CN106362703A - Improved carageenan-chitosan polyelectrolyte microspheres as well as preparation method and application thereof - Google Patents

Improved carageenan-chitosan polyelectrolyte microspheres as well as preparation method and application thereof Download PDF

Info

Publication number
CN106362703A
CN106362703A CN201610891001.9A CN201610891001A CN106362703A CN 106362703 A CN106362703 A CN 106362703A CN 201610891001 A CN201610891001 A CN 201610891001A CN 106362703 A CN106362703 A CN 106362703A
Authority
CN
China
Prior art keywords
shitosan
carrageenan
polyelectrolyte
kappa
microsphere
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610891001.9A
Other languages
Chinese (zh)
Other versions
CN106362703B (en
Inventor
张利
李玉宝
熊鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN201610891001.9A priority Critical patent/CN106362703B/en
Publication of CN106362703A publication Critical patent/CN106362703A/en
Application granted granted Critical
Publication of CN106362703B publication Critical patent/CN106362703B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Cosmetics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention belongs to the field of organic materials, particularly relates to an improved carageenan-chitosan polyelectrolyte microspheres as well as preparation method and application thereof, and aims to solve the technical problems of insufficient metal ion adsorption capacity, slow adsorption speed, low elution possibility and narrow application range of existing chitosan. The scheme for solving the technical problems is to provide the improved carageenan-chitosan polyelectrolyte microspheres. The invention also provides the preparation method and the application of the improved carageenan-chitosan polyelectrolyte microspheres.

