinder, add respectively 10 mg Temperature-sensitive Molecular Imprinted Polymers and the non-imprinted polymer of temperature sensitive type, be placed in the water bath with thermostatic control of differing temps and leave standstill 12 h, investigate the impact of temperature of reaction on sorbent material absorption property;
The phenol solution that 10 mL same concentrations are housed is joined in colorimetric cylinder, add respectively 10 mg Temperature-sensitive Molecular Imprinted Polymers and the non-imprinted polymer of temperature sensitive type, be placed on and in the water bath with thermostatic control of uniform temp, leave standstill 12 h, after sorbent material is separated, methyl alcohol and acetic acid (90:10 V/V) are mixed with to eluent, utilize eluent desorption in the water bath with thermostatic control of differing temps, investigate the impact of differential responses temperature on desorption effect;
After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, the not concentration ultraviolet spectral analysis of the phenol of absorption, and according to result calculate loading capacity (
q e, mg/g):
Wherein
c 0(mg/L) and
c e(mg/L) be respectively the concentration of phenol before and after absorption,
w(g) be sorbent material consumption,
v(mL) be test fluid volume.
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
1, utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, its preparation method carries out according to following step:
(1) prepare oil phase
By toluene, span-80 joins in the there-necked flask that hexanaphthene is housed and forms oil phase under the protection of nitrogen, wherein gate ring hexane, the ratio of toluene and span-80 is 130:3:0.5(mL/mL/g), this oil phase is under nitrogen protection, and temperature of reaction is 35 DEG C, and stirring velocity is 400 rpm/min, fully stir 1 h, until dissolve completely;
(2) prepare water
By phenol, acrylamide, NIPA, Potassium Persulphate, N, N-methylene-bisacrylamide is soluble in water, wherein controls phenol, acrylamide, NIPA, Potassium Persulphate, the ratio of N,N methylene bis acrylamide and water is: 0.3:1:4:0.4:1:30(g/g/g/g/g/mL).This water is under nitrogen protection, and stirring velocity is 400 rpm/min, fully stirs 10 min, until dissolve completely;
(3) Temperature-sensitive Molecular Imprinted Polymers is prepared in suspension polymerization
By the water of preparation in step (2), within 60 min, join dropwise in the oil phase of preparation in step (1), the volume ratio of oil phase and water is 133:30, stirring velocity is controlled at 400 rpm/min, and temperature is controlled at 70 DEG C, and the reaction times is 4 h.
The Temperature-sensitive Molecular Imprinted Polymers obtaining cleans 3 times with ethanol, then uses washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of methyl alcohol and acetic acid eluent, wherein methyl alcohol: the ratio of acetic acid is 90:10 (V/V), the Temperature-sensitive Molecular Imprinted Polymers preparing is cleaned 7 days in apparatus,Soxhlet's, then be washed till neutrality, natural air drying with deionized water in step (3).
What pay special attention to is, the preparation method of the non-imprinted polymer of temperature sensitive type (MNIPs) is identical with the preparation method of above-mentioned Temperature-sensitive Molecular Imprinted Polymers, just in the water preparation process of step (2), do not add template molecule phenol, and do not have step (4).
Fig. 1 is the pattern of Temperature-sensitive Molecular Imprinted Polymers of preparation in embodiment 1 under powerful microscope.As can be seen from the figure, Temperature-sensitive Molecular Imprinted Polymers is high dispersive, presents the spherical of rule.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Temperature-sensitive Molecular Imprinted Polymers configuration of surface of preparation in embodiment 1.As can be seen from the figure, there are a lot of holes in polymer surfaces, and this will be conducive to the absorption of polymkeric substance P-Chlorophenol pollutant.
2, absorption property analytical test:
(1) Static Adsorption test 1
The phenol solution that 10 mL different concns are housed is joined in colorimetric cylinder, concentration is respectively 10,50,100,150,200 and 300 mg/L, in colorimetric cylinder, add respectively 10 mg Temperature-sensitive Molecular Imprinted Polymers and the non-imprinted polymer of temperature sensitive type, colorimetric cylinder is placed on respectively to 25 DEG C, in the water bath with thermostatic control of 35 DEG C and 45 DEG C, leaves standstill 12h, investigate the impact of temperature on temperature sensitive type sorbent material absorption property; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and the not concentration ultraviolet spectral analysis of the phenol of absorption, according to formula calculation result.
