CN109438638A - The strong modification imprinting polymer and preparation method thereof of adsorption capacity - Google Patents
The strong modification imprinting polymer and preparation method thereof of adsorption capacity Download PDFInfo
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Abstract
For the deficiencies in the prior art, an object of the present invention is to provide a kind of preparation method of modification imprinting polymer for improving adsorption capacity, and the cost of the preparation method is low, and method is simple.The second purpose of invention is to provide a kind of modification imprinting polymer for improving adsorption capacity, it has excellent selectivity and adsorptivity to heavy metal ion, can be realized the quick detection and processing of heavy metal ion in pollutant.
Description
Present patent application is divisional application, and parent application number is 2017114931341, and parent application day is in December, 2017
30 days.
Technical field
The present invention relates to imprinting technical field of polymer, and in particular to a kind of modification trace that adsorption capacity is strong is high
Molecularly Imprinted Polymer and preparation method thereof.
Background technique
Molecularly imprinted polymer (moleculaly imprinted polymer, abbreviation MIP) is to utilize molecular engram skill
The high molecular polymer of art preparation having and template molecule exactly matches on space structure and binding site.1972
WulffG research group successfully prepares MIP for the first time, and the research of this respect is made to produce breakthrough.It is non-covalent after the eighties
Year Mosbach of the appearance of type template polymer, especially 1993 et al. is reported in relation to the research of theophylline molecularly imprinted polymer, is made
This technology has new development in biosensor, artificial antibody's simulation and chromatography solid phase in terms of, thus make its at
For one of the emerging field that chemistry and biology intersects, gazes at and rapidly develop to the world.MIP has template molecule single-minded
Recognition reaction, compared with other molecular recognition materials, MIP has three big features: first is that precordainment, i.e., it can be according to different
Purpose prepares different MIP, to meet a variety of different needs；Second is that identity, i.e. MIP be it is customized according to template molecule,
It can exclusively recognition template molecule；Third is that practicability, i.e., it can be with natural biomolecule identifying system such as enzyme-to-substrate, anti-
It is former comparable with antibody, receptor and hormone, since it is prepared by chemically synthesized method, there is natural molecule identification again
The ability of anti-adverse environment not available for system, to show the stability and long service life of height.
Currently, in industrial processes (such as mining, steel and iron manufacturing, non-ferrous metal metallurgy, machine-building, chemical industry,
Electronics, instrument) waste water containing heavy metal ion (cadmium, chromium, copper, mercury, cobalt, nickel etc.) that can generate is a huge sum of money to water environment pollution
Belong to ion primary pollution source；The processing of waste water at present has 4 kinds: chemical precipitation method, activated carbon adsorption, solvent extraction and ion are handed over
Absorption is changed, and absorption method is widely used in the processing of the sewage containing heavy metal ion.But for current adsorbent kind, still
So there are the small selective adsorption capacity differences lower so as to cause processing capacity, to different metal ions of saturated adsorption capacity
Greatly, undesirable to the lower water treatment effect of concentration of heavy metal ion, heavy metal removal is difficult, regeneration effect is bad,
There are secondary pollution, discard the deficiencies of rear biodegradability is poor.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of modification for improving adsorption capacity
The cost of the preparation method of imprinting polymer, the preparation method is low, and method is simple.
The second purpose of invention is to provide a kind of modification imprinting polymer for improving adsorption capacity, it is to heavy metal
Ion has excellent selectivity and adsorptivity, can be realized the quick detection and processing of heavy metal ion in pollutant.
The present inventor has found that molecular engram in the prior art is poly- during long-term disposal heavy metal ion
It is big to different heavy metal ion selective differences to close object, targetedly a certain or several heavy metal ion can only be detected
And absorption, cannot contents of many kinds of heavy metal ion be detected and be adsorbed simultaneously, and the molecularly imprinted polymer of the prior art is to gold
The adsorption capacity for belonging to ion is poor, cannot be removed effectively heavy metal ions in wastewater.
