CN106311188A - Chitosan/palygorskite/polyacrylamide composite hydrogel preparation method - Google Patents

Chitosan/palygorskite/polyacrylamide composite hydrogel preparation method Download PDF

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CN106311188A
CN106311188A CN201610828084.7A CN201610828084A CN106311188A CN 106311188 A CN106311188 A CN 106311188A CN 201610828084 A CN201610828084 A CN 201610828084A CN 106311188 A CN106311188 A CN 106311188A
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chitosan
quality
paligorskite
solution
preparation
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俞洁
张志超
陆泉芳
郑继东
王星
张晓敏
杨恕修
杨武
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Northwest Normal University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/56—Acrylamide; Methacrylamide
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Abstract

A chitosan/palygorskite/polyacrylamide composite hydrogel preparation method includes: adding acetic acid into Na2SO4 solution to obtain acidized Na2SO4 solution; adding chitosan into the acidized Na2SO4 solution in a mass being 60-100 times of that of the chitosan, and stirring; adding palygorskite in a mass being 0.1-1 time of that of the chitosan, and stirring; adding acrylamide and N,N'-methylene bisacrylamide, and stirring to form mixed liquid dispersed uniformly; inserting two electrodes into the liquid, discharging under a voltage of 650-720V, stirring, cooling to the room temperature, washing, and drying to obtain chitosan/palygorskite/polyacrylamide composite hydrogel. The preparation method is mild in condition and free of N2 protection and addition of chemical initiators, so that environment friendliness is achieved. The hydrogel prepared according to the method is an adsorbent excellent in performance and can be hopefully applied to purification of heavy metal wastewater.

Description

The preparation method of chitosan/Paligorskite/polyacrylamide composite aquogel
Technical field
The invention belongs to functional high polymer material field, relate to the chitosan/Paligorskite of a kind of Adsorption of Heavy Metal Ions/poly- The preparation method of acrylamide organic/inorganic compound hydrogel material.
Background technology
Along with the fast development of modern industry, heavy metal ion has become the most universal to the pollution of aquatic ecosystem The environmental problem paid close attention to.Heavy metal ion in water body is mainly derived from metal exploitation, smelts and process the Industry Waste of discharge Water, remaining in the heavy metal in water body (particularly lead, cadmium, hydrargyrum, chromium, copper) can not be biodegradable, but can be in the life of food chain Under thing amplification, it is progressively enriched with, finally enters in consumer's body, human security is constituted great threat.Therefore, water is removed Heavy metal ion in body is most important to environmental conservation.In purifying water body, the common method of heavy metal ion mainly has chemistry heavy Shallow lake, oxidoreduction, electrolysis, reverse osmosis, solvent extraction, ion exchange, absorption etc..Wherein, absorption method due to have simple to operate, Environmental protection, removal efficiency advantages of higher, have broad application prospects in terms of waste water process.The most frequently used adsorbent is alive Property charcoal, but adsorbance is low.Recently, with hydrogel as adsorbent for heavy metal by people's extensive concern.
Hydrogel is the polymer that a class has three-dimensional net structure, and it can absorb sole mass hundred times very in water To the water of thousands of times, and can continue to after water absorption and swelling keep its original structure to be not dissolved；Hydrogel has the suction of uniqueness Water, water conservation and bionical characteristic, specific surface area is big, and mechanical property is high, is widely used in agricultural gardening, medical and health, biological work The field such as journey, sewage purification.In terms of sewage purification, hydrogel is mainly by following two mechanism Adsorption of Heavy Metal Ions: one It is physical absorption, by intermolecular Van der Waals force；Two is chemisorbed, such as hydroxyl, amino, amide Han hydrophilic radical in hydrogel Base, sulfonic group, carboxyl etc., they can exchange with heavy metal generation ion, chelating ligands.Due to hydrogel synthesis with low cost, Adsorbance is higher, reusable edible, has been acknowledged as a kind of removal from industrial wastewater and natural water having development potentiality Or reclaim the new material of heavy metal.At present, mainly prepare hydrogel with oil product such as acrylic acid etc. for raw material, there is raw material and hold high Expensive, condition is harsh, product has the problems such as certain toxicity, difficult for biological degradation.
