CN106040194A - Chitosan magnetic composite spherule adsorbent with core-brush structure as well as preparation method and application thereof - Google Patents
Chitosan magnetic composite spherule adsorbent with core-brush structure as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN106040194A CN106040194A CN201610466908.0A CN201610466908A CN106040194A CN 106040194 A CN106040194 A CN 106040194A CN 201610466908 A CN201610466908 A CN 201610466908A CN 106040194 A CN106040194 A CN 106040194A
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- China
- Prior art keywords
- adsorbent
- magnetic composite
- chitosan
- chitosan magnetic
- composite pellets
- 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.)
- Pending
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 217
- 239000003463 adsorbent Substances 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 153
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 26
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 25
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 21
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000008188 pellet Substances 0.000 claims description 114
- 239000000243 solution Substances 0.000 claims description 67
- 230000015572 biosynthetic process Effects 0.000 claims description 62
- 239000011324 bead Substances 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 238000004132 cross linking Methods 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 235000019394 potassium persulphate Nutrition 0.000 claims description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 18
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
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- 229960001193 diclofenac sodium Drugs 0.000 abstract description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 2
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- 230000004048 modification Effects 0.000 description 23
- 238000012986 modification Methods 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 21
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- 229910017135 Fe—O Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
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- 238000010438 heat treatment Methods 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- -1 chitosan Chemical class 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
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- LKAPTZKZHMOIRE-KVTDHHQDSA-N (2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolane-2-carbaldehyde Chemical compound OC[C@H]1O[C@H](C=O)[C@@H](O)[C@@H]1O LKAPTZKZHMOIRE-KVTDHHQDSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
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- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
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Classifications
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Abstract
The invention discloses a chitosan magnetic composite spherule adsorbent with core-brush structure as well as a preparation method and application thereof and belongs to the technical field of adsorbents. The preparation method comprises the following steps of adding a mixed liquor containing ferric ions and ferrous ions into a solution containing chitosan by use of a magnetic carrier technology, so as to obtain non-crosslinked chitosan magnetic composite spherules; then adding a glutaraldehyde solution so as to obtain crosslinked chitosan magnetic composite spherules; weighing the crosslinked chitosan magnetic composite spherule, triggering with potassium peroxodisulfate, and then adding a monomer (poly-methylacryloyl MAETAC, polyacrylic acid or polymethyl methacrylate), thereby obtaining the modified chitosan magnetic composite spherule adsorbent with the core-brush structure. According to the adsorption experiments, the synthetized modified chitosan magnetic composite spherule adsorbent with the core-brush structure has the characteristics of biodegradable property, easiness for separation from water, reusability, favorable adsorption effect on chemical diclofenac sodium and the like.
Description
Technical field
The invention belongs to technical field of absorbent, more particularly, it relates to a kind of chitosan magnetic with core-brush configuration
Composite pellets adsorbent and preparation method and application.
Background technology
Along with industry and the fast development of enterprise, the sharply increasing of quantity of wastewater effluent, cause the pollutant in natural water
Concentration and kind are also continuously increased, and water environment pollution is increasingly severe along with the acceleration of process of industrialization.In recent years, scholars
The emphasis paying close attention to the Research on kinds of pollutant in water body has turned to emerging pollutant from tradition pollutant.Its Chinese medicine is typical case
One of emerging pollutant.Although it often exists with relatively low concentration in water body, but due to they in the environment difficult degradation and
There is stronger biological accumulation, the most still cause the extensive concern of the public.Such drug contamination thing tool is removed from water
There is important meaning.
In numerous method for removing pollutant, absorption method is owing to having low cost, easy and simple to handle and excellent without mud formation etc.
Point, is widely used.Conventional commercialization adsorbent includes activated carbon and synthetic macromolecule resin, and they are removing organic contamination
Thing aspect has good effect.Such as Chinese Patent Application No. is 201510573838.4, and Shen Qing Publication day is in JIUYUE, 2015
The patent application document of 10 days discloses a kind of amido modified type that passes through mutually resin sorbent, has aperture big, and surface area is moderate,
The features such as regenerative adsorption is effective.But such adsorbent relatively costly and easily cause secondary in preparation with during using
Pollute.By contrast, biopolymer (such as chitosan, cellulose, starch etc.) is reproducible and eco-friendly, meets
The requirement of Green Chemistry, the adsorbent with biopolymer as base material well solves above-mentioned problem.Sandhya Babel
Deng (Sandhya Babel, Tonni Agustiono Kurniawan.Low-cost adsorbents for heavy
metals uptake from contaminated water:a review.Journal of Hazardous
Materials.2003,97,219-243) have studied the adsorption of the biopolymer ABSORBENTS ABSORPTION metals such as chitosan, real
Test result and show that this type of adsorbent has good adsorption effect.Although the adsorbent with biopolymer as base material has well
Biodegradability, and abundance, cost are relatively low, but the gel that formed of this type of adsorbent is difficult to from water body point
From.To this end, use magnetic carrier technology (introducing Fe 3 O 4 magnetic particle in biopolymer gels particle) to show
Write ground and strengthen water treatment efficiency so that adsorbent can readily be separated from the water.(Jiang Wei, the Wang such as Jiang Wei
Wenfeng,Pan Bingcai,Zhang Quanxing,Zhang Weiming,Lv Lu.Facile fabrication of
magnetic chitosan beads of fast kinetics and high capacity for copper
Removal.ACS Applied Materials&Interfaces.2014,6,3421-3426) synthesize with chitosan as base
The magnetic adsorbent of material, and metal copper ion is had remove ability efficiently.Although this type of adsorbent is easily from water
In separate, and have certain absorbability, but the functional group limited amount on biopolymer.Therefore, make
By small molecule-modified method, by the amidation on the esterification on oh group and etherificate and amino group, increase
Add the quantity of functional group on biopolymer.Such as Chinese Patent Application No. is 201210110877.7, Shen Qing Publication day
It is that the patent application document on April 16th, 2012 discloses a kind of straw being modified to amphoteric adsorbent, namely at fiber
2-hydroxypropyl-trimethyl ammonium chloride and aceticoceptor it is grafted so that it is possess higher absorption complexation energy on element or lignin molecule chain
Power, has the feature such as biodegradable, hypotoxicity simultaneously.But the magnetic absorption with biopolymer as base material of above-mentioned synthesis
Agent is only to carry out small molecule-modified to biopolymer, although adsorption effect has promoted, but functional group quantity is still
Less.In order to introduce more functional group in a step modifying process, glycerol polymerization is a more preferable selection.It is grafted
The magnetic adsorbent with biopolymer as base material of polymeric chain has special core-brush configuration (with biological high score
Sub-magnetic coupling bead is as core, and the polymeric long chain component of grafting is that brush is distributed in outer layer).Merit on biopolymer framework
Energy group may be by sterically hindered impact, and after adsorbent enters aqueous phase, the long-chain of grafting can be for greater flexibility in water
Stretch, so that the probability that the functional group on adsorbent contacts drug contamination thing molecule in water is greatly promoted.But, close
Have not been reported in the research removing medicine with the magnetic adsorbent with biopolymer as base material having core-brush configuration.