Description

Modified carrageenan-shitosan polyelectrolyte microsphere and its production and use
Technical field
The invention belongs to organic material field and in particular to a kind of modification carrageenan-shitosan polyelectrolyte microsphere and its Preparation method and purposes.
Background technology
In the discharge process of industrial wastewater, considerable degree of heavy metal element is had 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 ecosystem.Heavy metal There is waste water with various chemical forms and enter environment, even if concentration very little, also can retain accumulation in algae and bed mud, by fish and The body surface enrichment of shellfish, produces food chain and concentrates, thus causing public hazards.Different from the pollution of other organic compound, heavy metal-polluted Dye can not pass through nature physics itself, chemistry or biology purification, so that harmfulness is reduced or release, its pollution has latent In property and hysteresis quality, it is one of emphasis and difficulties of global environmental protection.The processing method of heavy metal wastewater thereby mainly has thing Logos, chemical method, biological treatment.All using method of chemical treatment on 90%: neutralization coagulating sedimentation, sulphide precipitation, ferrum Oxysome method, chelate precipitation, ion floatation method, electrolysis, activated carbon adsorption is sent out, ion-exchange-resin process etc..
Applying of shitosan all achieves great progress in numerous areas.Its amido of shitosan easily forms level Four Amine cation, has weakly-basic anion exchange interaction, and due to the presence of free amine group, shitosan class has sun in an acidic solution Ion-type gathers dielectric property, as flocculating agent, but can be able to dissolve in an acidic solution, stability is poor.Difficult to form granule Structure, the balancing speed of impact mass transport process.Fixed bed is restricted as resin application.At present, chitosan resin The preparation method of ball can be divided into chemical crosslink technique, ionic cross-linking, complex coacervation, spray drying method and emulsion process etc..In doctor The fields such as medicine, food, agricultural, environmental protection, daily use chemicals obtain and are widely applied.Polymer microsphere due to its have polymolecularity and big than The feature on surface, is a kind of carrier material of excellent performance, at aspects such as drug controlled release, biological engineering, wastewater treatments It is widely studied, have broad application prospects.Chitosan material is prepared into polymer microsphere, makes shitosan and macromolecule micro- The excellent properties of ball organically combine be also more focus both at home and abroad at present research field in terms of environmental protection shitosan class have free Amino exist, there is cationic poly dielectric property in an acidic solution, as flocculating agent, water can be clarified, separately Outer shitosan heavy metal ion trapping, is used for sewage disposal and noble metal reclaims, and shitosan class can be used for radioactivity The trapping of element uranium and the process of nuclear industry sewage.But the absorbability of chitosan microball heavy metal ion itself is tied by it Structure characteristic and the impact of surface chemistry, activated adoption center is less, adsorbance, and adsorption rate is all relatively low.
Content of the invention
The technical problem to be solved in the present invention is that existing shitosan class heavy metal ionic adsorption amount is inadequate, and adsorbs Speed is slower, is difficult eluting, and range of application is narrow.
The scheme that invention solves above-mentioned technical problem is to provide a kind of modification carrageenan-shitosan polyelectrolyte microsphere.
Above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere, be mixed to form by shitosan and carrageenan insoluble Compound polyelectrolyte and be obtained.
Wherein, described shitosan and the mass ratio of carrageenan are 1 9～9 1.Preferably, described shitosan and carrageenan Mass ratio is 46.
The particle diameter of above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere is 990 μm～1010 μm.
Present invention also offers the preparation method of above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere, walk including following Rapid:
1) dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere: carrageenan and shitosan is dissolved in acid respectively molten In liquid；Then the acid solution of shitosan is incubated 1.5～4h at 50～80 DEG C, the acid solution of carrageenan is incubated at 35～45 DEG C 30～60min, subsequently by the two mix homogeneously, obtains mixed liquor；Again above-mentioned mixed liquor is instilled in aqueous slkali, obtain shitosan Microsphere；Deionized water rinses chitosan microball again, to the ph=7 of flushing water, obtains kappa-carrageenan-shitosan polyelectrolyte micro- Ball；
2) in above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere add deionized water, then with ethylene glycol (+)-2,3-Epoxy-1-propanol Ether reacts 54～6h at 35～55 DEG C, then uses washes of absolute alcohol, then deionized water cleaning, filters, is dried, obtains crosslinking Kappa-carrageenan-shitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-shitosan polyelectrolyte microsphere is added in oxolane 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 proceed to React 12～24 hours under room temperature；Reaction is filtered after terminating, and first uses washes of absolute alcohol, then deionized water cleaning, drying It is fixed the kappa-carrageenan-shitosan polyelectrolyte microsphere of initiator；
4) in the kappa-carrageenan-shitosan polyelectrolyte microsphere of above-mentioned fixing initiator, ionized water, methanol and first are added Base glycidyl acrylate, is passed through nitrogen, then sequentially adds cubr, cubr2, and 2,2'- bipyridyl, then proceed to logical nitrogen Gas drains air, reacts 3.5～6h then at 35～45 DEG C, and then deionized water is cleaned, is dried；Add polyethyleneimine and Deionized water, reacts 3～6h at 45～65 DEG C, then uses washes of absolute alcohol, then deionized water cleaning, is dried, is drawn Enter the kappa-carrageenan-shitosan polyelectrolyte microsphere of amido；