Result shows: Temperature-sensitive Molecular Imprinted Polymers has responsiveness to temperature, and along with the rising of temperature, the loading capacity of sorbent material becomes greatly gradually, and the loading capacity of trace type sorbent material is apparently higher than non-trace type sorbent material.
embodiment 2:
1, utilize suspension polymerization to prepare the method for magnetic molecularly imprinted polymer, carry out according to the following steps:
(1) prepare oil phase
By toluene, span-80 joins in the there-necked flask that hexanaphthene is housed and forms oil phase under the protection of nitrogen, wherein gate ring hexane, the ratio of toluene and span-80 is 140:4:0.6(mL/mL/g), this oil phase is under nitrogen protection, and temperature of reaction is 35 DEG C, and stirring velocity is 400 rpm/min, fully stir 2 h, until dissolve completely;
(2) prepare water
By phenol, acrylamide, NIPA, Potassium Persulphate, N, N-methylene-bisacrylamide is soluble in water, wherein controls phenol, acrylamide, NIPA, Potassium Persulphate, the ratio of N,N methylene bis acrylamide and water is: 0.4:1.2:4.5:0.5:1.2:40 (g/g/g/g/g/mL).This water is under nitrogen protection, and stirring velocity is 400 rpm/min, fully stirs 20 min, until dissolve completely;
(3) Temperature-sensitive Molecular Imprinted Polymers is prepared in suspension polymerization
By the water of preparation in step (2), within 60 min, join dropwise in the oil phase of preparation in step (1), the volume ratio of oil phase and water is 144:40, stirring velocity is controlled at 400 rpm/min, and temperature is controlled at 70 DEG C, and the reaction times is 4 h.
The Temperature-sensitive Molecular Imprinted Polymers obtaining cleans 3 times with ethanol, then uses washed with de-ionized water 2 times.
(4) wash-out template molecule
With the preparation of methyl alcohol and acetic acid eluent, wherein methyl alcohol: the ratio of acetic acid is 90:10 (V/V), the Temperature-sensitive Molecular Imprinted Polymers preparing is cleaned 10 days in apparatus,Soxhlet's, then be washed till neutrality, natural air drying with deionized water in step (3).
What pay special attention to is, the preparation method of the non-imprinted polymer of temperature sensitive type (MNIPs) is identical with the preparation method of above-mentioned Temperature-sensitive Molecular Imprinted Polymers, just in the water preparation process of step (2), do not add template molecule phenol, and do not have step (4).
Fig. 3 is nitrogen adsorption desorption thermoisopleth and the pore size distribution curve of embodiment 2.The specific surface area of Temperature-sensitive Molecular Imprinted Polymers is 397 m
2/ g, the mean pore size of Temperature-sensitive Molecular Imprinted Polymers is 6 nm.
2, absorption property analytical test:
(1) Static Adsorption test 1
10 mL will be housed, concentration is that the phenol solution of 100 mg/L joins in colorimetric cylinder, add respectively 10 mg Temperature-sensitive Molecular Imprinted Polymers and the non-imprinted polymer of temperature sensitive type, be placed on and in the water bath with thermostatic control of 25 DEG C, leave standstill 12 h, after sorbent material is separated, methyl alcohol and acetic acid (90:10 V/V) are mixed with to eluent, utilize eluent at 25 DEG C, desorption in the water bath with thermostatic control of 35 DEG C and 45 DEG C, investigates the impact of differential responses temperature on desorption effect;
Result demonstration, in desorption process, along with the rising of temperature, the phenol of wash-out reduces gradually, and this conclusion has been verified the response of Temperature-sensitive Molecular Imprinted Polymers to temperature.
