CN106362703B - Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application - Google Patents
Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic material fields, and in particular to a kind of modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application.The technical problem to be solved by the present invention is to existing chitosan class is inadequate to heavy metal ion adsorbed amount, and adsorption rate is slower, is not easy to elute, application range is narrow.The scheme that invention solves above-mentioned technical problem is to provide a kind of modified carragheen-chitosan polyelectrolyte microsphere.The present invention also provides the preparation methods and purposes of above-mentioned modified carragheen-chitosan polyelectrolyte microsphere.Modified carragheen-chitosan polyelectrolyte microsphere provided by the invention is adsorbance bigger, the heavy metal chelating agent of small toxicity.
Description
Technical field
The invention belongs to organic material fields, and in particular to a kind of modified carragheen-chitosan polyelectrolyte microsphere and its
Preparation method and purposes.
Background technology
In the discharge process of industrial wastewater, there is considerable degree of heavy metal element to be deposited in water body.In the environment,
Hg, Cd, Pb, Cr etc. have toxicity to human body, and Zn, Cu, Ni, Sn etc. have notable toxic effect to the ecosystem.Heavy metal
With various chemical forms, there are waste water to be discharged into environment, even if accumulation can be retained in algae and bed mud if concentration very little, by fish and
The body surface of shellfish is enriched with, and food chain concentration is generated, to cause public hazards.It is different from the pollution of other organic compounds, it is heavy metal-polluted
Dye cannot make harmfulness reduce or release, pollution has latent by nature physics itself, chemical or biological purification
It is one of key points and difficulties problem of global environmental protection in property and hysteresis quality.The processing method of heavy metal wastewater thereby mainly has object
Logos, chemical method, biological treatment.Method of chemical treatment is all made of on 90%：Neutralize coagulating sedimentation, sulphide precipitation, iron
Oxysome method, chelate precipitation, ion floatation method, electrolysis, activated carbon adsorption hair, ion-exchange-resin process etc..
Applying for chitosan all achieves great progress in numerous areas.Its amido of chitosan easily forms level Four
Amine cation has weakly-basic anion exchange interaction, and due to the presence of free amine group, chitosan class has sun in an acidic solution
Ionic gathers dielectric property, can be used as flocculating agent, but can dissolve in an acidic solution, stability is poor.It is difficult to form particle
Structure influences the balancing speed of mass transport process.It is restricted as resin application in fixed bed.Currently, chitosan resin
The preparation method of ball can be divided into chemical crosslink technique, ionic cross-linking, complex coacervation, spray drying process and emulsion process etc..It is curing
The fields such as medicine, food, agricultural, environmental protection, daily use chemicals are widely applied.Polymer microsphere is since it is with polymolecularity and big ratio
The characteristics of surface is a kind of carrier material haveing excellent performance, drug controlled release, bioengineering, wastewater treatment etc.
It is widely studied, has broad application prospects.Chitosan material is prepared into polymer microsphere, keeps chitosan and macromolecule micro-
The excellent properties combination of ball and the at present research field of domestic and international more hot spot chitosan class in terms of environmental protection have free
Amino exist, in an acidic solution have the dielectric property of cationic poly, can be used as flocculating agent and water clarified, separately
Outer chitosan counterweight trapping metal ion, is used for sewage disposal and noble metal recycling, and chitosan class can be used for radioactivity
The processing of the trapping and nuclear industry sewage of element uranium.But chitosan microball itself is tied the adsorption capacity of heavy metal ion by it
The influence of structure characteristic and surface chemistry, activated adoption center is less, adsorbance, and adsorption rate is all relatively low.
Invention content
The technical problem to be solved by the present invention is to existing chitosan class is inadequate to heavy metal ion adsorbed amount, and adsorb
Speed is slower, is not easy to elute, application range is narrow.
The scheme that invention solves above-mentioned technical problem is to provide a kind of modified carragheen-chitosan polyelectrolyte microsphere.
Above-mentioned modified carragheen-chitosan polyelectrolyte microsphere, be mixed to form with carragheen by chitosan it is insoluble
Compound polyelectrolyte and be made.
Wherein, the mass ratio of the chitosan and carragheen is 1 ︰, 9~9 ︰ 1.Preferably, the chitosan and carragheen
Mass ratio is 4 ︰ 6.
The grain size of above-mentioned modified carragheen-chitosan polyelectrolyte microsphere is 990 μm~1010 μm.