To achieve the goals above, the present invention provides a kind of system of modification imprinting polymer for improving adsorption capacity
Preparation Method, comprising the following steps:
(1) preparation of improved silica, comprising the following steps:
(1.1) by esters of silicon acis in alkaline solution 5~10h of precipitation, be washed out to neutrality, obtain partial size be 200~
The Nano particles of silicon dioxide of 500nm；
(1.2) Nano particles of silicon dioxide is uniformly mixed in organic solvent with silane coupling agent, at 60~90 DEG C
1~3h is stirred, improved silica is obtained.
(2) by beta-cyclodextrin, citric acid and sodium hypophosphite under aqueous conditions after mixing, in 120 DEG C of reaction 3-
5h, by reaction product with 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide water-soluble
After stirring 30~45min in liquid, chitosan 30~45min of precipitation at 60~80 DEG C is added, the source M is then added, in indifferent gas
Under body protection, 1~5h is stirred at 75~100 DEG C, obtains complex；
(3) complex, acrylamide, cellulose are uniformly dispersed to form suspension in organic solvent, are stirred at room temperature
It mixes and 0.5~2h of self-assembling reaction occurs, then spray drying forms function microcapsules monomer；
(4) improved silica, ethylene glycol dimethacrylate and function microcapsules monomer are surpassed in organic solvent
Sound is uniformly dispersed, and obtains preceding pre-polymer solution；Then, initiator is added under inert gas protection, polymerize at 60~85 DEG C
React 1~5h；
(5) it is filtered after the product of step (4) being impregnated 30~60min in an acidic solution, filtered solid is washed
To neutrality, then wash products are dried in vacuo, are improved the modification imprinting polymer of adsorption capacity；
The M is at least one of copper, chromium, manganese, mercury, cadmium, lead, arsenic, zinc, tin, nickel, cobalt, antimony and bismuth.
Preferably, in step (1.2), the silane coupling agent is selected from aminopropyl triethoxysilane, aminopropyl front three
Oxysilane, 2- aminoethyl amino propyl trimethoxy silane, divinyl triammonium base propyl trimethoxy silicane, aminoethylaminopropyl
Methyl dimethoxysilane, aminoethylaminopropyl triethoxysilane, ureidopropyltriethoxysilane and ureido-propyl front three
At least one of oxysilane.
Preferably, in step (2), the beta-cyclodextrin, the molar ratio of citric acid and sodium hypophosphite is 1:(3~5):
(1~2).
Preferably, the mass ratio of the complex, acrylamide and cellulose is 1:(0.8~1.2): (3~12).
Preferably, in step (3), it is fine that the cellulose is selected from carboxymethyl cellulose, methylcellulose, hydroxypropyl methyl
Tie up at least one of element, hydroxyethyl cellulose, ethyl cellulose.
Preferably, in step (4), the improved silica, ethylene glycol dimethacrylate and function microcapsules
The mass ratio of monomer is 1:(0.5~1.8): (2~5).
Preferably, the organic solvent is selected from least one of acetonitrile, toluene, acetone and ethylene glycol；And/or described draw
Hair agent is azodiisobutyronitrile.
The present invention also provides a kind of modification imprinting polymer for improving adsorption capacity, according to above-mentioned preparation method
It is prepared.
Through the above technical solutions, the present invention has following technical effect that
(1) by preparing molecular engram on improved silica surface, surface imprinted process marking site position can be passed through
The position close to surface is lived in the surface of polymer, mass transfer can be improved, improves separative efficiency and recognition capability.
(2) modified chitosan contains the surface functional group of systematicness, is capable of providing more imprinted sites, and a large amount of
Metal ion be coordinated；And chitosan itself is nontoxic, and biodegradability is good, secondary pollution is not generated after use, so
There is unique advantage in the treatment of waste water.
(3) metal ion can be made to be uniformly dispersed in polymer using microcapsule structure, avoids the occurrence of reunion, improved
The uniformities of imprinted sites.
To sum up, molecularly imprinted polymer of the invention can be cooperated with various metals, and have more and distribution equal
Even imprinted sites significantly improve its adsorption capacity to metal ion.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.