Summary of the invention
Problem to be solved
For existing adsorbent exist when application cannot biodegradation, to easily cause secondary pollution, cost high, in water body
Be not readily separated, the problem such as adsorption effect difference, the present invention provides a kind of absorption of the chitosan magnetic composite pellets with core-brush configuration
Agent and preparation method and application.Use magnetic carrier technology, the solution containing chitosan adds ferric ion and bivalence
Iron ion mixed liquor obtains uncrosslinked chitosan magnetic composite pellets, is subsequently adding glutaraldehyde solution, and the shell obtaining crosslinking gathers
Sugar magnetic coupling bead.After weighing the chitosan magnetic composite pellets of crosslinking, use potassium peroxydisulfate to cause, add monomer (poly-
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, polyacrylic acid or polymethyl methacrylate) obtain that there is changing of core-brush configuration
Property chitosan magnetic composite pellets adsorbent.Being found by adsorption test, the modification of chitosan magnetic of the core-brush configuration of synthesis is multiple
Close bead adsorbent have biodegradable, be easily separated from the water, reusable, excellent to medicine diclofenac sodium adsorption effect
The feature such as good.
2. technical scheme
In order to solve the problems referred to above, the technical solution adopted in the present invention is as follows:
Synthesizing a kind of modification of chitosan magnetic coupling bead adsorbent with core-brush configuration, its core portion structure is that shell gathers
Sugar and the bead of Fe 3 O 4 magnetic mix particles, surface grafting monomer (polymethyl acyloxyethyl trimethyl ammonium chloride,
Or polyacrylic acid, or polymethyl methacrylate).Final synthesis is had the modification of chitosan magnetic coupling of core-brush configuration
Bead adsorbent carries out quantitative analysis: the water content ranges utilizing drying technology to obtain adsorbent is 70%～90%, utilizes height
It is 1:(0.31～0.67 that temperature calcination technology obtains the mass ratio of ferroso-ferric oxide and organic component in adsorbent), utilize element to divide
It is (0.05～2.32) that analysis technology obtains the mass ratio of macromolecular grafted chain and chitosan in adsorbent organic component: 1.This absorption
The basic structure formula of agent is as follows:
In formula, P is
The preparation method of above-mentioned a kind of modification of chitosan magnetic coupling bead adsorbent with core-brush configuration, its step
Suddenly it is:
(1) weigh chitosan, add deionized water, be then directly added into concentrated hydrochloric acid (chitosan is completely dissolved), then weigh
FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution, dissolves, ultrasonic, obtains mixed solution；
(2) by the mixed solution in step (1), in peristaltic pump instills sodium hydroxide-alcohol-water mixed solution, (solution needs
Magneton stirs), mixed solution rapidly becomes graininess bead, obtains uncrosslinked chitosan magnetic composite pellets after filtration；
(3), after the uncrosslinked chitosan magnetic composite pellets in step (2) being added to the water, glutaraldehyde is added molten
Liquid, room temperature magnetic agitation 6-24h, react afterwash, obtain the chitosan magnetic composite pellets of crosslinking；
(4) the chitosan magnetic composite pellets of crosslinking in step (3) is accurately weighed, after being added in four-necked bottle, adds water,
Agitating heating at 40～60 DEG C；Then measure potassium peroxydisulfate, be added in water dissolving and obtain aqueous solution；Weigh certain monomer (poly-first
Base acrylyl oxy-ethyl-trimethyl salmiac, or polyacrylic acid, or polymethyl methacrylate) it is added in water, dissolve and obtain water
Solution.Put up experimental provision, monomer solution is placed in Dropping funnel, it is ensured that the air-tightness of device, logical nitrogen 10～25min
After, add potassium persulfate solution, continue logical nitrogen 5～10min.Be warmed up to 40-60 DEG C, slowly drip monomer solution (10～
20min), after dropping, react 3～6h.After reaction terminates, solution washs in acetone, puts in water, thus is had
The modification of chitosan magnetic coupling bead adsorbent of core-brush configuration.
Further, the viscosity-average molecular weight of the chitosan described in step (1) is 10～200,000, chitosan and FeCl3·
6H2O、FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:(2.32～3.48): (0.85～1.28): (50～80): (0.5
～2), ultrasonic 5min.
Further, sodium hydroxide, ethanol, the mass ratio of water in sodium hydroxide-alcohol-water mixed solution in step (2)
For 1:3:6, the mass ratio of the mixed solution of above-mentioned synthesis and the mixed solution of sodium hydroxide-alcohol-water is 1:(3～5), mixed
The rate of addition closing solution is 1mL/min, and magneton rotating speed is at 80r/min.
Further, uncrosslinked in step (3) chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:
(0.0005～0.005): (0.5～2.5), the mass fraction of glutaraldehyde solution is 25%, and mixing speed is 20～60r/min.