The present invention also provides the preparation methods of above-mentioned modified carragheen-chitosan polyelectrolyte microsphere, including following step
Suddenly：
1) dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere：It is molten that carragheen and chitosan are dissolved in acid respectively
In liquid；Then the acid solution of chitosan at 50~80 DEG C is kept the temperature to 1.5~4h, the acid solution of carragheen is kept the temperature at 35~45 DEG C
The two is then uniformly mixed by 30~60min, obtains mixed liquor；Above-mentioned mixed liquor is instilled in aqueous slkali again, obtains chitosan
Microballoon；Chitosan microball is rinsed with deionized water again, until the pH=7 of flushing water, it is micro- to obtain kappa-carrageenan-chitosan polyelectrolyte
Ball；
2) be added deionized water in above-mentioned kappa-carrageenan-chitosan polyelectrolyte microsphere, then with ethylene glycol glycidol
Ether reacts 54~6h at 35~55 DEG C, then uses washes of absolute alcohol, then cleaned with deionized water, filters, dries, be crosslinked
Kappa-carrageenan-chitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere is added in tetrahydrofuran and triethylamine, in 0~
It 6 DEG C, is passed through nitrogen and drains air, be then slowly added into bromo isobutyl acylbromide, and continue to react 1~3h at 0~6 DEG C, then be transferred to
It is reacted 12~24 hours under room temperature；It filters after reaction, washes of absolute alcohol is first used, then cleaned with deionized water, through drying
Obtain kappa-carrageenan-chitosan polyelectrolyte microsphere of fixed initiator；
4) in kappa-carrageenan-chitosan polyelectrolyte microsphere of above-mentioned fixed initiator, ionized water, methanol and first is added
Base glycidyl acrylate is passed through nitrogen, then sequentially adds CuBr, CuBr2And 2,2'- bipyridyls then proceed to logical nitrogen
Gas drains air, then at 35~45 DEG C of 3.5~6h of reaction, is then cleaned with deionized water, is dry；Add polyethyleneimine and
Deionized water reacts 3~6h at 45~65 DEG C, then uses washes of absolute alcohol, then cleaned with deionized water, dry, is drawn
Enter kappa-carrageenan-chitosan polyelectrolyte microsphere of amido；
5) at room temperature, in the above-mentioned kappa-carrageenan for being introduced into amido-chitosan polyelectrolyte microsphere be added methanol and go from
40% sodium hydroxide solution is slowly added dropwise in sub- water, reacts 2~4h and then the mixed solution of carbon disulfide and ethyl alcohol is added dropwise, instead
Answer 20min；Then heat to 45~60 DEG C, reaction 16~for 24 hours, in being cleaned with deionized water and alcohol mixeding liquid and being in liquid
Property, it is dry, obtain modified carragheen-chitosan polyelectrolyte microsphere.
The preparation method of above-mentioned modified carragheen-chitosan polyelectrolyte microsphere, the acid solution described in step 1) are ice vinegar
The aqueous solution of any one in acid, ethanedioic acid, lactic acid, succinic acid, malic acid, oxalic acid or dilute hydrochloric acid；The quality of the acid solution
A concentration of 1%~5%；The acid solution is 0.1 ︰, 1 ︰, 9~0.4 ︰, 9 ︰ 1 with the molar ratio of carragheen or chitosan.
Above-mentioned preparation method, the step 1) aqueous slkali are the deionized water solution of sodium hydroxide or potassium hydroxide；It is described
The molar ratio of sodium hydroxide or potassium hydroxide and deionized water is 1 ︰ 1.
Above-mentioned preparation method, the addition of the step 2) deionized water are to keep kappa-carrageenan-chitosan polyelectrolyte micro-
The mass concentration of ball is 3%~9%；The quality of the ethylene glycol contracting glycerin ether and kappa-carrageenan-chitosan polyelectrolyte microsphere
Than for 9 ︰, 50~7 ︰ 20.
The step of above-mentioned preparation method, the step 2) drying is：Crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere exists
In rotary vacuum evaporator drying, in 40~55 DEG C of dry 5~10h, the then vacuum in vacuum drying chamber 35~45 DEG C
Dry 10-36h.
Above-mentioned preparation method, the step 3) THF (tetrahydrofuran) are used with triethylamine as solvent.The THF and three
The molar ratio of ethamine is 4 ︰, 3~2 ︰ 1；The matter of the bromo isobutyl acylbromide and crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere
Amount is than being 9 ︰, 20~3 ︰ 5.
Above-mentioned preparation method, the step 4) ionized water, glycidyl methacrylate, fix initiator at methanol
The molar ratio of kappa-carrageenan-chitosan polyelectrolyte microsphere is 5 ︰, 1 ︰, 0.4 ︰, 2~8 ︰, 3 ︰, 0.4 ︰ 2；The κ-of the fixed initiator
Carragheen-chitosan polyelectrolyte microsphere, BPY (2,2'- bipyridyls), CuBr, CuBr2Molar ratio be 100 ︰, 2 ︰, 1 ︰ 0.2~
400 ︰, 3 ︰, 1 ︰ 0.2；The kappa-carrageenan of the fixed initiator-chitosan polyelectrolyte microsphere, polyethyleneimine, deionized water
Molar ratio is 1 ︰, 0.4 ︰, 1~2 ︰, 1 ︰ 1.
Above-mentioned preparation method, step 2) and it is 4) described cleaned with deionized water, refer to cleaning to deionized water be neutrality.
Above-mentioned preparation method, the step 5) kappa-carrageenan-chitosan polyelectrolyte microsphere for introducing amido, are gone methanol
The molar ratio of ionized water is 2 ︰, 0.3 ︰, 1~4 ︰, 0.1 ︰ 1；Kappa-carrageenan-chitosan the polyelectrolyte microsphere for introducing amido, two
Nitric sulfid, ethyl alcohol mass ratio be 2 ︰, 4 ︰, 1~3 ︰, 2 ︰ 0.5；In the mixed liquor of the deionized water and ethyl alcohol, deionized water and second
The volume ratio of alcohol is 1 ︰, 100~1 ︰ 1.