The present invention provides a kind of preparation method of modification imprinting polymer for improving adsorption capacity, including following step
It is rapid:
(1) preparation of improved silica:
(2) by beta-cyclodextrin, citric acid and sodium hypophosphite under aqueous conditions after mixing, in 120 DEG C of reaction 3-
5h, by reaction product with 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide water-soluble
After stirring 30~45min in liquid, chitosan 30~45min of precipitation at 60~80 DEG C is added, the source M is then added, in indifferent gas
Under body protection, 1~5h is stirred at 75~100 DEG C, obtains complex；
(3) complex, acrylamide, cellulose are uniformly dispersed to form suspension in organic solvent, are stirred at room temperature
It mixes and 0.5~2h of self-assembling reaction occurs, then spray drying forms function microcapsules monomer；
(4) improved silica, ethylene glycol dimethacrylate and function microcapsules monomer are surpassed in organic solvent
Sound is uniformly dispersed, and obtains preceding pre-polymer solution；Then, initiator is added under inert gas protection, polymerize at 60~85 DEG C
React 1~5h；
(5) it is filtered after the product of step (4) being impregnated 30~60min in an acidic solution, filtered solid is washed
To neutrality, then wash products are dried in vacuo, are improved the modification imprinting polymer of adsorption capacity.
The present invention does not have special requirement to the type of metal ion, and the present invention can select metal for the type of sewage
The type of ion, such as the metal ion can be common heavy metal ion in sewage, be specifically as follows copper, chromium, manganese,
At least one of mercury, cadmium, lead, arsenic, zinc, tin, nickel, cobalt, antimony and bismuth.
According to the present invention, in step (1), the preparation method of the improved silica the following steps are included:
(1.1) by esters of silicon acis in alkaline solution 5~10h of precipitation, be washed out to neutrality, obtain partial size be 200~
The Nano particles of silicon dioxide of 500nm；
(1.2) Nano particles of silicon dioxide is uniformly mixed in organic solvent with silane coupling agent, at 60~90 DEG C
1~3h is stirred, improved silica is obtained, by being modified to silica, can be introduced on the surface of silica double
Key improves its stability to make that chemical bond can be generated between imprint molecule and silica.
According to the present invention, in step (1.2), the silane coupling agent is selected from aminopropyl triethoxysilane, aminopropyl
Trimethoxy silane, 2- aminoethyl amino propyl trimethoxy silane, divinyl triammonium base propyl trimethoxy silicane, aminoethyl ammonia
Hydroxypropyl methyl dimethoxysilane, aminoethylaminopropyl triethoxysilane, ureidopropyltriethoxysilane and ureido-propyl
At least one of trimethoxy silane.
Chitosan is unique alkaline polysaccharide polymer existing for nature, itself is nontoxic, and biodegradability is good, is used
Secondary pollution is not generated afterwards, so having unique advantage in the treatment of waste water.Preparing adsorbent as matrix using chitosan has original
The advantages that material is abundant, adsorptive selectivity is high, biodegradable, nontoxic and biocompatibility is good, the heavy metal in each field are useless
It has broad application prospects in terms of water process.In order to further increase chitosan to the adsorption capacity of metal ion, it is preferred that
The present invention is modified chitosan, introduces a large amount of functional group on the surface of chitosan, is capable of providing more imprinted sites,
It is coordinated with a large amount of metal ion, improves its mating capability to metal ion.
According to the present invention, in step (2), the proportion of each substance be influence chitin modified performance an important factor for, it is excellent
Select, the beta-cyclodextrin, the molar ratio of citric acid and sodium hypophosphite is 1:(3~5): (1~2).
It is further preferred that the mass ratio of the complex, acrylamide and cellulose is 1:(0.8~1.2): (3~
12)。
The present invention can be such that metal ion is uniformly dispersed in polymer using microcapsule structure, avoid the occurrence of reunion,
Improve the uniformity of imprinted sites.In step (3), cellulose can make each substance it is uniform and stable be distributed in mixed system
In, the present invention does not have special requirement to the type of cellulose, as long as stable environment, example can be provided for mixed system
If the cellulose can be carboxymethyl cellulose, methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, ethyl
At least one of cellulose.
According to the present invention, in step (4), the proportion of each substance is an important factor for influencing microsphere performance, preferably
, the quality of the improved silica, ethylene glycol dimethacrylate and function microcapsules monomer is 1:(0.5~1.8):
(2~5).