Preferably, the chitosan magnetic composite pellets of crosslinking and the mass ratio of water are 1:5 in step (4), potassium peroxydisulfate and
The mass ratio of water be the mass ratio of 1:20, monomer and water be (0.03～0.25): 1.00, potassium peroxydisulfate, monomer, crosslinking shell gather
The mass ratio of sugar magnetic coupling bead is 0.0125:(0.01～0.5): 1, acetone and the solution quality ratio after being finally synthesizing are
1:3。
The application in water processes of the above-mentioned modification of chitosan magnetic coupling bead adsorbent with core-brush configuration.
Above-mentioned have the modification of chitosan magnetic coupling bead adsorbent of core-brush configuration containing diclofenac sodium class waste water
Application in process field.
The innovative point of the present invention is:
(1) use magnetic carrier technology, make Fe 3 O 4 magnetic particle mix with natural polymer chitosan,
Thus cause the adsorbent with chitosan as base material finally synthesized to have magnetic, it is simple to process and reclaim.
(2) use reversed-phase precipitation technology, the mixed solution of chitosan and Fe 3 O 4 magnetic particle is instilled hydroxide
Separating out after the mixed solution of sodium-alcohol-water, the chitosan magnetic composite pellets adsorbent of formation is easily isolated, thus avoids
Water body is caused secondary pollution.
(3) use natural polymer chitosan as the framing structure of sorbent material, not only acted as biodegradable,
Avoid the effect of environmental pollution, and a large amount of amino groups in chitosan molecule have the ability of good absorption pollutant, more
Prepare for next step grafted monomers.
(4) use crosslinking technological after glutaraldehyde, make in chitosan magnetic composite pellets chitosan crosslinked together, structure
Tightr, thus form more stable structure, it is therefore prevented that chitosan magnetic composite pellets is destroyed in water body.
(5) use graft copolymerization technology, chitosan magnetic composite pellets is grafted monomer, obtain that there is core-brush knot
The adsorbent of structure, thus considerably increase the effective efficiency group of composite pellets and show in water body and more contact position
Point, to such an extent as to have more preferable adsorption effect.
3. beneficial effect
Compared to prior art, the invention have the benefit that
(1) the present invention is directed to existing adsorbent application time exist cannot biodegradation, easily cause secondary pollution, cost
High, be not readily separated in water body, the problem such as adsorption effect difference, use bioabsorbable polymer material chitosan and Fe 3 O 4 magnetic
Grafted monomers again after particle is compound, i.e. synthesizes a kind of modification of chitosan magnetic coupling bead adsorbent with core-brush configuration, from
And the problems referred to above can be solved: on the one hand, use bioabsorbable polymer material chitosan as base material so that the adsorbent phase of synthesis
Having non-secondary pollution, low cost and other advantages for other adsorbents, the chitosan magnetic composite pellets after crosslinking has more steady
Fixed structure, and use chitosan to become magnetic coupling bead with Fe 3 O 4 magnetic mix particles, it is simple to reclaim；The opposing party
Face, grafting is formed after monomer the adsorbent of core-brush configuration, has more effective efficiency group and contact site, thus to spy
Fixed medicine diclofenac sodium has more preferable adsorption effect；
(2) in the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration of the present invention, ferroso-ferric oxide magnetic
Property particle is distributed in inside chitosan, has Magneto separate character, makes adsorbent be prone to be separated from the water；
(3) present invention uses Measurement of Biopolymer Chitosan as the base material of adsorbent, can reach the effect of environmental protection, and
Chitosan itself is also good adsorbent base material, has substantial amounts of amino group；
(4) the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration of the present invention has been grafted monomer, thus
Add the specific surface area of adsorbent so that it is have more effectively functional group and contact site, thus adding adsorbent to medicine
The absorbability of thing diclofenac sodium；
(5), on the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration of the present invention, chitosan passes through penta
Dialdehyde cross-links, so that the stability of composite pellets is greatly increased, is difficult to be destroyed；
(6) preparation method of the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration of the present invention, operation
Simply, generated time short, and the adsorbent synthesized can be recycled for multiple times and keep higher absorption property.
Accompanying drawing explanation
Fig. 1 is that the modification of chitosan magnetic coupling bead adsorbent basic structure formula with core-brush configuration of the present invention is shown
It is intended to；
Fig. 2 is modification of chitosan magnetic coupling bead adsorbent and the comparative example 1 in embodiment 1-3 with core-brush configuration
The infrared spectrum of middle chitosan magnetic coupling bead adsorbent；
Fig. 3 is that in embodiment 1, the chitosan magnetic composite pellets of the grafted polyacrylic acid with core-brush configuration of synthesis is inhaled
The TEM of attached dose；
Fig. 4 is the grafting polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration of synthesis in embodiment 2
The TEM of chitosan magnetic composite pellets adsorbent；
Fig. 5 is that in embodiment 3, the chitosan magnetic of the grafting polymethyl methacrylate with core-brush configuration of synthesis is multiple
Close the TEM of bead adsorbent；
Fig. 6 is that in embodiment 4, the chitosan magnetic of the grafting polymethyl methacrylate with core-brush configuration of synthesis is multiple
Close the TEM of bead adsorbent；
Fig. 7 is the grafting polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration of synthesis in embodiment 5
The TEM of chitosan magnetic composite pellets adsorbent；
Fig. 8 is that in embodiment 6, the chitosan magnetic composite pellets of the grafted polyacrylic acid with core-brush configuration of synthesis is inhaled
The TEM of attached dose；
Fig. 9 is the TEM of the chitosan magnetic composite pellets adsorbent of synthesis in comparative example 1；
Figure 10 is that the core-brush that has in embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 is tied
In the modification of chitosan magnetic coupling bead adsorbent of structure and comparative example 1, the chitosan magnetic composite pellets adsorbent of synthesis is inhaled
The absorption spirogram of attached medicine diclofenac sodium.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described below.