The present invention also provides above-mentioned modified carragheen-chitosan polyelectrolyte microspheres to recycle in sewage disposal and noble metal
In purposes.
The beneficial effects of the present invention are：1, it is basic material with chitosan and carragheen, prepares kappa-carrageenan-chitosan
Polyelectrolyte microsphere.It is modified DTC obtained by a series of surfaces and is modified kappa-carrageenan-chitosan polyelectrolyte microsphere, it can be with
As a kind of new adsorbent, mechanicalness and acid resistance are stronger, and usage range is wider, adsorbance bigger, adsorption rate faster, more
Easily elution.2, the present invention uses chitosan and carragheen for basic material, good environment intermiscibility, recyclability, resource
The advantages that abundant and cheap and easy to get.The advantages of combining both chitosan and carragheen improves mechanical strength, exists simultaneously
Hydroxyl, amino and other groups, can borrow hydrogen bond also borrow it is saline and alkaline formed with reticular structure cage molecule, can to heavy metal from
Son (Cr2+、U6+、Te3+、Co3+、Se6+、Pu3+、Hg2+,Mn4+) chelated, therefore can effectively in adsorbent solution important gold
Belong to ion, it also can a series of grafting activities of strengthening subsequent.3, the present invention uses Transfer Radical Polymerization (ATRP), in κ-
Carragheen-chitosan polyelectrolyte microsphere surface grafting polymerization brush, obtained polymerization brush density bigger.It is introduced in amino group
DTC groups afterwards introduce, and modified kappa-carrageenan-chitosan polyelectrolyte microsphere adsorbance bigger, the heavy metal of small toxicity is made to catch
Collect agent.
Specific implementation mode
The preparation method of modified carragheen-chitosan polyelectrolyte microsphere, includes the following steps：
1) dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere：It is molten that carragheen and chitosan are dissolved in acid respectively
In liquid；Then the acid solution of chitosan at 50~80 DEG C is kept the temperature to 1.5~4h, the acid solution of carragheen is kept the temperature at 35~45 DEG C
The two is then uniformly mixed by 30~60min, obtains mixed liquor；Above-mentioned mixed liquor is instilled in aqueous slkali again, obtains chitosan
Microballoon；Chitosan microball is rinsed with deionized water again, until the pH=7 of flushing water, it is micro- to obtain kappa-carrageenan-chitosan polyelectrolyte
Ball；
2) be added deionized water in above-mentioned kappa-carrageenan-chitosan polyelectrolyte microsphere, then with ethylene glycol glycidol
Ether reacts 54~6h at 35~55 DEG C, then uses washes of absolute alcohol, then cleaned with deionized water, filters, dries, be crosslinked
Kappa-carrageenan-chitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere is added in tetrahydrofuran and triethylamine, in 0~
It 6 DEG C, is passed through nitrogen and drains air, be then slowly added into bromo isobutyl acylbromide, and continue to react 1~3h at 0~6 DEG C, then be transferred to
It is reacted 12~24 hours under room temperature；It filters after reaction, washes of absolute alcohol is first used, then cleaned with deionized water, through drying
Obtain kappa-carrageenan-chitosan polyelectrolyte microsphere of fixed initiator；
4) in kappa-carrageenan-chitosan polyelectrolyte microsphere of above-mentioned fixed initiator, ionized water, methanol and first is added
Base glycidyl acrylate is passed through nitrogen, then sequentially adds CuBr, CuBr2And 2,2'- bipyridyls then proceed to logical nitrogen
Gas drains air, then at 35~45 DEG C of 3.5~6h of reaction, is then cleaned with deionized water, is dry；Add polyethyleneimine and
Deionized water reacts 3~6h at 45~65 DEG C, then uses washes of absolute alcohol, then cleaned with deionized water, dry, is drawn
Enter kappa-carrageenan-chitosan polyelectrolyte microsphere of amido；
5) at room temperature, in the above-mentioned kappa-carrageenan for being introduced into amido-chitosan polyelectrolyte microsphere be added methanol and go from
40% sodium hydroxide solution is slowly added dropwise in sub- water, reacts 2~4h and then the mixed solution of carbon disulfide and ethyl alcohol is added dropwise, instead
Answer 20min；Then heat to 45~60 DEG C, reaction 16~for 24 hours, in being cleaned with deionized water and alcohol mixeding liquid and being in liquid
Property, it is dry, obtain modified carragheen-chitosan polyelectrolyte microsphere.
The preparation method of above-mentioned modified carragheen-chitosan polyelectrolyte microsphere, the acid solution described in step 1) are ice vinegar
The aqueous solution of any one in acid, ethanedioic acid, lactic acid, succinic acid, malic acid, oxalic acid or dilute hydrochloric acid；The quality of the acid solution
A concentration of 1%~5%；The acid solution is 0.1 ︰, 1 ︰, 9~0.4 ︰, 9 ︰ 1 with the molar ratio of carragheen or chitosan.