The preparation method of hydrogel mainly has chemistry initiation, light-initiated, microwave causes, radiation causes, glow discharge electrolysis Plasma initiations etc., these methods are respectively arranged with quality.Although chitosan-based hydrogel such as chitosan/acrylic acid (application number 201210542341.2), chitosan/Polyethylene Glycol/acrylic acid (ACTA Scientiae Circumstantiae, 2016) and clay-based hydrogel such as slope thread Stone/poly-(2-acrylamide-2-methylpro panesulfonic acid-co-acrylic acid) resistance to salt resin (application number 201410003027.6), trematodiasis Stone/poly-(2-acrylamide-2-methylpro panesulfonic acid-co-acrylic acid) water-absorbing resin (fine chemistry industry, 2015) all can be put with aura Prepared by electricity electrolytic plasma method, but be that raw material passes through glow discharge electrolysis plasma with chitosan, Paligorskite and acrylamide Body or additive method initiation are prepared organic/inorganic hydrogel and be have not been reported, and such hydrogel is used for heavy metal containing sewage The report purified is less.
Summary of the invention
It is an object of the invention to provide a kind of not chitosan/Paligorskite/polyacrylamide with oil product as raw material multiple The preparation method of Heshui gel, raw material is cheap, mild condition, and prepared hydrogel is biodegradable.
For achieving the above object, the technical solution adopted in the present invention is: a kind of chitosan/Paligorskite/polyacrylamide The preparation method of compound hydrogel material, it is characterised in that this preparation method specifically sequentially includes the following steps:
Step 1:Na2SO4Solution adds acetic acid, Na must be acidified2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4's Quality is 1g, and the quality of acetic acid is this acidifying Na2SO4The 1% of solution quality；
Step 2: chitosan is added the acidifying Na that quality is chitosan mass 60～100 times2SO4In solution；At 60～80 DEG C At a temperature of stir 30～60 min, being subsequently adding quality is chitosan mass 0.1～the Paligorskite of 1 times, continue stirring；The most again Add acrylamide and N, N'-methylene-bisacrylamide, stirring, form finely dispersed mixing liquid；
Step 3: continuously stirred, inserts two electrodes in finely dispersed liquid, under the voltage of 650～720 V discharge 1～ 10min, stirs 2～5h at a temperature of 60～80 DEG C, is cooled to room temperature, obtains product；Wash this product, dry, pulverize, obtain Chitosan/Paligorskite/polyacrylamide composite aquogel.
Preparation method hinge structure of the present invention has the advantage that
1. prepare chitosan/Paligorskite/polyacrylamide copolymer hydrogel with glow discharge electrolysis plasma initiation, side Method is novel.
2., with chitosan, Paligorskite and acrylamide as raw material, N, N'-methylene-bisacrylamide is cross-linking agent, at water Solution cause a step to prepare chitosan/Paligorskite/polyacrylamide copolymer hydrogel with glow discharge electrolysis plasma, Raw material is easy to get, and technique is simple, synthesizes low cost, and product is biodegradable.
3. preparation condition is gentle, it is not necessary to N2Protection, it is not necessary to add chemical initiator, environmental protection, be not required to other initiation sides Formula, it is to avoid secondary pollution that initiator brings and cause the material structure of synthesis uneven.
The most whole preparation process is to carry out in water solution system, simplifies the Enrichment purification technique of hydrogel, decreases The emulsifying agent pollution to material, enhances its biological safety.
5. the hydrogel heat stability of preparation is higher, is difficult to decompose before 200 DEG C, and the scope of application is wider.
6. the hydrogel of preparation can be used for purification and the separation of heavy metal ion-containing waste water.
Accompanying drawing explanation
Fig. 1 is the structural formula of chitosan.
Fig. 2 is at acidifying with acetic acid Na2SO4In solution, glow discharge electrolysis plasma prepares the volt-ampere characteristic song of hydrogel Line.
When Fig. 3 is to apply 700 V voltage, it is acidified Na2SO4The typical emission spectra figure of solution.
Fig. 4 is the infrared spectrogram of composite aquogel raw materials used and prepared in preparation method of the present invention.
Fig. 5 is the XRD spectra of chitosan.
Fig. 6 is the XRD spectra of Paligorskite.