Embodiment 1
Weighing chitosan (viscosity-average molecular weight is 200,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:2.32:0.85:60:1), dissolving, ultrasonic 5min, obtain mixed solution.Warp
The mixed solution of above-mentioned synthesis is instilled (hydrogen-oxygen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min by peristaltic pump
Changing sodium hydroxide, ethanol, the mass ratio of water in sodium-alcohol-water mixed solution is 1:3:6, the mixed solution of above-mentioned synthesis and hydrogen
The mass ratio of the mixed solution of sodium oxide-alcohol-water is 1:3；Solution needs magneton to stir, and magneton rotating speed is at 80r/min), mixed
Close solution and rapidly become graininess bead, after filtration, obtain uncrosslinked chitosan magnetic composite pellets.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.0025:2), room temperature magnetic force
Stirring 18h, mixing speed is 40r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 45 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；The polyacrylic acid weighing certain mass is added in water, dissolves
(mass ratio of polyacrylic acid and water is 0.2:1, potassium peroxydisulfate, polyacrylic acid, the chitosan magnetic coupling of crosslinking to obtain aqueous solution
The mass ratio of bead is 0.0125:0.2:1).Put up experimental provision, polyacrylic acid aqueous solution be placed in Dropping funnel, it is ensured that
The air-tightness of device, after logical nitrogen 15min, adds potassium persulfate solution, continues logical nitrogen 10min.It is warmed up to 45 DEG C, slowly drips
Addition polymerization acrylic acid aqueous solution (15min), after dropping, reacts 5h.Reaction terminate after, solution wash in acetone (acetone and
Solution quality after being finally synthesizing is than for 3:1), finally pour into (submerged in water) in beaker, obtain that there is core-brush configuration
It is grafted polyacrylic chitosan magnetic composite pellets adsorbent.
Result:
Fig. 2 shows in the present embodiment synthesis there is core-brush configuration be grafted polyacrylic chitosan magnetic
The infrared spectrum of composite pellets adsorbent.At about 3449cm-1, 1637cm-1And 609cm-1There is characteristic peak at place, is-OH respectively ,-
NH2And Fe3O4The absworption peak of middle Fe-O, it is meant that the successful synthesis of chitosan magnetic composite pellets.And there is C=O above
(1718cm-1, from carboxyl) characteristic peak.Prove that carboxyl is introduced in magnetic material, it was demonstrated that polyacrylic acid chain is successfully grafted on
On chitosan magnetic composite pellets adsorbent.Fig. 3 be in embodiment 1 synthesis there is core-brush configuration be grafted polyacrylic acid
The TEM of chitosan magnetic composite pellets adsorbent.Seeing from Fig. 3, Fe 3 O 4 magnetic particle divides with nano level form
Cloth is in the inside of adsorbent, and black part is divided into chitosan molecule, and edge transparent part is the polyacrylic acid long-chain in grafting.
The polyacrylic chitosan magnetic composite pellets adsorbent that has been grafted with core-brush configuration of final synthesis is carried out
Quantitative analysis: utilizing drying technology to obtain adsorbent water content is 80%, utilizes high temperature sintering technology to obtain four oxygen in adsorbent
The mass ratio changing three-iron and organic component is 1:0.48, utilize element analysis technology obtain in adsorbent organic component grafted chain with
The mass ratio of chitosan is 0.45:1.
Embodiment 2
Weighing chitosan (viscosity-average molecular weight is 100,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:3.48:1.28:50:2), dissolving, ultrasonic 5min, obtain mixed solution.Warp
The mixed solution of above-mentioned synthesis is instilled (hydrogen-oxygen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min by peristaltic pump
Changing sodium hydroxide, ethanol, the mass ratio of water in sodium-alcohol-water mixed solution is 1:3:6, the mixed solution of above-mentioned synthesis and hydrogen
The mass ratio of the mixed solution of sodium oxide-alcohol-water is 1:5；Solution needs magneton to stir, and magneton rotating speed is at 80r/min), mixed
Close solution and rapidly become graininess bead, after filtration, obtain uncrosslinked chitosan magnetic composite pellets.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.005:0.5), normal temperature magnetic
Power stirring 12h, mixing speed is 50r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 50 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；Weigh the polymethyl acyloxyethyl front three of certain mass
Ammonium chloride is added in water, and dissolving obtains aqueous solution, and (mass ratio of polymethyl acyloxyethyl trimethyl ammonium chloride and water is
0.25:1, potassium peroxydisulfate, polymethyl acyloxyethyl trimethyl ammonium chloride, the quality of chitosan magnetic composite pellets of crosslinking
Ratio is 0.0125:0.5:1).Put up experimental provision, polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium is placed in dropping liquid
In funnel, it is ensured that the air-tightness of device, after logical nitrogen 25min, add potassium persulfate solution, continue logical nitrogen 5min.It is warmed up to
50 DEG C, slowly dropping polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium (20min), after dropping, react 4h.Instead
After should terminating, solution washs (acetone and the solution quality after being finally synthesizing than for 3:1) in acetone, finally pours in beaker
(submerged in water), obtains the chitosan being grafted polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration
Magnetic coupling bead adsorbent.
Result:
Fig. 2 shows in the present embodiment synthesis there is core-brush configuration be grafted polymethyl acyloxyethyl three
The infrared spectrum of the chitosan magnetic composite pellets adsorbent of ammonio methacrylate.At about 3449cm-1, 1637cm-1And 609cm-1
There is characteristic peak at place, is-OH ,-NH respectively2And Fe3O4The absworption peak of middle Fe-O, it is meant that the successful conjunction of chitosan magnetic ball
Become.Simultaneously at 1722cm-1There is the characteristic peak of carbonyl at place, at 1259cm-1There is the absworption peak of ester group at place, at 1377cm-1There is C-N at place
The absworption peak of (from quaternary ammonium group).Thus prove that polymethyl acyloxyethyl trimethyl ammonium chloride is successfully received chitosan
On magnetic coupling bead adsorbent.Fig. 4 be in embodiment 2 synthesis there is core-brush configuration be grafted polymethyl acyl-oxygen
The TEM of the chitosan magnetic composite pellets adsorbent of ethyl-trimethyl salmiac.See from Fig. 4, Fe 3 O 4 magnetic particle
With nano level formal distribution in the inside of adsorbent, black part is divided into chitosan molecule, and edge transparent part is in grafting
Polymethyl acyloxyethyl trimethyl ammonium chloride long-chain.