Above-mentioned preparation method, the step 1) aqueous slkali are the deionized water solution of sodium hydroxide or potassium hydroxide；It is described
The molar ratio of sodium hydroxide or potassium hydroxide and deionized water is 1 ︰ 1.
Above-mentioned preparation method, the addition of the step 2) deionized water are to keep kappa-carrageenan-chitosan polyelectrolyte micro-
The mass concentration of ball is 3%~9%；The quality of the ethylene glycol contracting glycerin ether and kappa-carrageenan-chitosan polyelectrolyte microsphere
Than for 9 ︰, 50~7 ︰ 20.
The step of above-mentioned preparation method, the step 2) drying is：Crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere exists
In rotary vacuum evaporator drying, in 40~55 DEG C of dry 5~10h, the then vacuum in vacuum drying chamber 35~45 DEG C
Dry 10-36h.
Above-mentioned preparation method, the step 3) THF (tetrahydrofuran) are used with triethylamine as solvent.The THF and three
The molar ratio of ethamine is 4 ︰, 3~2 ︰ 1；The matter of the bromo isobutyl acylbromide and crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere
Amount is than being 9 ︰, 20~3 ︰ 5.
Above-mentioned preparation method, the step 4) ionized water, glycidyl methacrylate, fix initiator at methanol
The molar ratio of kappa-carrageenan-chitosan polyelectrolyte microsphere is 5 ︰, 1 ︰, 0.4 ︰, 2~8 ︰, 3 ︰, 0.4 ︰ 2；The κ-of the fixed initiator
Carragheen-chitosan polyelectrolyte microsphere, BPY (2,2'- bipyridyls), CuBr, CuBr2Molar ratio be 100 ︰, 2 ︰, 1 ︰ 0.2~
400 ︰, 3 ︰, 1 ︰ 0.2；The kappa-carrageenan of the fixed initiator-chitosan polyelectrolyte microsphere, polyethyleneimine, deionized water
Molar ratio is 1 ︰, 0.4 ︰, 1~2 ︰, 1 ︰ 1.
Above-mentioned preparation method, step 2) and it is 4) described cleaned with deionized water, refer to cleaning to deionized water be neutrality.
Above-mentioned preparation method, the step 5) kappa-carrageenan-chitosan polyelectrolyte microsphere for introducing amido, are gone methanol
The molar ratio of ionized water is 2 ︰, 0.3 ︰, 1~4 ︰, 0.1 ︰ 1；Kappa-carrageenan-chitosan the polyelectrolyte microsphere for introducing amido, two
Nitric sulfid, ethyl alcohol mass ratio be 2 ︰, 4 ︰, 1~3 ︰, 2 ︰ 0.5；In the mixed liquor of the deionized water and ethyl alcohol, deionized water and second
The volume ratio of alcohol is 1 ︰, 100~1 ︰ 1.
Embodiment 1 is modified preparation (mass ratio=1/ of chitosan and carragheen of carragheen-chitosan polyelectrolyte microsphere
9)
1, dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere, and 0.9g carragheens and 0.1g chitosans are distinguished
It is dissolved in the glacial acetic acid of 1g/L, is made it dissolve with glass bar uniform stirring chitosan solution, seal beaker mouth with preservative film, then
Chitosan solution is transferred in 70 DEG C of water-bath and carries out constant temperature 2 hours, carrageenan solutions are transferred in 45 DEG C of water-baths and are carried out
Constant temperature 30min, then mixes the two full and uniform, obtains mixed liquor.40g sodium hydroxides are weighed, the beaker of 1000ml is dissolved in
In, it is configured to the sodium hydroxide solution of 1mol/L, drawing above-mentioned mixed solution with syringe instills in sodium hydroxide solution, mixing
Solution moment when entering sodium hydroxide solution is frozen into the substance of opaque white color by orange solution, and gradually sinks to beaker
Bottom.By adjusting the dynamics of syringe injection and titration direction during ball processed, enable the mixed solution of instillation in hydrogen
Sodium oxide molybdena glomeration.Then the white chitosan microball that titration is formed is rinsed with deionized water to pH=7, is transferred to 200mL's
In flask, in case carrying out cross-linking reaction.
2, kappa-carrageenan-chitosan polyelectrolyte microsphere is fitted into 200mL flasks, adds 100mL deionized waters, with shifting
Liquid device is drawn 1mL glycol glycidyl ethers (EDGE) and is added in flask, as in 45 DEG C of water-baths, then carries out rotating speed
The magnetic agitation of 20rpm, reaction continues 5 hours, is then first cleaned with 95% ethyl alcohol, then clear with deionized water again
It washes, obtains crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere with filtered on buchner funnel, diameter is at 970 μm~985 μm.