5) under room temperature, in the above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere being introduced into amido add methanol and go from Sub- water, is slowly added dropwise 40% sodium hydroxide solution, after reaction 2～4h, then the mixed solution of Deca Carbon bisulfide and ethanol, instead Answer 20min；Then heat to 45～60 DEG C, react 16～24h, deionized water and alcohol mixeding liquid clean in liquid being in Property, it is dried, obtain modified carrageenan-shitosan polyelectrolyte microsphere.
Above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere preparation method, step 1) described in acid solution be 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 described acid solution Concentration is 1%～5%；Described acid solution is 0.1 1 9～0.4 91 with the mol ratio of carrageenan or shitosan.
Above-mentioned preparation method, step 1) described aqueous slkali be sodium hydroxide or potassium hydroxide deionized water solution；Described Sodium hydroxide or potassium hydroxide are 11 with the mol ratio of deionized water.
Above-mentioned preparation method, step 2) addition of described deionized water is to make kappa-carrageenan-shitosan polyelectrolyte micro- The mass concentration of ball is 3%～9%；Described ethylene glycol contracting glycerin ether and the quality of kappa-carrageenan-shitosan polyelectrolyte microsphere Than for 9 50～7 20.
Above-mentioned preparation method, step 2) step of described drying is: crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere exists During rotary vacuum evaporator is dried, in 40～55 DEG C of drying 5～10h, then vacuum at 35～45 DEG C in vacuum drying oven 10-36h is dried.
Above-mentioned preparation method, step 3) described thf (oxolane) used as solvent with triethylamine.Described thf and three The mol ratio of ethamine is 4 3～2 1；Described bromo isobutyl acylbromide and the matter of crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere Amount ratio is 9 20～3 5.
Above-mentioned preparation method, step 4) described ionized water, methanol, glycidyl methacrylate, fixing initiator The mol ratio of kappa-carrageenan-shitosan polyelectrolyte microsphere is 51 0.4 2～8 3 0.4 2；The κ of described fixing initiator- Carrageenan-shitosan polyelectrolyte microsphere, bpy (2,2'- bipyridyl), cubr, cubr2Mol ratio be 100 21 0.2～ 400 31 0.2；The kappa-carrageenan of described fixing initiator-shitosan polyelectrolyte microsphere, polyethyleneimine, deionized water Mol ratio is 1 0.4 1～2 11.
Above-mentioned preparation method, step 2) and 4) described deionized water cleaning, referring to clean to deionized water is neutrality.
Above-mentioned preparation method, step 5) the described kappa-carrageenan-shitosan polyelectrolyte microsphere introducing amido, methanol, go The mol ratio of ionized water is 2 0.3 1～4 0.1 1；Described introduce amido kappa-carrageenan-shitosan polyelectrolyte microsphere, two Nitric sulfid, the mass ratio of ethanol are 24 1～3 2 0.5；In the mixed liquor of described deionized water and ethanol, deionized water and second The volume ratio of alcohol is 1 100～1 1.
Present invention also offers above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere reclaims in sewage disposal and noble metal In purposes.
The beneficial effects of the present invention is: 1, material based on shitosan and carrageenan, prepare kappa-carrageenan-shitosan Polyelectrolyte microsphere.A series of dtc modification kappa-carrageenan-shitosan polyelectrolyte microsphere being obtained through surface modifications, permissible As a kind of new adsorbent, mechanicalness and acid resistance are higher, and usage range is wider, and adsorbance is bigger, adsorption rate faster, more Easily eluting.2nd, the present invention adopts material based on shitosan and carrageenan, its good environment intermiscibility, recyclability, resource Abundant and cheap and easy to get the advantages of.The advantage combining shitosan and carrageenan, improves mechanical strength, exists simultaneously Hydroxyl, amino and other groups, also can have cancellated cage molecule by means of saline and alkaline formation by means of hydrogen bond, can heavy metal from Sub (cr2+、u6+、te3+、co3+、se6+、pu3+、hg2+,mn4+) chelated, important gold that therefore can effectively in adsorbent solution Belong to ion, also can a series of strengthening subsequent grafting activity.3rd, the present invention adopt Transfer Radical Polymerization (atrp), κ- Carrageenan-shitosan polyelectrolyte microsphere surface grafting polymerization brush, the polymerization brush density obtaining is bigger.Introduce it in amino group Rear dtc group introduces, and makes that modified kappa-carrageenan-shitosan polyelectrolyte microsphere adsorbance is bigger, and the heavy metal of small toxicity is caught Collection agent.
Specific embodiment
The preparation method of modified carrageenan-shitosan polyelectrolyte microsphere, comprises the following steps:
1) dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere: carrageenan and shitosan is dissolved in acid respectively molten In liquid；Then the acid solution of shitosan is incubated 1.5～4h at 50～80 DEG C, the acid solution of carrageenan is incubated at 35～45 DEG C 30～60min, subsequently by the two mix homogeneously, obtains mixed liquor；Again above-mentioned mixed liquor is instilled in aqueous slkali, obtain shitosan Microsphere；Deionized water rinses chitosan microball again, to the ph=7 of flushing water, obtains kappa-carrageenan-shitosan polyelectrolyte micro- Ball；
2) in above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere add deionized water, then with ethylene glycol (+)-2,3-Epoxy-1-propanol Ether reacts 54～6h at 35～55 DEG C, then uses washes of absolute alcohol, then deionized water cleaning, filters, is dried, obtains crosslinking Kappa-carrageenan-shitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-shitosan polyelectrolyte microsphere is added in oxolane 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 proceed to React 12～24 hours under room temperature；Reaction is filtered after terminating, and first uses washes of absolute alcohol, then deionized water cleaning, drying It is fixed the kappa-carrageenan-shitosan polyelectrolyte microsphere of initiator；