In the present invention, organic solvent is not only reaction medium in the reaction, in the preparation process of microsphere, You Jirong
Agent also acts as the effect of pore-foaming agent, it is preferred that the organic solvent in acetonitrile, toluene, acetone and ethylene glycol at least one
Kind.
, according to the invention it is preferred to, the initiator is azodiisobutyronitrile.
The present invention also provides a kind of modification imprinting polymer for improving adsorption capacity, according to above-mentioned preparation method
It is prepared.
The present invention will be described in detail by way of examples below.
Embodiment 1
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 12 sodium hydroxide solution in precipitation 8h, mistake
Filter, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 300nm；
(1.2) by 50g Nano particles of silicon dioxide and 3.6g divinyl triammonium base propyl trimethoxy silicane in 100mL second
It is uniformly mixed in nitrile, stirs 2h at 80 DEG C, obtain improved silica.
(2) be in molar ratio by 11.35g beta-cyclodextrin, 8.4g citric acid and 2.52g sodium hypophosphite 1:4:1.5 ratio
Example in aqueous solution after mixing, in 120 DEG C of reaction 4h, by reaction product and 4.5g 1- (3- dimethylamino-propyl) -3- second
After base carbodiimide hydrochloride, 13.6g n-hydroxysuccinimide stir 30min in aqueous solution, 50g chitosan is added and exists
Then copper chloride, chromium chloride, manganese chloride, mercury chloride, caddy, lead chloride, chromium chloride, chlorination is added in precipitation 30min at 70 DEG C
Arsenic, zinc chloride, stannic chloride, nickel chloride, cobalt chloride, antimony chloride, bismuth chloride stir 2h at 85 DEG C under nitrogen protection, will produce
After object filtering, filtered solid is washed with water three times, after vacuum drying, complex is obtained；
(3) 50g complex, 50g acrylamide, 400g hydroxyethyl cellulose are uniformly dispersed in 300mL toluene and are formed
Suspension is stirred at room temperature and self-assembling reaction 1h occurs, and then spray drying forms function microcapsules monomer；
(4) 20g improved silica, 24g ethylene glycol dimethacrylate and 60g function microcapsules monomer are existed
Ultrasonic disperse is uniform in toluene in 120mL acetonitrile, obtains preceding pre-polymer solution；Then, it is different that azo two is added under nitrogen protection
Butyronitrile, the polymerization reaction 2h at 75 DEG C；
(5) it is filtered after the product of step (4) being impregnated 45min in the hydrochloric acid solution that pH is 3.2, by filtered solid
Then wash products are dried in vacuo to neutrality, are improved the modification imprinting polymer of adsorption capacity by washing.
Simulated experiment:
Experimental method: taking four small flasks, respectively with solution shown in sample 1-4 in tabulation 1, is then respectively adding
The modification imprinting polymer of the raising adsorption capacity of 0.05g the present embodiment, four small beakers are shaken 1 hour respectively
Afterwards, supernatant is taken to be centrifuged 30min respectively, then the concentration for taking the supernatant after centrifugation to survey its absorbance and lead ion respectively, from
And the modification imprinting polymer for calculating raising adsorption capacity imitates the absorption of the metallic ion mixed liquor of various concentration
Rate.
Table 1:
Embodiment 2
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 13 sodium hydroxide solution in middle precipitation 6h,
Filtering, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 250nm；
(1.2) 50g Nano particles of silicon dioxide is mixed in 100mL acetone with 5g ureidopropyltriethoxysilane
It is even, 1.5h is stirred at 70 DEG C, obtains improved silica.