The chitosan being grafted polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration of final synthesis
Magnetic coupling bead adsorbent carries out quantitative analysis: utilizing drying technology to obtain adsorbent water content is 75%, utilizes high temperature to burn
It is 1:0.67 that burning technology obtains the mass ratio of ferroso-ferric oxide and organic component in adsorbent, utilizes element analysis technology to be inhaled
In attached dose of organic component, grafted chain is 2.32:1 with the mass ratio of chitosan.
Embodiment 3
Weighing chitosan (viscosity-average molecular weight is 150,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:2.78:1.02:50:80:0.5), dissolve, ultrasonic 5min, obtain mixing molten
Liquid.Through peristaltic pump, the mixed solution of above-mentioned synthesis is instilled in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min
(in sodium hydroxide-alcohol-water mixed solution, sodium hydroxide, ethanol, the mass ratio of water are 1:3:6, the mixed solution of above-mentioned synthesis
It is 1:4 with the mass ratio of the mixed solution of sodium hydroxide-alcohol-water；Solution needs magneton to stir, and magneton rotating speed is at 80r/
Min), mixed solution rapidly becomes graininess bead, obtains uncrosslinked chitosan magnetic composite pellets after filtration.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.05:2.5), room temperature magnetic force
Stirring 24h, mixing speed is 60r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 55 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；The polymethyl methacrylate weighing certain mass is added to water
In, dissolving obtains aqueous solution, and (mass ratio of polymethyl methacrylate and water is 0.03:1, potassium peroxydisulfate, polymethylacrylic acid
Methyl ester, the mass ratio of chitosan magnetic composite pellets of crosslinking are 0.0125:0.01:1).Put up experimental provision, poly-methyl-prop
E pioic acid methyl ester aqueous solution is placed in Dropping funnel, it is ensured that the air-tightness of device, after logical nitrogen 10min, adds potassium persulfate solution,
Continue logical nitrogen 10min.It is warmed up to 55 DEG C, slowly dropping polymethyl methacrylate aqueous solution (10min), after dropping,
Reaction 6h.After reaction terminates, solution washs (acetone and the solution quality after being finally synthesizing than for 3:1) in acetone, finally
Pour into (submerged in water) in beaker, obtain the chitosan magnetic being grafted polymethyl methacrylate with core-brush configuration
Composite pellets adsorbent.
Result:
Fig. 2 shows the shell being grafted polymethyl methacrylate with core-brush configuration of synthesis in the present embodiment
The infrared spectrum of polysaccharide magnetic coupling bead adsorbent.At about 3449cm-1, 1637cm-1And 609cm-1There is characteristic peak at place, point
It is not-OH ,-NH2And Fe3O4The absworption peak of middle Fe-O, it is meant that the successful synthesis of chitosan magnetic ball.Find simultaneously
From the C-H (2995cm of methyl-1, 2951cm-1) characteristic peak, and C=O (1730cm-1) and ester group (1271cm-1) absorption
Peak, also demonstrates the successful synthesis of the chitosan magnetic composite pellets adsorbent being grafted polymethyl methacrylate.Fig. 5 is real
Execute the chitosan magnetic composite pellets adsorbent being grafted polymethyl methacrylate with core-brush configuration of synthesis in example 3
TEM.Seeing from Fig. 5, Fe 3 O 4 magnetic particle is divided in the inside of adsorbent, black part with nano level formal distribution
Chitosan molecule, and edge transparent part is the polymethyl methacrylate long-chain in grafting.
The chitosan magnetic composite pellets being grafted polymethyl methacrylate with core-brush configuration of final synthesis is inhaled
Attached dose carries out quantitative analysis: utilizing drying technology to obtain adsorbent water content is 90%, utilizes high temperature sintering technology to be adsorbed
In agent, ferroso-ferric oxide is 1:0.31 with the mass ratio of organic component, utilizes element analysis technology to obtain in adsorbent organic component
Grafted chain is 0.05:1 with the mass ratio of chitosan.
Embodiment 4
Weighing chitosan (viscosity-average molecular weight is 200,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:2.55:0.94:70:2), dissolving, ultrasonic 5min, obtain mixed solution.Warp
The mixed solution of above-mentioned synthesis is instilled (hydrogen-oxygen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min by peristaltic pump
Changing sodium hydroxide, ethanol, the mass ratio of water in sodium-alcohol-water mixed solution is 1:3:6, the mixed solution of above-mentioned synthesis and hydrogen
The mass ratio of the mixed solution of sodium oxide-alcohol-water is 1:5；Solution needs magneton to stir, and magneton rotating speed is at 80r/min), mixed
Close solution and rapidly become graininess bead, after filtration, obtain uncrosslinked chitosan magnetic composite pellets.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.002:1.5), normal temperature magnetic
Power stirring 24h, mixing speed is 20r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 45 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；The polymethyl methacrylate weighing certain mass is added to water
In, dissolving obtains aqueous solution, and (mass ratio of polymethyl methacrylate and water is 0.1:1, potassium peroxydisulfate, poly-methyl methacrylate
Ester, the mass ratio of chitosan magnetic composite pellets of crosslinking are 0.0125:0.25:1).Put up experimental provision, polymethyl
Acid methyl ester aqueous solution is placed in Dropping funnel, it is ensured that the air-tightness of device, after logical nitrogen 25min, adds potassium persulfate solution, continues
Continuous logical nitrogen 5min.It is warmed up to 45 DEG C, slowly dropping polymethyl methacrylate aqueous solution (20min), after dropping, reaction
3h.After reaction terminates, solution washs (acetone and the solution quality after being finally synthesizing than for 3:1) in acetone, finally pours into
In beaker (submerged in water), obtain the chitosan magnetic coupling being grafted polymethyl methacrylate with core-brush configuration
Bead adsorbent.