4) in the kappa-carrageenan-shitosan polyelectrolyte microsphere of above-mentioned fixing initiator, ionized water, methanol and first are added Base glycidyl acrylate, is passed through nitrogen, then sequentially adds cubr, cubr2, and 2,2'- bipyridyl, then proceed to logical nitrogen Gas drains air, reacts 3.5～6h then at 35～45 DEG C, and then deionized water is cleaned, is dried；Add polyethyleneimine and Deionized water, reacts 3～6h at 45～65 DEG C, then uses washes of absolute alcohol, then deionized water cleaning, is dried, is drawn Enter the kappa-carrageenan-shitosan polyelectrolyte microsphere of amido；
5) under room temperature, in the above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere being introduced into amido add methanol and go from Sub- water, is slowly added dropwise 40% sodium hydroxide solution, after reaction 2～4h, then the mixed solution of Deca Carbon bisulfide and ethanol, instead Answer 20min；Then heat to 45～60 DEG C, react 16～24h, deionized water and alcohol mixeding liquid clean in liquid being in Property, it is dried, obtain modified carrageenan-shitosan polyelectrolyte microsphere.
Above-mentioned modification carrageenan-shitosan polyelectrolyte microsphere preparation method, step 1) described in acid solution be 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 described acid solution Concentration is 1%～5%；Described acid solution is 0.1 1 9～0.4 91 with the mol ratio of carrageenan or shitosan.
Above-mentioned preparation method, step 1) described aqueous slkali be sodium hydroxide or potassium hydroxide deionized water solution；Described Sodium hydroxide or potassium hydroxide are 11 with the mol ratio of deionized water.
Above-mentioned preparation method, step 2) addition of described deionized water is to make kappa-carrageenan-shitosan polyelectrolyte micro- The mass concentration of ball is 3%～9%；Described ethylene glycol contracting glycerin ether and the quality of kappa-carrageenan-shitosan polyelectrolyte microsphere Than for 9 50～7 20.
Above-mentioned preparation method, step 2) step of described drying is: crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere exists During rotary vacuum evaporator is dried, in 40～55 DEG C of drying 5～10h, then vacuum at 35～45 DEG C in vacuum drying oven 10-36h is dried.
Above-mentioned preparation method, step 3) described thf (oxolane) used as solvent with triethylamine.Described thf and three The mol ratio of ethamine is 4 3～2 1；Described bromo isobutyl acylbromide and the matter of crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere Amount ratio is 9 20～3 5.
Above-mentioned preparation method, step 4) described ionized water, methanol, glycidyl methacrylate, fixing initiator The mol ratio of kappa-carrageenan-shitosan polyelectrolyte microsphere is 51 0.4 2～8 3 0.4 2；The κ of described fixing initiator- Carrageenan-shitosan polyelectrolyte microsphere, bpy (2,2'- bipyridyl), cubr, cubr2Mol ratio be 100 21 0.2～ 400 31 0.2；The kappa-carrageenan of described fixing initiator-shitosan polyelectrolyte microsphere, polyethyleneimine, deionized water Mol ratio is 1 0.4 1～2 11.
Above-mentioned preparation method, step 2) and 4) described deionized water cleaning, referring to clean to deionized water is neutrality.
Above-mentioned preparation method, step 5) the described kappa-carrageenan-shitosan polyelectrolyte microsphere introducing amido, methanol, go The mol ratio of ionized water is 2 0.3 1～4 0.1 1；Described introduce amido kappa-carrageenan-shitosan polyelectrolyte microsphere, two Nitric sulfid, the mass ratio of ethanol are 24 1～3 2 0.5；In the mixed liquor of described deionized water and ethanol, deionized water and second The volume ratio of alcohol is 1 100～1 1.
Preparation (mass ratio=1/ of shitosan and carrageenan of the modified carrageenan-shitosan polyelectrolyte microsphere of embodiment 1 9)
1st, dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere, by 0.9g carrageenan and 0.1g shitosan difference It is dissolved in the glacial acetic acid of 1g/l, so that it is dissolved with Glass rod uniform stirring chitosan solution, seal beaker mouth with preservative film, then Carry out constant temperature 2 hours in water-bath chitosan solution being proceeded to 70 DEG C, carrageenan solutions are proceeded in 45 DEG C of water-baths and carries out Constant temperature 30min, subsequently will be full and uniform for the two mixing, obtains mixed liquor.Weigh 40g sodium hydroxide, be dissolved in the beaker of 1000ml In, it is configured to the sodium hydroxide solution of 1mol/l, draw above-mentioned mixed solution with syringe and instill in sodium hydroxide solution, mixing Solution moment when entering sodium hydroxide solution is frozen into the material of opaque white color by orange solution, and gradually sinks to beaker Bottom.Pass through to adjust the dynamics of syringe injection and titration direction during ball processed, the mixed solution enabling instillation is in hydrogen Sodium oxide glomeration.Then the white chitosan microball deionized water forming titration is rinsed to ph=7, proceeds to 200ml's In flask, in case carrying out cross-linking reaction.
2nd, kappa-carrageenan-shitosan polyelectrolyte microsphere loads in 200ml flask, adds 100ml deionized water, with moving Liquid device is drawn 1ml diglycidyl ether of ethylene glycol (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 carried out with 95% ethanol, then deionized water is clear again Wash, obtain crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere with filtered on buchner funnel, diameter is at 970 μm～985 μm.
3rd, the kappa-carrageenan after cross-linking reaction-shitosan polyelectrolyte microsphere is rinsed well, proceed to 100ml flask In, it is dried 9 hours with rotary vacuum evaporator, baking temperature is 42 DEG C, the cross-linked chitosan after being then just dried proceeds to very It is dried 2 days in empty drying baker.Crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere after vacuum drying puts into the flask of 50ml In, add oxolane (thf) 3.5ml, 0.5ml triethylamine and 2cm stirrer, rotating speed is adjusted to 20rpm, puts in ice-water bath, Cover bottleneck with preservative film, then poke breather in preservative film insertion flask and be passed through nitrogen 30min.Treat nitrogen ventilation knot Bundle, uses rubber stopper seal flask, draws 0.4ml bromo isobutyl acylbromide (bibb) with syringe and is slowly injected into flask, wink in flask Between white solid occurs, and continue in ice-water bath react 1 hour, then proceed under room temperature react 24 hours, last filtration under diminished pressure, First use 95% ethanol purge, then deionized water cleaning, proceed to vacuum drying oven and be dried.