3, the kappa-carrageenan after cross-linking reaction-chitosan polyelectrolyte microsphere is rinsed well, is transferred to 100mL flasks
In, it is dried 9 hours with rotary vacuum evaporator, drying temperature is 42 DEG C, and then the cross-linked chitosan just after drying is transferred to very
It is 2 days dry in empty drying box.Crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere after vacuum drying is put into the flask of 50mL
In, tetrahydrofuran (THF) 3.5mL, 0.5mL triethylamine is added and 2cm stirrers, rotating speed are adjusted to 20rpm, is put into ice-water bath,
Bottleneck is covered with preservative film, then snorkel is poked in preservative film insertion flask and is passed through nitrogen 30min.Wait for nitrogen ventilation knot
Beam is drawn 0.4ml bromo isobutyl acylbromides (BIBB) with syringe and is slowly injected into flask with rubber stopper seal flask, wink in flask
Between there is white solid, and continue to react 1 hour in ice-water bath, then be transferred under room temperature and react 24 hours, finally be filtered under diminished pressure,
It is first cleaned with 95% ethyl alcohol, then is cleaned with deionized water, be transferred to vacuum drying chamber drying.
4, kappa-carrageenan-chitosan polyelectrolyte microsphere after fixed initiator is transferred in the flask of 50mL, is added
0.25mL deionized waters, 2.5mL methanol and 1mL GMA, are put into stirrer and are sealed with preservative film, are passed through nitrogen 30min, then press
According to (monomer：BPY：CuBr：CuBr2=100:2:1:0.2) CuBr 10mg, CuBr, are weighed23.1mg, 2,2'- bipyridyls
21.9mg is sequentially added in flask, then proceedes to logical nitrogen 10 minutes.It is sealed with rubber stopper, is placed in 35 DEG C of water-bath, rotating speed
20rpm reacts 4 hours, and then cleaning is put into vacuum drying chamber.
Kappa-carrageenan-chitosan polyelectrolyte microsphere after ATRP is reacted is placed in the flask of 50ml, weighs 0.5g
Flask is added in polyethyleneimine, then addition 5mL deionized waters, and in magnetic stirring apparatus, rotating speed determines 200rpm, anti-in 50 DEG C of conditions
It answers 5 hours, is then first cleaned with 95% ethyl alcohol, then cleaned with deionized water, be transferred to vacuum drying chamber kept dry.Diameter exists
990 μm~1000 μm.
5, the kappa-carrageenan-chitosan polyelectrolyte microsphere being introduced into 4 after amido is placed in flask, 40mL first is added
Alcohol and 7mL deionized waters, stir evenly, and 40% sodium hydroxide solutions of 20ml are slowly added dropwise.After reacting 2h, curing is added dropwise
The mixed solution (carbon disulfide 8mL, ethyl alcohol 15mL) of carbon and ethyl alcohol, 2h is dripped, and reaction 20min. is warming up to 45 DEG C of reactions
16h, 50 DEG C of reaction 1h. reactions terminate, and deionized water and alcohol mixeding liquid are cleaned.Vacuum tank is dried, and modified carragheen-shell is obtained
Glycan polyelectrolyte microsphere, diameter is in 990 μm~1000 μm
6, at room temperature, it weighs (1g) and is modified carragheen-chitosan polyelectrolyte microsphere, be added to 50mL concentration excess
It in Cr (III) solution, under conditions of pH=5, is reacted 4 hours on magnetic stirring apparatus, investigates DTC and be modified kappa-carrageenan-chitosan
Polyelectrolyte microsphere is 1.2mmol/g to the saturated extent of adsorption of Cr ions.
In order to further probe into the adsorption dynamics adsorption kinetics performance of microballoon, using pseudo- First order dynamic model (PFO) and pseudo- two level
Kinetic model (PSO) is fitted adsorpting data of the CCS and CCS-g-PMAA microballoons to Cr (III) ion, to select suitable mould
Type.PFO and PSO kinetic models.ksIt is the rate constant of pseudo-second-order equation Adsorption Model (PSO), unit is g/ (mmol
min)。
The adsorption rate K of the present embodiments×10-3=0.343g/mmol-1·min-1。
Embodiment 2 is modified preparation (chitosan and carragheen mass ratio=2/ of carragheen-chitosan polyelectrolyte microsphere shell
3)
1, dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere, and 0.6g carragheens and 0.4g chitosans are distinguished
It is dissolved in the glacial acetic acid of 1g/L, is made it dissolve with glass bar uniform stirring chitosan solution, seal beaker mouth with preservative film, then
Chitosan solution is transferred in 70 DEG C of water-bath and carries out constant temperature 2 hours, carrageenan solutions are transferred in 45 DEG C of water-baths and are carried out
Constant temperature 30min.Then the two is mixed full and uniform, obtains mixed liquor.40g sodium hydroxides are weighed, the beaker of 1000mL is dissolved in
In, it is configured to the sodium hydroxide solution of 1mol/L, drawing above-mentioned mixed solution with syringe instills in sodium hydroxide solution, mixing
Solution moment when entering sodium hydroxide solution is frozen into the substance of opaque white color by orange solution, and gradually sinks to beaker
Bottom.By adjusting the dynamics of syringe injection and titration direction during ball processed, enable the mixed solution of instillation in hydrogen
Sodium oxide molybdena glomeration.Then the white chitosan microball that titration is formed is rinsed with deionized water to pH=7, is transferred to 200mL's
In flask, in case carrying out cross-linking reaction.