Result:
The chitosan magnetic coupling being grafted polymethyl methacrylate with core-brush configuration of synthesis in the present embodiment
The infrared spectrum of bead adsorbent is similar with the infrared spectrum shown by embodiment in Fig. 23.At about 3449cm-1, 1637cm-1With
And 609cm-1There is characteristic peak at place, is-OH ,-NH respectively2And Fe3O4The absworption peak of middle Fe-O, it is meant that chitosan magnetic ball
Successful synthesis.Find the C-H (2995cm from methyl simultaneously-1, 2951cm-1) characteristic peak, and C=O (1730cm-1)
With ester group (1271cm-1) absworption peak, also demonstrate be grafted polymethyl methacrylate chitosan magnetic composite pellets inhale
The successful synthesis of attached dose.Fig. 6 is the shell being grafted polymethyl methacrylate with core-brush configuration of synthesis in embodiment 4
The TEM of polysaccharide magnetic coupling bead adsorbent.Seeing from Fig. 6, Fe 3 O 4 magnetic particle exists with nano level formal distribution
The inside of adsorbent, black part is divided into chitosan molecule, and edge transparent part is that the polymethyl methacrylate in grafting is long
Chain.
The chitosan magnetic composite pellets being grafted polymethyl methacrylate with core-brush configuration of final synthesis is inhaled
Attached dose carries out quantitative analysis: utilizing drying technology to obtain adsorbent water content is 78%, utilizes high temperature sintering technology to be adsorbed
In agent, ferroso-ferric oxide is 1:0.49 with the mass ratio of organic component, utilizes element analysis technology to obtain in adsorbent organic component
Grafted chain is 1.07:1 with the mass ratio of chitosan.
Embodiment 5
Weighing chitosan (viscosity-average molecular weight is 150,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:3.25:1.19:60:1.5), dissolving, ultrasonic 5min, obtain mixed solution.
Through peristaltic pump, the mixed solution of above-mentioned synthesis is instilled (hydrogen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min
In sodium oxide-alcohol-water mixed solution, sodium hydroxide, ethanol, the mass ratio of water are 1:3:6, the mixed solution of above-mentioned synthesis and
The mass ratio of the mixed solution of sodium hydroxide-alcohol-water is 1:4；Solution needs magneton to stir, and magneton rotating speed is at 80r/min),
Mixed solution rapidly becomes graininess bead, obtains uncrosslinked chitosan magnetic composite pellets after filtration.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.004:2), room temperature magnetic force
Stirring 6h, mixing speed is 30r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 60 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；Weigh the polymethyl acyloxyethyl front three of certain mass
Ammonium chloride is added in water, and dissolving obtains aqueous solution, and (mass ratio of polymethyl acyloxyethyl trimethyl ammonium chloride and water is
0.2:1, potassium peroxydisulfate, polymethyl acyloxyethyl trimethyl ammonium chloride, the quality of chitosan magnetic composite pellets of crosslinking
Ratio is 0.0125:0.4:1).Put up experimental provision, polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium is placed in dropping liquid
In funnel, it is ensured that the air-tightness of device, after logical nitrogen 15min, add potassium persulfate solution, continue logical nitrogen 10min.It is warmed up to
60 DEG C, slowly dropping polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium (15min), after dropping, react 6h.Instead
After should terminating, solution washs (acetone and the solution quality after being finally synthesizing than for 3:1) in acetone, finally pours in beaker
(submerged in water), obtains the chitosan being grafted polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration
Magnetic coupling bead adsorbent.
Result:
In the present embodiment synthesis there is core-brush configuration be grafted polymethyl acyloxyethyl trimethyl ammonium chloride
The infrared spectrum of chitosan magnetic composite pellets adsorbent is similar with the infrared spectrum shown by embodiment in Fig. 22.About
3449cm-1, 1637cm-1And 609cm-1There is characteristic peak at place, is-OH ,-NH respectively2And Fe3O4The absworption peak of middle Fe-O, meaning
Taste the successful synthesis of chitosan magnetic ball.Simultaneously at 1722cm-1There is the characteristic peak of carbonyl at place, at 1259cm-1There is ester group at place
Absworption peak, at 1377cm-1There is the absworption peak of C-N (from quaternary ammonium group) at place.Thus prove polymethyl acyloxyethyl three
Ammonio methacrylate is successfully received on chitosan magnetic composite pellets adsorbent.Fig. 7 be in embodiment 5 synthesis there is core-brush
The TEM of the chitosan magnetic composite pellets adsorbent being grafted polymethyl acyloxyethyl trimethyl ammonium chloride of structure.From
Fig. 7 sees, Fe 3 O 4 magnetic particle is with nano level formal distribution in the inside of adsorbent, and black part is divided into chitosan to divide
Son, and edge transparent part is the polymethyl acyloxyethyl trimethyl ammonium chloride long-chain in grafting.
The chitosan being grafted polymethyl acyloxyethyl trimethyl ammonium chloride with core-brush configuration of final synthesis
Magnetic coupling bead adsorbent carries out quantitative analysis: utilizing drying technology to obtain adsorbent water content is 70%, utilizes high temperature to burn
It is 1:0.61 that burning technology obtains the mass ratio of ferroso-ferric oxide and organic component in adsorbent, utilizes element analysis technology to be inhaled
In attached dose of organic component, grafted chain is 1.96:1 with the mass ratio of chitosan.