Fig. 7 is the XRD spectra of the composite aquogel using the inventive method to prepare.
Fig. 8 is the TG curve chart of composite aquogel raw materials used and prepared in preparation method of the present invention.
Fig. 9 is the SEM figure of Paligorskite.
Figure 10 is the SEM figure of the composite aquogel using preparation method of the present invention to prepare.
Figure 11 is the rectangular histogram of the composite aquogel heavy metal ionic adsorption amount that preparation method of the present invention prepares.
Detailed description of the invention
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.
The invention provides the preparation method of a kind of not composite aquogel with oil product as raw material, concrete by following step Suddenly carry out:
Step 1:Na2SO4Solution adds acetic acid (HAc), carries out being acidified (acidifying with acetic acid is to prepare for dissolving chitosan), Acidifying Na2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4Quality be 1g, the quality of acetic acid is this acidifying Na2SO4Molten The 1% of liquid quality；
Step 2: by the acidifying Na that chitosan (CS) addition quality is chitosan mass 60～100 times2SO4In solution；60～ With the rotating speed of 90～120 r/min at a temperature of 80 DEG C, stirring 30～60 min, make chitosan dissolve, being subsequently adding quality is shell Polysaccharide quality 0.1～the Paligorskite (PGS) of 1 times, continue stirring 20～40 min and make Paligorskite be uniformly dispersed；Add acrylamide (AM) and N, N'-methylene-bisacrylamide (MBA), the quality of acrylamide used is 5～12 times of chitosan mass, used The quality of N, N'-methylene-bisacrylamide is the 1～5% of acrylamide quality used, continues stirring 10～20 min, is formed Finely dispersed mixing liquid；
Step 3: continuously stirred, inserts two electrodes in mixing liquid, and discharge under the voltage of 650～720 V 1～10 min, This mixing liquid becomes thick, continues stirring 2～5 h, be cooled to room temperature, obtain product at a temperature of 60～80 DEG C；Use water After repeatedly washing this product, dry, pulverize at a temperature of 50～70 DEG C, obtain chitosan/Paligorskite/polyacrylamide Compound Water Gel.
It is said that in general, hydrogel preparation mostly by one or more monomers 65～80 DEG C, reduced pressure, N2Under protection, With potassium peroxydisulfate as initiator, through multistep reaction, final initiation is polymerized and cross-links and obtain.Preparation method of the present invention need not appointed In the case of what chemical initiator, directly with chitosan, Paligorskite and acrylamide as raw material, with N, N'-methylene bisacrylamide Amide is cross-linking agent, in aqueous, causes one-step synthesis of chitosan/slope thread with glow discharge electrolysis plasma (GDEP) Stone/polyacrylamide (CS/PGS/PAM) hydrogel.This preparation method technique is simple, and mild condition is (without N2Protection), reaction Controlled (controlling reaction by controlling voltage), without any chemical initiator, non-secondary pollution, environmental protection, required temperature Spend low (65～80 DEG C), a step can complete the preparation of product, be one and meet the environment amenable green of " sustainable development " Color causes new synthesis technology.
Chitosan (Chitosan, CS) is a kind of natural polymers that chitin obtains through deacetylation, Being made up of 2-Acetamido-2-deoxy-D-glucose unit and glucosamine unit, its structural formula is shown in Fig. 1.Chitosan abundance, can give birth to Thing is degraded, and has the biocompatibility of uniqueness.The intramolecular C of CS6-OH、C3-OH and C2-NH2Can be by hydrogen bond and ion Key-like becomes to have similar cancellated cage molecule, many heavy metal ion can be coordinated, chelates and is effectively enriched with Reclaim, thus utilize this raw material development and exploitation several functions material to have important Research Significance and market prospect. But, amino free in chitosan molecule can accept proton and become salt (-NH3 +), dissolve in the solution that acidity is stronger, cause Chitosan runs off, and seriously limits its application.In order to make up these shortcomings, people have carried out a large amount of study on the modification to it, such as shell The chemical reactions such as polysaccharide can be condensed, complexation, alkylation, acylation, carboxy methylation, sulfonation, generate the shell insoluble in acid and gather Sugar derivatives makes it have a good application prospect in terms of effluent containing heavy metal ions process., with existing condensation, network The modified chitosan derivatives bio-refractory of the methods such as conjunction, alkylation, acylation, carboxy methylation, sulfonation, specific surface area Little, adsorbance is low.