2, kappa-carrageenan-chitosan polyelectrolyte microsphere is fitted into 200mL flasks, adds 100mL deionized waters, with shifting
Liquid device is drawn 1mL glycol glycidyl ethers (EDGE) and is added in flask, as in 45 DEG C of water-baths, then carries out rotating speed
The magnetic agitation of 20rpm, reaction continues 5 hours, is then first cleaned with 95% ethyl alcohol, then clear with deionized water again
It washes, obtains crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere with filtered on buchner funnel, diameter is in 970um~985um.
3, the kappa-carrageenan after cross-linking reaction-chitosan polyelectrolyte microsphere is rinsed well, is transferred to 100mL flasks
In, it is dried 9 hours with rotary vacuum evaporator, drying temperature is 42 DEG C, and then the cross-linked chitosan just after drying is transferred to very
It is 2 days dry in empty drying box.Crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere after vacuum drying is put into the flask of 50mL
In, tetrahydrofuran (THF) 3.5mL, 0.5mL triethylamine is added and 2cm stirrers, rotating speed are adjusted to 20rpm, is put into ice-water bath,
Bottleneck is covered with preservative film, then snorkel is poked in preservative film insertion flask and is passed through nitrogen 30min.Wait for nitrogen ventilation knot
Beam is drawn 0.4mL bromo isobutyl acylbromides (BIBB) with syringe and is slowly injected into flask with rubber stopper seal flask, wink in flask
Between there is white solid, and continue to react 1 hour in ice-water bath, then be transferred under room temperature and react 24 hours, finally be filtered under diminished pressure,
It is first cleaned with 95% ethyl alcohol, then is cleaned with deionized water, be transferred to vacuum drying chamber drying.
4, kappa-carrageenan-chitosan polyelectrolyte microsphere after fixed initiator is transferred in the flask of 50ml, is added
0.25mL deionized waters, 2.5mL methanol and 1mL glycidyl methacrylate (GMA), are put into stirrer and are sealed with preservative film
Mouthful, it is passed through nitrogen 30min, then according to (monomer：BPY：CuBr：CuBr2=100:2:1:0.2) 10mg CuBr, are weighed,
3.1mg, 21.9mg 2,2'- bipyridyl, sequentially add in flask, then proceed to logical nitrogen 10 minutes.It is sealed, is set with rubber stopper
In 35 DEG C of water-bath, rotating speed 20rpm reacts 4 hours, and then cleaning is put into vacuum drying chamber.
Kappa-carrageenan-chitosan polyelectrolyte microsphere after ATRP is reacted is placed in the flask of 50mL, weighs 0.5g
Flask is added in polyethyleneimine, then addition 5mL deionized waters, and in magnetic stirring apparatus, rotating speed determines 200rpm, anti-in 50 DEG C of conditions
It answers 5 hours, is then first cleaned with 95% ethyl alcohol, then cleaned with deionized water, be transferred to vacuum drying chamber kept dry.Diameter exists
990 μm~1000 μm.
5, the kappa-carrageenan-chitosan polyelectrolyte microsphere being introduced into 4 after amido is placed in flask, 40ml first is added
Alcohol and 7mL deionized waters, stir evenly, and 40% sodium hydroxide solutions of 20mL are slowly added dropwise.After reacting 2h, curing is added dropwise
The mixed solution (carbon disulfide 8mL, ethyl alcohol 15mL) of carbon and ethyl alcohol, 2h is dripped, and reaction 20min. is warming up to 45 DEG C of reactions
16h, 50 DEG C of reaction 1h. reactions terminate, and deionized water and alcohol mixeding liquid are cleaned.Vacuum tank is dried, and modified carragheen-shell is obtained
Glycan polyelectrolyte microsphere, diameter is in 990 μm~1000 μm
6, at room temperature, claim 1g to be modified kappa-carrageenan-chitosan polyelectrolyte microsphere, be added to the Cr of 50mL concentration excess
(III) it in solution, under conditions of PH=5, is reacted 4 hours on magnetic stirring apparatus, investigates the poly- electrolysis of modified carragheen-chitosan
Matter microballoon is 2.1mmol/g to the saturated extent of adsorption of Cr ions.
The adsorption rate K of the present embodiments×10-3=0.916g/mmol-1·min-1。
Embodiment 3 is modified the preparation of carragheen-chitosan polyelectrolyte microsphere shell (chitosan matches=9/1 with carragheen)
1, dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere, and 0.1g carragheens and 0.9g chitosans are distinguished
It is dissolved in the glacial acetic acid of 1g/L, is made it dissolve with glass bar uniform stirring chitosan solution, seal beaker mouth with preservative film, then
Chitosan solution is transferred in 70 DEG C of water-bath and carries out constant temperature 2 hours, carrageenan solutions are transferred in 45 DEG C of water-baths and are carried out
Constant temperature 30min. then mixes the two full and uniform, obtains mixed liquor.40g sodium hydroxides are weighed, the beaker of 1000mL is dissolved in
In, it is configured to the sodium hydroxide solution of 1mol/L, drawing above-mentioned mixed solution with syringe instills in sodium hydroxide solution, mixing
Solution moment when entering sodium hydroxide solution is frozen into the substance of opaque white color by orange solution, and gradually sinks to beaker
Bottom.By adjusting the dynamics of syringe injection and titration direction during ball processed, enable the mixed solution of instillation in hydrogen
Sodium oxide molybdena glomeration.Then the white chitosan microball that titration is formed is rinsed with deionized water to pH=7, is transferred to 200mL's
In flask, in case carrying out cross-linking reaction.