(2) by 11.35g beta-cyclodextrin, 44.1g citric acid and 2g sodium hypophosphite in 100mL water after mixing,
120 DEG C of reaction 4.5h, by reaction product and 3g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 10g N- hydroxyl
After base succinimide stirs 45min in aqueous solution, 50g chitosan precipitation 45min at 75 DEG C is added, chlorination is then added
Chromium, copper chloride and lead chloride stir 3h at 80 DEG C under nitrogen protection, after product is filtered, by filtered solid water
Washing three times, after vacuum drying, obtains complex；
(3) 50g complex, 50g acrylamide, 100g carboxymethyl cellulose are uniformly dispersed in 300mL toluene and are formed
Suspension is stirred at room temperature and self-assembling reaction 1.5h occurs, and then spray drying forms function microcapsules monomer；
(4) 20g improved silica, 30g ethylene glycol dimethacrylate and 80g function microcapsules monomer are existed
Ultrasonic disperse is uniform in ethylene glycol in 100mL acetonitrile, obtains preceding pre-polymer solution；Then, azo two is added under nitrogen protection
Isobutyronitrile, the polymerization reaction 3h at 70 DEG C；
(5) it is filtered after the product of step (4) being impregnated 45min in the hydrochloric acid solution that pH is 4.0, by filtered solid
Then wash products are dried in vacuo to neutrality, are improved the modification imprinting polymer of adsorption capacity by washing.
According to 1 method of embodiment, the adsorption capacity of the present embodiment product is tested, experimental result is as shown in table 2.
Table 2
Embodiment 3
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 12.6 sodium hydroxide solution in middle precipitation
9h, filtering, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 300nm；
(1.2) by 50g Nano particles of silicon dioxide and 8g aminoethylaminopropyl methyl dimethoxysilane in 100mL acetonitrile
In be uniformly mixed, stir 2h at 75 DEG C, obtain improved silica.
(2) by 11.35g beta-cyclodextrin, 9.45g citric acid and 3g sodium hypophosphite in 100mL water after mixing,
120 DEG C of reaction 3.5h, by reaction product and 2g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 12g N- hydroxyl
After base succinimide stirs 45min in aqueous solution, 50g chitosan precipitation 30min at 80 DEG C is added, chlorination is then added
Nickel, chromium chloride, cobalt chloride stir 1.5h at 90 DEG C under nitrogen protection, and after product is filtered, filtered solid is used
Water washing three times, after vacuum drying, obtain complex；
50g complex, 40g acrylamide, 250g hydroxypropyl methyl cellulose are uniformly dispersed in 300mL acetonitrile and to be formed
Suspension is stirred at room temperature and self-assembling reaction 1h occurs, and then spray drying forms function microcapsules monomer；
By 20g improved silica, 20g ethylene glycol dimethacrylate and 60g function microcapsules monomer in 150mL second
Ultrasonic disperse is uniform in toluene in nitrile, obtains preceding pre-polymer solution；Then, azodiisobutyronitrile is added under nitrogen protection,
Polymerization reaction 2h at 80 DEG C；
It is filtered after the product of step (4) is impregnated 45min in the hydrochloric acid solution that pH is 5.6, filtered solid is washed
It washs to neutrality, is then dried in vacuo wash products, be improved the modification imprinting polymer of adsorption capacity.
According to 1 method of embodiment, the adsorption capacity of the present embodiment product is tested, experimental result is as shown in table 3.
Table 3
Embodiment 4
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 13.5 sodium hydroxide solution in middle precipitation
5h, filtering, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 200nm；
(1.2) 50g Nano particles of silicon dioxide is mixed in 100mL acetone with 3g aminopropyl triethoxysilane
It is even, 3h is stirred at 60 DEG C, obtains improved silica.
(2) by 11.35g beta-cyclodextrin, 6.3g citric acid and 3.36g sodium hypophosphite in 100mL water after mixing,
In 120 DEG C of reaction 5h, by reaction product and 2.5g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 11.8g
After n-hydroxysuccinimide stirs 30min in aqueous solution, 50g chitosan precipitation 45min at 60 DEG C is added, is then added
Copper chloride, caddy, arsenic chloride stir 5h at 75 DEG C under nitrogen protection, after product is filtered, by filtered solid
It is washed with water three times, after vacuum drying, obtains complex；
(3) 50g complex, 60g acrylamide, 600g hydroxyethyl cellulose are uniformly dispersed shape in 300mL ethylene glycol
It at suspension, is stirred at room temperature and self-assembling reaction 2h occurs, then spray drying forms function microcapsules monomer；
(4) 20g improved silica, 10g ethylene glycol dimethacrylate and 40g function microcapsules monomer are existed
Ultrasonic disperse is uniform in ethylene glycol in 150mL acetonitrile, obtains preceding pre-polymer solution；Then, azo two is added under nitrogen protection
Isobutyronitrile, the polymerization reaction 5h at 60 DEG C；
(5) it is filtered after the product of step (4) being impregnated 60min in the hydrochloric acid solution that pH is 3.9, by filtered solid
Then wash products are dried in vacuo to neutrality, are improved the modification imprinting polymer of adsorption capacity by washing.