4th, the kappa-carrageenan-shitosan polyelectrolyte microsphere after fixing initiator is proceeded in the flask of 50ml, add 0.25ml deionized water, 2.5ml methanol and 1ml gma, put into the sealing of stirrer preservative film, are passed through nitrogen 30min, then press According to (monomer: bpy:cubr:cubr2=100:2:1:0.2), weigh cubr 10mg, cubr23.1mg, 2,2'- bipyridyls 21.9mg, sequentially adds in flask, then proceedes to logical nitrogen 10 minutes.With rubber stopper sealing, it is placed in 35 DEG C of water-bath, rotating speed 20rpm, reacts 4 hours, vacuum drying oven is put in then cleaning.
Kappa-carrageenan after atrp is reacted-shitosan polyelectrolyte microsphere is placed in the flask of 50ml, weighs 0.5g Polyethyleneimine adds flask, is subsequently adding 5ml deionized water, in magnetic stirring apparatuss, rotating speed determines 200rpm, anti-in 50 DEG C of conditions Answer 5 hours, then first use 95% ethanol purge, then deionized water cleaning, proceed to vacuum drying oven kept dry.Diameter exists 990 μm～1000 μm.
5th, the kappa-carrageenan after being introduced into amido in 4-shitosan polyelectrolyte microsphere is placed in flask, adds 40ml first Alcohol and 7ml deionized water, stir, and are slowly added dropwise 20ml 40% sodium hydroxide solution.After reaction 2h, Deca curing The mixed solution (Carbon bisulfide 8ml, ethanol 15ml) of carbon and ethanol, 2h drips, 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 obtains modified carrageenan-shell Polysaccharide polyelectrolyte microsphere, diameter is at 990 μm～1000 μm.
6th, at room temperature, weigh (1g) modification carrageenan-shitosan polyelectrolyte microsphere, be added to 50ml concentration excess In cr () solution, under conditions of ph=5, magnetic stirring apparatuss react 4 hours, investigate dtc modification kappa-carrageenan-shitosan Polyelectrolyte microsphere is 1.2mmol/g to the saturated extent of adsorption of cr ion.
In order to probe into the adsorption dynamics adsorption kinetics performance of microsphere further, using pseudo- First order dynamic model (pfo) and pseudo- two grades Kinetic model (pso) carrys out the matching ccs and ccs-g-pmaa microsphere adsorpting data to cr () ion, to select suitable mould Type.Pfo and pso kinetic model.ksIt is the speed 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.
Preparation (shitosan and carrageenan mass ratio=2/ of the modified carrageenan-shitosan polyelectrolyte microsphere shell of embodiment 2 3)
1st, dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere, by 0.6g carrageenan and 0.4g shitosan difference It is dissolved in the glacial acetic acid of 1g/l, so that it is dissolved with Glass rod uniform stirring chitosan solution, seal beaker mouth with preservative film, then Carry out constant temperature 2 hours in water-bath chitosan solution being proceeded to 70 DEG C, carrageenan solutions are proceeded in 45 DEG C of water-baths and carries out Constant temperature 30min.Subsequently will be full and uniform for the two mixing, obtain mixed liquor.Weigh 40g sodium hydroxide, be dissolved in the beaker of 1000ml In, it is configured to the sodium hydroxide solution of 1mol/l, draw above-mentioned mixed solution with syringe and instill in sodium hydroxide solution, mixing Solution moment when entering sodium hydroxide solution is frozen into the material of opaque white color by orange solution, and gradually sinks to beaker Bottom.Pass through to adjust the dynamics of syringe injection and titration direction during ball processed, the mixed solution enabling instillation is in hydrogen Sodium oxide glomeration.Then the white chitosan microball deionized water forming titration is rinsed to ph=7, proceeds to 200ml's In flask, in case carrying out cross-linking reaction.
2nd, kappa-carrageenan-shitosan polyelectrolyte microsphere loads in 200ml flask, adds 100ml deionized water, with moving Liquid device is drawn 1ml diglycidyl ether of ethylene glycol (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 carried out with 95% ethanol, then deionized water is clear again Wash, obtain crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere with filtered on buchner funnel, diameter is in 970um～985um.
3rd, the kappa-carrageenan after cross-linking reaction-shitosan polyelectrolyte microsphere is rinsed well, proceed to 100ml flask In, it is dried 9 hours with rotary vacuum evaporator, baking temperature is 42 DEG C, the cross-linked chitosan after being then just dried proceeds to very It is dried 2 days in empty drying baker.Crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere after vacuum drying puts into the flask of 50ml In, add oxolane (thf) 3.5ml, 0.5ml triethylamine and 2cm stirrer, rotating speed is adjusted to 20rpm, puts in ice-water bath, Cover bottleneck with preservative film, then poke breather in preservative film insertion flask and be passed through nitrogen 30min.Treat nitrogen ventilation knot Bundle, uses rubber stopper seal flask, draws 0.4ml bromo isobutyl acylbromide (bibb) with syringe and is slowly injected into flask, wink in flask Between white solid occurs, and continue in ice-water bath react 1 hour, then proceed under room temperature react 24 hours, last filtration under diminished pressure, First use 95% ethanol purge, then deionized water cleaning, proceed to vacuum drying oven and be dried.
4th, the kappa-carrageenan-shitosan polyelectrolyte microsphere after fixing initiator is proceeded in the flask of 50ml, add 0.25ml deionized water, 2.5ml methanol and 1ml glycidyl methacrylate (gma), put into stirrer preservative film and seal Mouthful, it is passed through nitrogen 30min, then according to (monomer: bpy:cubr:cubr2=100:2:1:0.2), weigh 10mg cubr, 3.1mg, 21.9mg 2,2'- bipyridyl, sequentially adds in flask, then proceedes to logical nitrogen 10 minutes.With rubber stopper sealing, put In 35 DEG C of water-bath, rotating speed 20rpm, react 4 hours, vacuum drying oven is put in then cleaning.
Kappa-carrageenan after atrp is reacted-shitosan polyelectrolyte microsphere is placed in the flask of 50ml, weighs 0.5g Polyethyleneimine adds flask, is subsequently adding 5ml deionized water, in magnetic stirring apparatuss, rotating speed determines 200rpm, anti-in 50 DEG C of conditions Answer 5 hours, then first use 95% ethanol purge, then deionized water cleaning, proceed to vacuum drying oven kept dry.Diameter exists 990 μm～1000 μm.