Embodiment 6
Weighing chitosan (viscosity-average molecular weight is 100,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:3.02:1.11:80:1), dissolving, ultrasonic 5min, obtain mixed solution.Warp
The mixed solution of above-mentioned synthesis is instilled (hydrogen-oxygen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min by peristaltic pump
Changing sodium hydroxide, ethanol, the mass ratio of water in sodium-alcohol-water mixed solution is 1:3:6, the mixed solution of above-mentioned synthesis and hydrogen
The mass ratio of the mixed solution of sodium oxide-alcohol-water is 1:4；Solution needs magneton to stir, and magneton rotating speed is at 80r/min), mixed
Close solution and rapidly become graininess bead, after filtration, obtain uncrosslinked chitosan magnetic composite pellets.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.001:1), room temperature magnetic force
Stirring 20h, mixing speed is 30r/min, reacts afterwash, obtains the chitosan magnetic composite pellets of crosslinking.
By the chitosan magnetic composite pellets of crosslinking obtained in the previous step, after being added in four-necked bottle, add the water (shell of crosslinking
The mass ratio of polysaccharide magnetic coupling bead and water is 1:5), agitating heating at 40 DEG C；Then measure potassium peroxydisulfate, be added in water molten
Solution obtains aqueous solution (mass ratio of potassium peroxydisulfate and water is 1:20)；The polyacrylic acid weighing certain mass is added in water, dissolves
(mass ratio of polyacrylic acid and water is 0.15:1, and potassium peroxydisulfate, polyacrylic acid, the chitosan magnetic of crosslinking are answered to obtain aqueous solution
The mass ratio closing bead is 0.0125:0.3:1).Put up experimental provision, polyacrylic acid aqueous solution is placed in Dropping funnel, really
The air-tightness of protection device, after logical nitrogen 25min, adds potassium persulfate solution, continues logical nitrogen 10min.It is warmed up to 40 DEG C, slowly
Dropping polyacrylic acid aqueous solution (10min), after dropping, reacts 5h.After reaction terminates, solution washs (acetone in acetone
Be finally synthesizing after solution quality than for 3:1), finally pour into (submerged in water) in beaker, obtain that there is core-brush configuration
Be grafted polyacrylic chitosan magnetic composite pellets adsorbent.
Result:
In the present embodiment, the polyacrylic chitosan magnetic composite pellets that has been grafted with core-brush configuration of synthesis is adsorbed
The infrared spectrum of agent is similar with the infrared spectrum shown by embodiment in Fig. 21.At about 3449cm-1, 1637cm-1And 609cm-1
There is characteristic peak at place, is-OH ,-NH respectively2And Fe3O4The absworption peak of middle Fe-O, it is meant that the one-tenth of chitosan magnetic composite pellets
Merit synthesizes.And there is C=O (1718cm above-1, from carboxyl) characteristic peak.Prove that carboxyl is introduced in magnetic material, it was demonstrated that
Polyacrylic acid chain is successfully grafted on chitosan magnetic composite pellets adsorbent.Fig. 8 be in embodiment 6 synthesis there is core-brush
The TEM being grafted polyacrylic chitosan magnetic composite pellets adsorbent of structure.See from Fig. 8, Fe 3 O 4 magnetic
Particle is with nano level formal distribution in the inside of adsorbent, and black part is divided into chitosan molecule, and edge transparent part is for connecing
Polyacrylic acid long-chain on branch.
The polyacrylic chitosan magnetic composite pellets adsorbent that has been grafted with core-brush configuration of final synthesis is carried out
Quantitative analysis: utilizing drying technology to obtain adsorbent water content is 83%, utilizes high temperature sintering technology to obtain four oxygen in adsorbent
The mass ratio changing three-iron and organic component is 1:0.53, utilize element analysis technology obtain in adsorbent organic component grafted chain with
The mass ratio of chitosan is 1.39:1.
Embodiment 7
A kind of application of the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration
In the conical flask of each 150mL, it is separately added into the modified shell with core-brush configuration prepared by 1g embodiment 1-6
Polysaccharide magnetic coupling bead adsorbent.Then, the diclofenac that 100mL pH is respectively the 100ppm of 4,6,8,10,12 is added
Sodium water solution.After covering tightly stopper, fully concussion conical flask, after 24 hours, measures each adsorbent adsorbance under the conditions of each pH,
Result is as shown in Figure 10.
From fig. 10 it can be seen that in the pH scope (4-12) surveyed, the core-brush that has synthesized in embodiment 1-6 is tied
The modification of chitosan magnetic coupling bead adsorbent of structure is respectively provided with the ability of certain removing medicine diclofenac sodium.Wherein, real
Execute the modification of chitosan magnetic coupling bead adsorbent with core-brush configuration of synthesis in example 2, there is under equal conditions maximum
Adsorbance.
Comparative example 1
Weighing chitosan (viscosity-average molecular weight is 200,000), add deionized water, (chitosan is complete to be then directly added into concentrated hydrochloric acid
CL), then weigh FeCl3·6H2O and FeCl2·4H2O is directly added into above-mentioned solution (chitosan and FeCl3·6H2O、
FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid are 1:2.32:0.85:70:1), dissolving, ultrasonic 5min, obtain mixed solution.Warp
The mixed solution of above-mentioned synthesis is instilled (hydrogen-oxygen in sodium hydroxide-alcohol-water mixed solution with the flow velocity of 1mL/min by peristaltic pump
Changing sodium hydroxide, ethanol, the mass ratio of water in sodium-alcohol-water mixed solution is 1:3:6, the mixed solution of above-mentioned synthesis and hydrogen
The mass ratio of the mixed solution of sodium oxide-alcohol-water is 1:4；Solution needs magneton to stir, and magneton rotating speed is at 80r/min), mixed
Close solution and rapidly become graininess bead, after filtration, obtain uncrosslinked chitosan magnetic composite pellets.
Uncrosslinked chitosan magnetic composite pellets obtained in the previous step being added in water, adding mass fraction is 25%
Glutaraldehyde solution (uncrosslinked chitosan magnetic composite pellets, glutaraldehyde, the mass ratio of water are 1:0.1:40), room temperature magnetic force stirs
Mixing 24h, mixing speed is 20r/min, reacts afterwash, obtains chitosan magnetic composite pellets adsorbent.