Paligorskite (Palygorskite, PGS) is a kind of zeopan clay mineral with layer structure, due to it -OH is contained on interlayer and surface, can form organic/inorganic copolymerization thing with double bond containing organic monomer generation graft copolymerization, improve material The performances such as the water suction of material, absorption.Acrylamido is a kind of multifunctional water-soluble non-ionic monomer, and amide groups makes it have very well Water solublity, hydrolytic stability, anti acid alkali performance and salt tolerance；Active C=C key is conducive to homopolymerization or is total to other vinyl monomers Poly-, industrial goods are with low cost.
Therefore, the cheaper starting materials that preparation method of the present invention uses is easy to get, reaction condition is gentle, be not required to any chemistry initiation Agent, without N2Protection, directly causes synthesis composite aquogel with glow discharge electrolysis plasma.This composite aquogel prepared Combine the characteristic of mineral shaped material, natural polymer and hydrogel, have with low cost, salt tolerance is high, biodegradable etc. Advantage.Meet the developing direction of high performance, multifunction and ep-type material.
Below by the current-voltage curve of glow discharge electrolysis, the qualification of active particle, the present invention side of preparation is described The advantage of method；By infrared spectrum, X-ray diffraction, thermogravimetric analysis, the structure of scanning electron microscope sign hydrogel, with hydrogel pair Its performance is evaluated by the adsorbance size of heavy metal ion.
1. glow discharge electrolysis plasma prepares the current-voltage curve of CS/PGS/PAM hydrogel
Use voltage range 0～1000 V of digital display, the LW100J2 DC voltage-stabilizing-stabilized current supply of current range 0～1000 mA Electric current in test polymerization process and voltage curve, obtain the current-voltage characteristic curve shown in Fig. 2.Whole process can be divided into: AB(voltage 0～290 V) section, voltage raises, and electric current rises, electric current and voltage linear relation, it then follows Ohm's law, often occurs The electrolytic process of rule；BC(voltage 290～470 V) section, along with the further rising of voltage, the liquid between two electrodes produces Substantial amounts of Joule heat, makes the solvent of surrounding them begin to boil off, and forms steam sheath, owing to steam sheath has insulating properties, and occurs Steam sheath is ascending, arrive the process disappeared again, thus electric current extremely unstable, numerical fluctuations is bigger；CD(voltage 470～560 V) section, electric current is relatively stable, produces stable steam sheath, is simultaneously emitted by faint flash of light, and this phenomenon is by scientist Kellogg Find the earliest, therefore referred to as Kellogg district, owing to the some particles in steam sheath ionizes under high energy electron bombards, but not Its saturated ionization degree can be reached, the phenomenon that electric current entirety is basically unchanged occurs；DE(voltage 560～720 V) section, electric current is with electricity Pressure raises and sharply increases, and steam bubble is punctured completely, produces violent aura, form plasma at anode needle point.Due to this Plasma is the gas of conduction, and electric current increases along with the rising of voltage, and voltage is gradually increased afterwards, aura intensity enhancing. In theory, voltage is the highest, and aura intensity is the biggest, produces plasma quantity the most, but voltage is the highest, and energy consumption increases, and When voltage is more than 720 V, the energy of plasma sputtered is higher, and platinum filament anode is easily melted damage.Therefore, preparation CS/ The voltage of PGS/PAM hydrogel is 560～720 V.