2, kappa-carrageenan-chitosan polyelectrolyte microsphere is fitted into 200ml flasks, adds 100mL deionized waters, with shifting
Liquid device is drawn 1mL EDGE and is added in flask, as in 45 DEG C of water-baths, then carries out the magnetic agitation of rotating speed 20rpm, instead
It should continue 5 hours, then first be cleaned with 95% ethyl alcohol, then cleaned again with deionized water, obtained with filtered on buchner funnel
To crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere, diameter is at 970 μm~985 μm.
3, the kappa-carrageenan after cross-linking reaction-chitosan polyelectrolyte microsphere is rinsed well, is transferred to 100mL flasks
In, it is dried 9 hours with rotary vacuum evaporator, drying temperature is 42 DEG C, and then the cross-linked chitosan just after drying is transferred to very
It is 2 days dry in empty drying box.Crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere after vacuum drying is put into the flask of 50mL
In, THF 3.5mL, 0.5mL triethylamines are added and 2cm stirrers, rotating speed are adjusted to 20rpm, is put into ice-water bath, is sealed with preservative film
Then snorkel is poked in preservative film insertion flask and is passed through nitrogen 30min by firmly bottleneck.To the end of nitrogen is ventilated, rubber stopper is used
Sealed flask draws 0.4mL bromo isobutyl acylbromides (BIBB) with syringe and is slowly injected into flask, and moment appearance white is solid in flask
Body, and continue to react 1 hour in ice-water bath, then be transferred under room temperature and react 24 hours, it is finally filtered under diminished pressure, first with 95% ethyl alcohol
Cleaning, then cleaned with deionized water, it is transferred to vacuum drying chamber drying.
4, kappa-carrageenan-chitosan polyelectrolyte microsphere after fixed initiator is transferred in the flask of 50mL, is added
0.25mL deionized waters, 2.5mL methanol and 1mL glycidyl methacrylate (GMA), are put into stirrer and are sealed with preservative film
Mouthful, it is passed through nitrogen 30min, then according to (monomer：BPY：CuBr：CuBr2=100:2:1:0.2) 10mg CuBr, are weighed,
3.1mg, 21.9mg 2,2'- bipyridyl, sequentially add in flask, then proceed to logical nitrogen 10 minutes.It is sealed, is set with rubber stopper
In 35 DEG C of water-bath, rotating speed 20rpm reacts 4 hours, and then cleaning is put into vacuum drying chamber.
Kappa-carrageenan-chitosan polyelectrolyte microsphere after ATRP is reacted is placed in the flask of 50mL, weighs 0.5g
Flask is added in polyethyleneimine, then addition 5mL deionized waters, and in magnetic stirring apparatus, rotating speed determines 200rpm, anti-in 50 DEG C of conditions
It answers 5 hours, is then first cleaned with 95% ethyl alcohol, then cleaned with deionized water, be transferred to vacuum drying chamber kept dry.Diameter exists
990 μm~1000 μm.
5, the kappa-carrageenan-chitosan polyelectrolyte microsphere being introduced into 4 after amido is placed in flask, 40mL first is added
Alcohol and 7mL deionized waters, stir evenly, and 40% sodium hydroxide solutions of 20mL are slowly added dropwise.After reacting 2h, curing is added dropwise
The mixed solution (carbon disulfide 8mL, ethyl alcohol 15mL) of carbon and ethyl alcohol, 2h is dripped, and reaction 20min. is warming up to 45 DEG C of reactions
16h, 50 DEG C of reaction 1h. reactions terminate, and deionized water and alcohol mixeding liquid are cleaned.Vacuum tank is dried, and modified carragheen-shell is obtained
Glycan polyelectrolyte microsphere, diameter is at 990 μm~1000 μm.
6, at room temperature, it weighs 1g and is modified carragheen-chitosan polyelectrolyte microsphere, be added to the Cr of 50mL concentration excess
(III) it in solution, under conditions of PH=5, is reacted 4 hours on magnetic stirring apparatus, investigates the poly- electrolysis of modified carragheen-chitosan
Matter microballoon is 1.3mmol/g to the saturated extent of adsorption of Cr ions.
The adsorption rate K of the present embodiments×10-3=0.738g/mmol-1·min-1。
Modified carragheen-chitosan polyelectrolyte microsphere provided by the invention, adsorbance bigger, small toxicity is outstanding
Heavy metal chelating agent.