5th, the kappa-carrageenan after being introduced into amido in 4-shitosan polyelectrolyte microsphere is placed in flask, adds 40ml first Alcohol and 7ml deionized water, stir, and are slowly added dropwise 20ml 40% sodium hydroxide solution.After reaction 2h, Deca curing The mixed solution (Carbon bisulfide 8ml, ethanol 15ml) of carbon and ethanol, 2h drips, 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 obtains modified carrageenan-shell Polysaccharide polyelectrolyte microsphere, diameter is at 990 μm～1000 μm.
6th, at room temperature, claim 1g modification kappa-carrageenan-shitosan polyelectrolyte microsphere, be added to the cr of 50ml concentration excess In () solution, under conditions of ph=5, magnetic stirring apparatuss react 4 hours, investigate modified carrageenan-shitosan and gather electrolysis Matter microsphere is 2.1mmol/g to the saturated extent of adsorption of cr ion.
The adsorption rate k of the present embodiments×10-3=0.916g/mmol-1·min-1.
The preparation (shitosan and carrageenan proportioning=9/1) of the modified carrageenan-shitosan polyelectrolyte microsphere shell of embodiment 3
1st, dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere, by 0.1g carrageenan and 0.9g shitosan difference It is dissolved in the glacial acetic acid of 1g/l, so that it is dissolved with Glass rod uniform stirring chitosan solution, seal beaker mouth with preservative film, then Carry out constant temperature 2 hours in water-bath chitosan solution being proceeded to 70 DEG C, carrageenan solutions are proceeded in 45 DEG C of water-baths and carries out Constant temperature 30min. subsequently will be full and uniform for the two mixing, obtains mixed liquor.Weigh 40g sodium hydroxide, be dissolved in the beaker of 1000ml In, it is configured to the sodium hydroxide solution of 1mol/l, draw above-mentioned mixed solution with syringe and instill in sodium hydroxide solution, mixing Solution moment when entering sodium hydroxide solution is frozen into the material of opaque white color by orange solution, and gradually sinks to beaker Bottom.Pass through to adjust the dynamics of syringe injection and titration direction during ball processed, the mixed solution enabling instillation is in hydrogen Sodium oxide glomeration.Then the white chitosan microball deionized water forming titration is rinsed to ph=7, proceeds to 200ml's In flask, in case carrying out cross-linking reaction.
2nd, kappa-carrageenan-shitosan polyelectrolyte microsphere loads in 200ml flask, adds 100ml deionized water, with moving 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 5 hours should be continued, be then first carried out with 95% ethanol, then deionized water cleaning again, is obtained with filtered on buchner funnel To crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere, diameter is at 970 μm～985 μm.
3rd, the kappa-carrageenan after cross-linking reaction-shitosan polyelectrolyte microsphere is rinsed well, proceed to 100ml flask In, it is dried 9 hours with rotary vacuum evaporator, baking temperature is 42 DEG C, the cross-linked chitosan after being then just dried proceeds to very It is dried 2 days in empty drying baker.Crosslinked kappa-carrageenan-shitosan polyelectrolyte microsphere after vacuum drying puts into the flask of 50ml In, add thf 3.5ml, 0.5ml triethylamine and 2cm stirrer, rotating speed is adjusted to 20rpm, puts in ice-water bath, sealed with preservative film Live bottleneck, then poke breather in preservative film insertion flask and be passed through nitrogen 30min.Treat that nitrogen ventilation terminates, use rubber stopper Sealed flask, draws 0.4ml bromo isobutyl acylbromide (bibb) with syringe and is slowly injected into flask, and in flask, moment white admittedly Body, and continue to react 1 hour in ice-water bath, then proceed to reaction 24 hours, last filtration under diminished pressure under room temperature, first use 95% ethanol Cleaning, then deionized water cleaning, proceed to vacuum drying oven and are dried.
4th, the kappa-carrageenan-shitosan polyelectrolyte microsphere after fixing initiator is proceeded in the flask of 50ml, add 0.25ml deionized water, 2.5ml methanol and 1ml glycidyl methacrylate (gma), put into stirrer preservative film and seal Mouthful, it is passed through nitrogen 30min, then according to (monomer: bpy:cubr:cubr2=100:2:1:0.2), weigh 10mg cubr, 3.1mg, 21.9mg 2,2'- bipyridyl, sequentially adds in flask, then proceedes to logical nitrogen 10 minutes.With rubber stopper sealing, put In 35 DEG C of water-bath, rotating speed 20rpm, react 4 hours, vacuum drying oven is put in then cleaning.
Kappa-carrageenan after atrp is reacted-shitosan polyelectrolyte microsphere is placed in the flask of 50ml, weighs 0.5g Polyethyleneimine adds flask, is subsequently adding 5ml deionized water, in magnetic stirring apparatuss, rotating speed determines 200rpm, anti-in 50 DEG C of conditions Answer 5 hours, then first use 95% ethanol purge, then deionized water cleaning, proceed to vacuum drying oven kept dry.Diameter exists 990 μm～1000 μm.
5th, the kappa-carrageenan after being introduced into amido in 4-shitosan polyelectrolyte microsphere is placed in flask, adds 40ml first Alcohol and 7ml deionized water, stir, and are slowly added dropwise 20ml 40% sodium hydroxide solution.After reaction 2h, Deca curing The mixed solution (Carbon bisulfide 8ml, ethanol 15ml) of carbon and ethanol, 2h drips, 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 obtains modified carrageenan-shell Polysaccharide polyelectrolyte microsphere, diameter is at 990 μm～1000 μm.
6th, at room temperature, weigh 1g modification carrageenan-shitosan polyelectrolyte microsphere, be added to the cr of 50ml concentration excess In () solution, under conditions of ph=5, magnetic stirring apparatuss react 4 hours, investigate modified carrageenan-shitosan and gather electrolysis Matter microsphere is 1.3mmol/g to the saturated extent of adsorption of cr ion.
The adsorption rate k of the present embodiments×10-3=0.738g/mmol-1·min-1.
Modified carrageenan-shitosan polyelectrolyte microsphere that the present invention provides, its adsorbance is bigger, and small toxicity, is outstanding Heavy metal chelating agent.