Claims (1)
1. utilize suspension polymerization to prepare the method for Temperature-sensitive Molecular Imprinted Polymers, carry out according to the following steps:
(1) prepare oil phase
By toluene, span-80 joins in the there-necked flask that hexanaphthene is housed and forms oil phase under the protection of nitrogen, wherein gate ring hexane, the ratio of toluene and span-80 is (130-140): (3-4): (0.5-0.6) (mL/mL/g), this oil phase is under nitrogen protection, and temperature of reaction is 35 DEG C, and stirring velocity is 400 rpm/min, fully stir 1-2 h, until dissolve completely;
(2) prepare water
By phenol, acrylamide, NIPA, Potassium Persulphate, N, N-methylene-bisacrylamide is soluble in water, wherein controls phenol, acrylamide, NIPA, Potassium Persulphate, the ratio of N,N methylene bis acrylamide and water is: (0.3-0.4): (1-1.2): (4-4.5): (0.4-0.5): (1-1.2): (30-40) (g/g/g/g/g/mL);
This water is under nitrogen protection, and stirring velocity is 400 rpm/min, fully stirs 10-20 min, until dissolve completely;
(3) Temperature-sensitive Molecular Imprinted Polymers is prepared in suspension polymerization
By the water of preparation in step (2), within 60 min, join dropwise in the oil phase of preparation in step (1), the volume ratio of oil phase and water is (133-144): (30-40), stirring velocity is controlled at 400 rpm/min, temperature is controlled at 70 DEG C, and the reaction times is 4 h;
The Temperature-sensitive Molecular Imprinted Polymers obtaining cleans 3 times with ethanol, then uses washed with de-ionized water 2 times;
(4) wash-out template molecule
With the preparation of methyl alcohol and acetic acid eluent, wherein methyl alcohol: the ratio of acetic acid is 90:10 (V/V), and the Temperature-sensitive Molecular Imprinted Polymers preparing in step (3) is cleaned to 7-10 days in apparatus,Soxhlet's, then be washed till neutrality, natural air drying with deionized water.
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| CN104140501A (en) * | 2014-07-22 | 2014-11-12 | 中国科学院烟台海岸带研究所 | Thermosensitive bisphenol A (BPA) imprinted polymeric microsphere and application thereof |
| CN104177547A (en) * | 2014-07-29 | 2014-12-03 | 江苏大学 | Method for preparing composite cellulose porous imprinting adsorbent |
| CN104788713A (en) * | 2015-03-27 | 2015-07-22 | 江苏大学 | Preparation method and application of phenol molecular imprinting doped membrane |
| CN105482025A (en) * | 2016-01-01 | 2016-04-13 | 兰州交通大学 | Method for preparing molecularly-imprinted polymer used for adsorbing methylene blue through inverse microemulsion polymerization method |
| CN110698596A (en) * | 2019-09-23 | 2020-01-17 | 浙江大学山东工业技术研究院 | Creatinine molecular imprinting polymer, screen printing electrode and preparation method thereof |
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| CN104140501A (en) * | 2014-07-22 | 2014-11-12 | 中国科学院烟台海岸带研究所 | Thermosensitive bisphenol A (BPA) imprinted polymeric microsphere and application thereof |
| CN104140501B (en) * | 2014-07-22 | 2016-08-24 | 中国科学院烟台海岸带研究所 | A kind of temperature sensitive bisphenol-A imprinted polymer microsphere and application thereof |
| CN104177547A (en) * | 2014-07-29 | 2014-12-03 | 江苏大学 | Method for preparing composite cellulose porous imprinting adsorbent |
| CN104177547B (en) * | 2014-07-29 | 2016-09-14 | 江苏大学 | A kind of preparation method of cellulose compound porous trace adsorbent |
| CN104788713A (en) * | 2015-03-27 | 2015-07-22 | 江苏大学 | Preparation method and application of phenol molecular imprinting doped membrane |
| CN104788713B (en) * | 2015-03-27 | 2018-01-16 | 江苏大学 | A kind of preparation method and applications of phenol molecular engram doping |
| CN105482025A (en) * | 2016-01-01 | 2016-04-13 | 兰州交通大学 | Method for preparing molecularly-imprinted polymer used for adsorbing methylene blue through inverse microemulsion polymerization method |
| CN110698596A (en) * | 2019-09-23 | 2020-01-17 | 浙江大学山东工业技术研究院 | Creatinine molecular imprinting polymer, screen printing electrode and preparation method thereof |
| CN110711568A (en) * | 2019-11-25 | 2020-01-21 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
| CN110711568B (en) * | 2019-11-25 | 2022-04-08 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
| CN112577937A (en) * | 2020-12-07 | 2021-03-30 | 首都师范大学 | Preparation method and application of novel lysozyme fluorescence sensor |
| CN113354781A (en) * | 2020-12-24 | 2021-09-07 | 兰州理工大学 | Preparation method of temperature-sensitive porous imprinted polymer |
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| CN114163565A (en) * | 2021-11-22 | 2022-03-11 | 北京理工大学 | Method for extracting nicotine from molecularly imprinted polymer |
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