According to 1 method of embodiment, the adsorption capacity of the present embodiment product is tested, experimental result is as shown in table 4.
Table 4
Embodiment 5
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 13.8 sodium hydroxide solution in middle precipitation
10h, filtering, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 500nm；
(1.2) 50g Nano particles of silicon dioxide is mixed in 100mL acetone with 5g aminopropyl trimethoxysilane
It is even, 1h is stirred at 90 DEG C, obtains improved silica.
(2) 11.35g beta-cyclodextrin, 10.5g citric acid and 1.68g sodium hypophosphite are uniformly mixed in 100mL water
Afterwards, in 120 DEG C of reaction 3h, by reaction product and 12.6g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, N-
After HOSu NHS stirs 30~45min in aqueous solution, be added 50g chitosan precipitation 30min at 75 DEG C, then plus
Enter zinc chloride, antimony chloride, bismuth chloride, under nitrogen protection, stirs 1h at 100 DEG C, it, will be filtered solid after product is filtered
Body is washed with water three times, after vacuum drying, obtains complex；
(3) 50g complex, 40g acrylamide, 150g methylcellulose are uniformly dispersed in acetonitrile in 300mL and are formed
Suspension is stirred at room temperature and self-assembling reaction 0.5h occurs, and then spray drying forms function microcapsules monomer；
(4) 20g improved silica, 36g ethylene glycol dimethacrylate and 100g function microcapsules monomer are existed
Ultrasonic disperse is uniform in 150mL acetonitrile, obtains preceding pre-polymer solution；Then, azodiisobutyronitrile is added under nitrogen protection,
Polymerization reaction 1h at 85 DEG C；
(5) it is filtered after the product of step (4) being impregnated 30min in the hydrochloric acid solution that pH is 4.8, by filtered solid
Then wash products are dried in vacuo to neutrality, are improved the modification imprinting polymer of adsorption capacity by washing.
According to 1 method of embodiment, the adsorption capacity of the present embodiment product is tested, experimental result is as shown in table 5.
Table 5
Comparative example 1
According to the method for embodiment 5, the difference is that, it does not include the preparation of function microcapsules monomer during the preparation process, tool
Body is as follows:
A kind of preparation method for the modification imprinting polymer improving adsorption capacity, steps are as follows:
(1.1) preparation of improved silica: by 100g esters of silicon acis pH be 13.8 sodium hydroxide solution in middle precipitation
10h, filtering, solid particle is washed to neutrality, obtains the Nano particles of silicon dioxide that partial size is 500nm；
(1.2) 50g Nano particles of silicon dioxide is mixed in 100mL acetone with 5g aminopropyl trimethoxysilane
It is even, 1h is stirred at 90 DEG C, obtains improved silica.
(2) 11.35g beta-cyclodextrin, 10.5g citric acid and 1.68g sodium hypophosphite are uniformly mixed in 100mL water
Afterwards, in 120 DEG C of reaction 3h, by reaction product and 12.6g 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, N-
After HOSu NHS stirs 30~45min in aqueous solution, be added 50g chitosan precipitation 30min at 75 DEG C, then plus
Enter zinc chloride, antimony chloride, bismuth chloride, under nitrogen protection, stirs 1h at 100 DEG C, it, will be filtered solid after product is filtered
Body is washed with water three times, after vacuum drying, obtains complex；
(3) 50g complex, 40g acrylamide are stirred in acetonitrile in 300mL and self-assembling reaction 0.5h occurs, then
20g improved silica, 36g ethylene glycol dimethacrylate and 100g function microcapsules monomer are added into mixed system to exist
Ultrasonic disperse is uniform in 150mL acetonitrile, obtains preceding pre-polymer solution；Then, azodiisobutyronitrile is added under nitrogen protection,
Polymerization reaction 1h at 85 DEG C；
(5) it is filtered after the product of step (4) being impregnated 30min in the hydrochloric acid solution that pH is 4.8, by filtered solid
Then wash products are dried in vacuo to neutrality, are improved the modification imprinting polymer of adsorption capacity by washing.