Claims (12)

1. modified carrageenan-shitosan polyelectrolyte microsphere, is to be mixed to form insoluble poly- electrolysis by shitosan and carrageenan Matter complex and be obtained.
2. according to claim 1 modification carrageenan-shitosan polyelectrolyte microsphere it is characterised in that: described shitosan Mass ratio with carrageenan is 1 9～9 1.
3. according to claim 1 modification carrageenan-shitosan polyelectrolyte microsphere it is characterised in that: described shitosan Mass ratio with carrageenan is 46.
4. modification carrageenan-shitosan polyelectrolyte microsphere according to claim 1 it is characterised in that: described modified card The particle diameter drawing glue-shitosan polyelectrolyte microsphere is 990 μm～1010 μm.
5. the preparation method of modified carrageenan-shitosan polyelectrolyte microsphere, comprises the following steps:
1) dropping preparation method prepares kappa-carrageenan-shitosan polyelectrolyte microsphere: carrageenan and shitosan are dissolved in acid solution respectively； Then by the acid solution of shitosan 50～80 DEG C be incubated 1.5～4h, by the acid solution of carrageenan 35～45 DEG C be incubated 30～ 60min, subsequently by the two mix homogeneously, obtains mixed liquor；Again above-mentioned mixed liquor is instilled in aqueous slkali, obtain shitosan micro- Ball；Deionized water rinses chitosan microball again, to the ph=7 of flushing water, obtains kappa-carrageenan-shitosan polyelectrolyte micro- Ball；
2) add deionized water in above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere, then exist with diglycidyl ether of ethylene glycol 35～55 DEG C of reaction 54～6h, then use washes of absolute alcohol, then deionized water cleaning, filter, be dried, obtain crosslinked κ-card Draw glue-shitosan polyelectrolyte microsphere；
3) above-mentioned crosslinking kappa-carrageenan-shitosan polyelectrolyte microsphere is added in oxolane 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 proceed to room temperature Lower reaction 12～24 hours；Reaction is filtered after terminating, and first uses washes of absolute alcohol, then deionized water cleaning, and drying obtains Kappa-carrageenan-shitosan the polyelectrolyte microsphere of fixing initiator；
4) in the kappa-carrageenan-shitosan polyelectrolyte microsphere of above-mentioned fixing initiator, ionized water, methanol and methyl-prop are added Olefin(e) acid ethylene oxidic ester, is passed through nitrogen, then sequentially adds cubr, cubr2, and 2,2'- bipyridyl, then proceed to logical nitrogen row Air to the greatest extent, reacts 3.5～6h then at 35～45 DEG C, and then deionized water is cleaned, is dried；Add polyethyleneimine and go from Sub- water, reacts 3～6h at 45～65 DEG C, then uses washes of absolute alcohol, then deionized water cleaning, is dried, and obtains introducing amine The kappa-carrageenan of base-shitosan polyelectrolyte microsphere；
5), under room temperature, in the above-mentioned kappa-carrageenan-shitosan polyelectrolyte microsphere being introduced into amido, methanol and deionized water are added, It is slowly added dropwise 40% sodium hydroxide solution, after reaction 2～4h, then the mixed solution of Deca Carbon bisulfide and ethanol, reaction 20min；Then heat to 45～60 DEG C, react 16～24h, deionized water and alcohol mixeding liquid clean to liquid shows neutral, It is dried, obtain modified carrageenan-shitosan polyelectrolyte microsphere.
6. according to claim 5 modification carrageenan-shitosan polyelectrolyte microsphere preparation method it is characterised in that: Step 1) described in acid solution be glacial acetic acid, ethanedioic acid, lactic acid, succinic acid, malic acid, in oxalic acid or dilute hydrochloric acid any one Aqueous solution；The mass concentration of described acid solution is 1%～5%；Described acid solution with the mol ratio of carrageenan or shitosan is 0.1 1 9～0.4 91.
7. according to claim 5 modification carrageenan-shitosan polyelectrolyte microsphere preparation method it is characterised in that: Step 1) described aqueous slkali is the deionized water solution of sodium hydroxide or potassium hydroxide；Described sodium hydroxide or potassium hydroxide with go The mol ratio of ionized water is 11.
8. according to claim 5 modification carrageenan-shitosan polyelectrolyte microsphere preparation method it is characterised in that: Step 2) described deionized water addition be make kappa-carrageenan-shitosan polyelectrolyte microsphere mass concentration be 3%～ 9%；Described ethylene glycol contracting glycerin ether is 9 50～7 20 with the mass ratio of kappa-carrageenan-shitosan polyelectrolyte microsphere.
9. according to claim 5 modification carrageenan-shitosan polyelectrolyte microsphere preparation method it is characterised in that: Step 3) mol ratio of described oxolane and triethylamine is 4 3～2 1；Described bromo isobutyl acylbromide and crosslinked kappa-carrageenan- The mass ratio of shitosan polyelectrolyte microsphere is 9 20～3 5.
10. according to claim 5 modification carrageenan-shitosan polyelectrolyte microsphere preparation method it is characterised in that: Step 4) described ionized water, methanol, glycidyl methacrylate, the kappa-carrageenan-shitosan of fixing initiator gather electrolysis The mol ratio of matter microsphere is 51 0.4 2～8 3 0.4 2；The kappa-carrageenan of described fixing initiator-shitosan polyelectrolyte Microsphere, 2,2'- bipyridyl, cubr, cubr2Mol ratio be 100 21 0.2～400 31 0.2；Described fixing initiator Kappa-carrageenan-shitosan polyelectrolyte microsphere, polyethyleneimine, deionized water mol ratio be 1 0.4 1～2 11.
11. according to claim 5 modification carrageenan-shitosan polyelectrolyte microspheres preparation method it is characterised in that: Step 5) described introduce the kappa-carrageenan-shitosan polyelectrolyte microsphere of amido, methanol, the mol ratio of deionized water are 2 0.3 1～4 0.1 1；Described kappa-carrageenan-shitosan the polyelectrolyte microsphere introducing amido, Carbon bisulfide, the mass ratio of ethanol are 24 1～3 2 0.5；In the mixed liquor of described deionized water and ethanol, deionized water is 1 100～1 with the volume ratio of ethanol 1.
Modified carrageenan-shitosan polyelectrolyte microsphere described in 12. any one of Claims 1 to 4 is in sewage disposal and your gold Belong to the purposes in reclaiming.
CN201610891001.9A 2016-10-12 2016-10-12 Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application Expired - Fee Related CN106362703B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610891001.9A CN106362703B (en) 2016-10-12 2016-10-12 Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610891001.9A CN106362703B (en) 2016-10-12 2016-10-12 Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application