Result:
Fig. 2 is the infrared spectrum of the chitosan magnetic composite pellets adsorbent of synthesis in this comparative example.Chitosan magnetic is multiple
Close bead adsorbent at about 3449cm-1, 1637cm-1And 609cm-1There is characteristic peak at place, is-OH ,-NH respectively2And Fe3O4In
The absworption peak of Fe-O, it is meant that the successful synthesis of chitosan magnetic composite pellets.Fig. 9 is the chitose magnetic of synthesis in comparative example 1
The TEM of property composite pellets adsorbent.Adsorb by comparing the modification of chitosan magnetic coupling bead with core-brush configuration of synthesis
The TEM of agent, it appeared that grafting adsorbent have high transparency and low brightness, show modification adsorbent exist core-
Brush configuration.
By the adsorbent in embodiment 7 by " the modification of chitosan magnetic with core-brush configuration synthesized in embodiment 1-6
Property composite pellets adsorbent " make in comparative example the chitosan magnetic composite pellets adsorbent of synthesis into, remaining is equal to embodiment
7, obtain the adsorbance of the chitosan magnetic composite pellets adsorbent diclofenac sodium of synthesis in this comparative example, see Figure 10.
From fig. 10 it can be seen that although by having amino group, chitosan magnetic composite pellets adsorbent itself has certain suction
Attached amount, but, compared to having the modification of chitosan magnetic coupling bead adsorbent of core-brush configuration, chitosan magnetic coupling is little
The adsorbance of ball self absorption diclofenac sodium is the lowest.This illustrates again, and the core-brush that has synthesized in embodiment 1-6 is tied
In the modification of chitosan magnetic coupling bead adsorbent of structure, grafted monomers forms core-brush configuration adsorbent and plays absorption important
Effect；And chitosan magnetic composite pellets is in addition to avoiding secondary pollution, strengthening adsorbent separability, only play faint association
Same adsorption.
The chitosan magnetic composite pellets adsorbent of final synthesis carries out quantitative analysis: utilize drying technology to obtain adsorbent
Water content is 87%, and utilizing high temperature sintering technology to obtain the mass ratio of ferroso-ferric oxide and organic component in adsorbent is 1:
0.28。
Claims (10)
1. a chitosan magnetic composite pellets adsorbent with core-brush configuration, it is characterised in that: its basic structure formula is:
In formula, P is
A kind of chitosan magnetic composite pellets adsorbent with core-brush configuration the most according to claim 1, its feature exists
In: in described composite pellets adsorbent, macromolecular grafted chain is (0.05～2.32) with the mass ratio of chitosan: 1；Four oxidations
Three-iron is 1:(0.31～0.67 with the mass ratio of organic component).
3. the preparation method of the chitosan magnetic composite pellets adsorbent with core-brush configuration described in claim 1, its step
Suddenly it is:
(1) chitosan is dissolved in deionized water, is subsequently added concentrated hydrochloric acid, after chitosan dissolves, add FeCl3·6H2O and
FeCl2·4H2O ultrasonic dissolution obtains mixed solution；
(2) preparation sodium hydroxide-alcohol-water mixed solution, under agitation, instills it by the mixed solution in step (1)
Middle formation graininess bead, obtains uncrosslinked chitosan magnetic composite pellets after filtration；
(3) the uncrosslinked chitosan magnetic composite pellets in step (2) is added glutaraldehyde solution, stir 6～24h, reaction
Afterwash, obtains the chitosan magnetic composite pellets of crosslinking；
(4) the chitosan magnetic composite pellets of crosslinking in step (3) is dispersed in water, adds under the conditions of inert gas shielding
Initiator, then heats to 40～60 DEG C, continuously adds monomer solution reaction 3～6h, and reaction uses washing with acetone after terminating, and obtains
The described chitosan magnetic composite pellets adsorbent with core-brush configuration.
The preparation method of the chitosan magnetic composite pellets adsorbent with core-brush configuration the most according to claim 3, its
It is characterised by: chitosan and FeCl in step (1)3·6H2O、FeCl2·4H2O, water, the mass ratio of concentrated hydrochloric acid be 1:(2.32～
3.48): (0.85～1.28): (50～80): (0.5～2), ultrasonic 5min.
5. according to the preparation side of the chitosan magnetic composite pellets adsorbent with core-brush configuration described in claim 3 or 4
Method, it is characterised in that: in step (2), sodium hydroxide, ethanol, the mass ratio of water are 1:3:6；The mixed solution of step (1) and hydrogen
The mass ratio of sodium oxide-alcohol-water mixed solution is 1:(3～5), the rate of addition of mixed solution is 1mL/min, and stirring uses
Magneton stirs, and magneton rotating speed is 80r/min.
The preparation method of the chitosan magnetic composite pellets adsorbent with core-brush configuration the most according to claim 3, its
Be characterised by: chitosan magnetic composite pellets uncrosslinked in step (3), glutaraldehyde, the mass ratio of water be 1:(0.0005～
0.005): (0.5～2.5), mixing speed is 20-60r/min.
The preparation method of the chitosan magnetic composite pellets adsorbent with core-brush configuration the most according to claim 3, its
Being characterised by: the initiator described in step (4) is potassium peroxydisulfate, described monomer is polymethyl acyloxyethyl trimethyl
Ammonium chloride, polyacrylic acid or polymethyl methacrylate.
8. according to the preparation side of the chitosan magnetic composite pellets adsorbent with core-brush configuration described in claim 3 or 7
Method, it is characterised in that: the chitosan magnetic composite pellets of crosslinking is 1:5 with the mass ratio of water in step (4), initiator, monomer,
The mass ratio of the chitosan magnetic composite pellets of crosslinking is 0.0125:(0.01～0.5): 1.
The preparation method of the chitosan magnetic composite pellets adsorbent with core-brush configuration the most according to claim 3, its
It is characterised by: in step (4), acetone is 1:3 with the mass ratio of reaction solution.
10. the chitosan magnetic composite pellets adsorbent with core-brush configuration described in claim 1 or 2 processes neck at water
Application in territory.
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Application publication date: 20161026 |