According to 1 method of embodiment, the adsorption capacity of the present embodiment product is tested, experimental result is as shown in table 6.
Table 6
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction.In order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. the preparation method of property imprinting polymer, which comprises the following steps:
(1) preparation method of improved silica, comprising the following steps:
(1.1) by esters of silicon acis in alkaline solution 5~10h of precipitation, be washed out to neutrality, obtaining partial size is 200~500nm
Nano particles of silicon dioxide；
(1.2) Nano particles of silicon dioxide is uniformly mixed in organic solvent with silane coupling agent, stirs 1 at 60~90 DEG C
~3h, obtains improved silica, and the silane coupling agent is selected from aminopropyl triethoxysilane, aminopropyl trimethoxy silicon
Alkane, 2- aminoethyl amino propyl trimethoxy silane, divinyl triammonium base propyl trimethoxy silicane, aminoethylaminopropyl methyl two
Methoxy silane, aminoethylaminopropyl triethoxysilane, ureidopropyltriethoxysilane and ureido-propyl trimethoxy silicon
At least one of alkane；
(2) by beta-cyclodextrin, citric acid and sodium hypophosphite under aqueous conditions after mixing, will in 120 DEG C of reaction 3-5h
Reaction product and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide are in aqueous solution
After stirring 30~45min, chitosan 30~45min of precipitation at 60~80 DEG C is added, the source M is then added, is protected in inert gas
Under shield, 1~5h is stirred at 75~100 DEG C, obtains complex, the beta-cyclodextrin, mole of citric acid and sodium hypophosphite
Than for 1:(3~5): (1~2)；
(3) it is uniformly dispersed complex, acrylamide, cellulose to form suspension in organic solvent, hair is stirred at room temperature
Raw 0.5~2h of self-assembling reaction, then spray drying forms function microcapsules monomer；
(4) by improved silica, ethylene glycol dimethacrylate and function microcapsules monomer, ultrasound is divided in organic solvent
It dissipates uniformly, obtains preceding pre-polymer solution；Then, initiator is added under inert gas protection, the polymerization reaction 1 at 60~85 DEG C
~5h；
(5) it is filtered after the product of step (4) being impregnated 30~60min in an acidic solution, filtered solid is washed into
Property, then wash products are dried in vacuo, are improved the modification imprinting polymer of adsorption capacity；
The M is at least one of copper, chromium, manganese, mercury, cadmium, lead, arsenic, zinc, tin, nickel, cobalt, antimony and bismuth.
2. the preparation method of modified imprinting polymer according to claim 1, which is characterized in that in step (3)
In, the mass ratio of the complex, acrylamide and cellulose is 1:(0.8~1.2): (3~12).
3. the preparation method of modified imprinting polymer according to claim 2, which is characterized in that in step (3)
In, it is fine that the cellulose is selected from carboxymethyl cellulose, methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, ethyl
Tie up at least one of element.
4. the preparation method of modified imprinting polymer according to claim 1, which is characterized in that in step (4)
In, the quality of the improved silica, ethylene glycol dimethacrylate and function microcapsules monomer is 1:(0.5~1.8):
(2~5).
5. the preparation method of modification imprinting polymer described in any one, feature exist according to claim 1~4
In the organic solvent is selected from least one of acetonitrile, toluene, acetone and ethylene glycol；And/or
The initiator is azodiisobutyronitrile.
6. modified imprinting polymer, which is characterized in that preparation side described according to claim 1~any one of 5
Method is prepared.
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| CN111689589A (en) * | 2020-05-28 | 2020-09-22 | 南京奥伯尔环保设备有限公司 | Sewage treatment agent |
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