Publications (2)

Publication Number Publication Date
CN106362703A true CN106362703A (en) 2017-02-01
CN106362703B CN106362703B (en) 2018-10-30

Family

ID=57894961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610891001.9A Expired - Fee Related CN106362703B (en) 2016-10-12 2016-10-12 Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application

Country Status (1)

Country Link
CN (1) CN106362703B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597082A (en) * 2017-09-29 2018-01-19 江山海维科技有限公司 A kind of preparation method of Chinese gooseberry beverage adsorbent
CN108530670A (en) * 2018-02-07 2018-09-14 四川大学 Based on carragheen from anti-freezing heparan microballoon and the preparation method and application thereof
CN112209456A (en) * 2020-09-24 2021-01-12 成都玉龙化工有限公司 Water treatment agent and preparation method thereof
CN113999329A (en) * 2021-11-23 2022-02-01 江苏科技大学 Chitosan gel electrolyte grafted with nanoparticles and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102029144A (en) * 2009-09-29 2011-04-27 淮海工学院 Adsorbent for adsorbing heavy metal ions and dye in waste water and preparation method thereof
CN104927010A (en) * 2015-05-18 2015-09-23 复旦大学 Polyelectrolyte-rich core-shell type magnetic composite microspheres and preparation method therefor and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102029144A (en) * 2009-09-29 2011-04-27 淮海工学院 Adsorbent for adsorbing heavy metal ions and dye in waste water and preparation method thereof
CN104927010A (en) * 2015-05-18 2015-09-23 复旦大学 Polyelectrolyte-rich core-shell type magnetic composite microspheres and preparation method therefor and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A.V.VOLOD"KO ET AL.: ""Soluble chitosan–carrageenan polyelectrolyte complexes and theirgastroprotective activity"", 《CARBOHYDRATE》 *
张瑜等: ""κ-卡拉胶-壳聚糖聚电解质凝胶微丸的研制"", 《中国中药杂志》 *
陈晴川: ""环糊精聚合物微球及球形聚电解质刷选择性吸附苯酚和重金属离子的研究"", 《中国博士学位论文全文数据库工程科技I辑》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597082A (en) * 2017-09-29 2018-01-19 江山海维科技有限公司 A kind of preparation method of Chinese gooseberry beverage adsorbent
CN108530670A (en) * 2018-02-07 2018-09-14 四川大学 Based on carragheen from anti-freezing heparan microballoon and the preparation method and application thereof
CN108530670B (en) * 2018-02-07 2020-08-14 四川大学 Carrageenan-based self-anticoagulation heparinoid microspheres and preparation method and application thereof
CN112209456A (en) * 2020-09-24 2021-01-12 成都玉龙化工有限公司 Water treatment agent and preparation method thereof
CN113999329A (en) * 2021-11-23 2022-02-01 江苏科技大学 Chitosan gel electrolyte grafted with nanoparticles and preparation method and application thereof
CN113999329B (en) * 2021-11-23 2022-10-25 江苏科技大学 Chitosan gel electrolyte grafted with nanoparticles and preparation method and application thereof

Also Published As

Publication number Publication date
CN106362703B (en) 2018-10-30

Similar Documents

Publication Publication Date Title
CN104262536B (en) A kind of activity/controllable oxidization Graphene surface ion imprinted polymer and preparation method thereof and application
CN106362703B (en) Modified carragheen-chitosan polyelectrolyte microsphere and its preparation method and application
CN101314123B (en) Magnetic biological adsorption agent and preparation method thereof
Wei et al. Carboxymethyl cellulose fiber as a fast binding and biodegradable adsorbent of heavy metals
CN102161781B (en) Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof
Chen et al. Uranium removal by novel graphene oxide-immobilized Saccharomyces cerevisiae gel beads
CN107082894B (en) A kind of double-network hydrogel adsorbent and preparation method thereof and application as heavy metal absorbent
CN107442082A (en) A kind of magnetic polyacrylamide/alginic acid zirconium gel ball and its preparation method and application
CN104801262A (en) Preparation method and application of magnetic composite uranium adsorbent
CN106040194A (en) Chitosan magnetic composite spherule adsorbent with core-brush structure as well as preparation method and application thereof
CN109261138A (en) It is a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof
CN107282013A (en) The porous magnetic chitosan gel rubber microballoon and preparation method of a kind of size tunable
CN103894159A (en) Dye adsorbent capable of effectively removing anions from wastewater and preparation method of dye adsorbent
CN102277742A (en) Preparation method of cleaning material of heavy metal ions in reusable water
CN105399896A (en) Preparation method of gel material for adsorbing heavy metal ions and phenolic compound and product of gel material
CN108514870B (en) Hydrotalcite-poly (m-phenylenediamine) composite material and preparation method and application thereof
CN108047361B (en) A kind of Properties of Magnetic Chelating Resins, preparation method and its application in combined pollution water body purification
CN109317061A (en) A kind of preparation method of the chitosan loaded graphite oxide aerogel of hydrated ferric oxide
CN104492391A (en) Preparation method of chitosan modified albumin nanosphere heavy metal adsorption material
CN102863579B (en) Barbituric acid chelating resin and preparation method and application thereof
CN105664864A (en) Preparation method and application of vascular plant based porous oxidative polymerization chelating adsorption material
CN103937779A (en) Preparation and application method of magnetic chitosan biological immobilized particles
CN110090627A (en) A kind of calcium ion blotting chitosan adsorbent and the preparation method and application thereof
CN103041765B (en) Nano magnetic biological heavy metal trapping agent and preparation method and application thereof
CN105921128A (en) Preparing method for magnetic hydrogel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181030

Termination date: 20191012

CF01 Termination of patent right due to non-payment of annual fee