Claims (7)
1. being modified the preparation method of carragheen-chitosan polyelectrolyte microsphere, include the following steps：
1) dropping preparation method prepares kappa-carrageenan-chitosan polyelectrolyte microsphere：Carragheen and chitosan are dissolved in acid solution respectively；
Then the acid solution of chitosan is kept the temperature to 1.5~4h at 50~80 DEG C, the acid solution of carragheen keeps the temperature at 35~45 DEG C to 30~
The two is then uniformly mixed by 60min, obtains mixed liquor；Above-mentioned mixed liquor is instilled in aqueous slkali again, it is micro- to obtain chitosan
Ball；Chitosan microball is rinsed with deionized water again, until the pH=7 of flushing water, it is micro- to obtain kappa-carrageenan-chitosan polyelectrolyte
Ball；
2) deionized water is added in above-mentioned kappa-carrageenan-chitosan polyelectrolyte microsphere, then exists with glycol glycidyl ethers
35~55 DEG C of 54~6h of reaction, then use washes of absolute alcohol, then cleaned with deionized water, filter, dry, and obtain crosslinking κ-card
Draw glue-chitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-chitosan polyelectrolyte microsphere is added in tetrahydrofuran and triethylamine, in 0~6 DEG C,
It is passed through nitrogen and drains air, be then slowly added into bromo isobutyl acylbromide, and continue to react 1~3h at 0~6 DEG C, then be transferred to room temperature
Lower reaction 12~24 hours；It filters after reaction, washes of absolute alcohol is first used, then cleaned with deionized water, through being dried to obtain
Kappa-carrageenan-chitosan polyelectrolyte microsphere of fixed initiator；
4) in kappa-carrageenan-chitosan polyelectrolyte microsphere of above-mentioned fixed initiator, deionized water, methanol and methyl is added
Glycidyl acrylate is passed through nitrogen, then sequentially adds CuBr, CuBr2And 2,2'- bipyridyls then proceed to logical nitrogen
Air is drained, then at 35~45 DEG C of 3.5~6h of reaction, is then cleaned with deionized water, is dry；It adds polyethyleneimine and goes
Ionized water reacts 3~6h at 45~65 DEG C, then uses washes of absolute alcohol, then cleaned with deionized water, dry, is introduced
The kappa-carrageenan of amido-chitosan polyelectrolyte microsphere；
5) methanol and deionized water at room temperature, are added in the above-mentioned kappa-carrageenan for being introduced into amido-chitosan polyelectrolyte microsphere,
40% sodium hydroxide solution is slowly added dropwise, react 2~4h and then the mixed solution of carbon disulfide and ethyl alcohol is added dropwise, reaction
20min；Then heat to 45~60 DEG C, reaction 16~for 24 hours, it is cleaned to liquid shows neutral with deionized water and alcohol mixeding liquid,
It is dry, obtain modified carragheen-chitosan polyelectrolyte microsphere.
2. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
Acid solution described in step 1) is any one in glacial acetic acid, ethanedioic acid, lactic acid, succinic acid, malic acid, oxalic acid or dilute hydrochloric acid
Aqueous solution；The mass concentration of the acid solution is 1%~5%；The molar ratio of the acid solution and carragheen and chitosan is
0.1 ︰, 1 ︰, 9~0.4 ︰, 9 ︰ 1.
3. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
Step 1) the aqueous slkali is the deionized water solution of sodium hydroxide or potassium hydroxide；The sodium hydroxide or potassium hydroxide with go
The molar ratio of ionized water is 1 ︰ 1.
4. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
The addition of the step 2) deionized water be make kappa-carrageenan-chitosan polyelectrolyte microsphere mass concentration be 3%~
9%；The mass ratio of the ethylene glycol contracting glycerin ether and kappa-carrageenan-chitosan polyelectrolyte microsphere is 9 ︰, 50~7 ︰ 20.
5. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
The molar ratio of the step 3) tetrahydrofuran and triethylamine is 4 ︰, 3~2 ︰ 1；The bromo isobutyl acylbromide and crosslinking kappa-carrageenan-
The mass ratio of chitosan polyelectrolyte microsphere is 9 ︰, 20~3 ︰ 5.
6. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
The poly- electricity of kappa-carrageenan-chitosan of the step 4) deionized water, methanol, glycidyl methacrylate, fixed initiator
The molar ratio for solving matter microballoon is 5 ︰, 1 ︰, 0.4 ︰, 2~8 ︰, 3 ︰, 0.4 ︰ 2；The poly- electrolysis of kappa-carrageenan-chitosan of the fixed initiator
Matter microballoon, 2,2'- bipyridyls, CuBr, CuBr2Molar ratio be 100 ︰, 2 ︰, 1 ︰, 0.2~400 ︰, 3 ︰, 1 ︰ 0.2；The fixed initiation
The kappa-carrageenan of agent-chitosan polyelectrolyte microsphere, polyethyleneimine, deionized water molar ratio be 1 ︰, 0.4 ︰, 1~2 ︰, 1 ︰ 1.
7. the preparation method of modified carragheen-chitosan polyelectrolyte microsphere according to claim 1, it is characterised in that：
Step 5) is described introduce kappa-carrageenan-chitosan polyelectrolyte microsphere of amido, methanol, deionized water molar ratio be 2 ︰, 0.3 ︰
1~4 ︰, 0.1 ︰ 1；It is described introduce kappa-carrageenan-chitosan polyelectrolyte microsphere of amido, carbon disulfide, ethyl alcohol mass ratio be
2 ︰, 4 ︰, 1~3 ︰, 2 ︰ 0.5；In the mixed liquor of the deionized water and ethyl alcohol, the volume ratio of deionized water and ethyl alcohol is 1 ︰, 100~1 ︰
1。
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