2. the active ion analysis produced in discharge process
Use AvaSpec-ULS 2,048 8 passage high-resolution fiber spectrometer when 200～1100 nm test 700 V etc. from Daughter emission spectrum, its resolution is 0.07 nm, minimum integration time 1.1 ms.Na it is acidified when Fig. 3 is voltage 700 V2SO4Molten Typical emission spectra figure in liquid.As seen from Figure 3, wavelength be the intense line of 283.0～306 nm be OH (A-X) transition spectrum Band；Two spectral line H of H atom are occurred that at wavelength 486.1 nm and wavelength 656.3 nmβAnd Hα；Wavelength 777.1 nm and ripple The transition spectral line of excited state O atom is occurred in that at long 844.6 nm.This be due in discharge process the water of surrounding them be vaporized, Excite, decomposition water molecule produces a large amount of HO, H, O free radicals.The spectrum of wavelength 397.2 nm belongs to the second of nitrogen the just band system Transition N2(C-B), from the discharge excitation of nitrogen in water.Meanwhile, have at wavelength 588.9 nm and wavelength 819.3 nm stronger Na spectral line, illustrates to have in electrolyte Na+。
During glow discharge electrolysis, the hydrone in steam sheath is collided by high energy electron, the moisture being excited Son is 10-13 Decomposing free radicals such as generating H, OH and O in second, main decomposition reacts sees formula (1-4):
H2O + e → H˙(1s) + HO˙(X) 5.1 e (1)
→H˙(1s) + HO˙(A) 9.2 eV (2)
→H˙(n=3) + HO˙(X)17.2 eV (3)
HO˙ → H˙(2s) + O˙(3p) 4.4 eV (4)
Certainly, hydrone is excited between the various free radicals produced and also can react, and is explained as follows:
H˙ +H˙→H2 (5)
HO˙ +HO˙→H2O2 (6)
OH + OH → H2O + O (7)
O˙ +O˙→O2 +O˙→O3 (8)
Thus illustrate, glow discharge electrolysis plasma process can produce H, OH, O, H2O2、O3Deng high activity grain Son, they are applied to the synthesis of hydrogel is a free radical polymerization process.
3. infrared test
With DIGILAB FTS 3000 FT-IR type infrared spectrometer (KBr tabletting) at 400～4000 cm–1Characterize hydrogel Structure changes.Fig. 4 is the infrared spectrogram of composite aquogel raw materials used and prepared in preparation method of the present invention.In Fig. 4: bent Line a is the infrared spectrogram of chitosan, 3433 cm-1Place's broad peak is the superposition of N-H and O-H stretching vibration absworption peak in chitosan； 2876 cm-1Place is the C-H stretching vibration absworption peak of methine on saccharide residue；1599 cm-1Place is N-H bending vibration absworption peak； 1382 cm-1Place is the deformation vibration peak of the amide III bands of a spectrum (in-plane bending vibration of N H) of chitosan；1157 cm-1Place is C-O-C(glycosidic bond is special) characteristic absorption peak；1082 cm-1Place is secondary hydroxyl groups C on chitosan3The stretching vibration of-OH absorbs Peak；1030 cm-1Place is chitosan molecule upper level hydroxyl C6The characteristic absorption peak of-OH.Curve b is the ultrared spectrum of acrylamide Figure, 3200～3500 cm-1The wide absorption band at place is-NH2Stretching vibration, 1674 cm-1Place is the stretching of C=O key in amide groups Contracting vibration, 1612 cm-1Place is the stretching vibration peak of C=C；1428 cm-1Place is CH bending vibration peak；1355 cm-1Place is amide The deformation vibration peak of III bands of a spectrum (in-plane bending vibration of N H)；1136 cm-1Place is the C N stretching vibration peak of amide.Curve c For the infrared spectrogram of PGS, 470 cm-1Place is the bending vibration absworption peak of Si-O-Si key；1028 cm-1Place is Paligorskite Si- The stretching vibration absworption peak of O-Si key；3615 cm-1Place is the Si-OH stretching vibration peak of PGS；3545 cm-1With 3411 cm-1Place For the stretching vibration of-OH in PGS absorption water, zeolite water.Curve d is the infrared spectrum of composite aquogel, 1717 cm-1Place is C=O Stretching vibration peak；1456 cm-1Place is CH bending vibration peak；1034 cm-1Place is Si-O-Si stretching vibration absworption peak；466 cm-1Place is Si-O-Si bending vibration absworption peak.It addition, from curve d it can be seen that 3557 cm of Paligorskite after graft copolymerization-1Place The absworption peak of Mg-OH disappears, and Paligorskite is at 1028 cm−1Place's feature Si-O-Si absworption peak shifts to Gao Bo after forming polymer Several 1034 cm−1Place；1082 cm–1The stretching vibration of place C O C moves on to 1095 cm−1, lay respectively at 1382 cm-1With 1355 cm-1High wave number is shifted at the deformation vibration peak of the amide III bands of a spectrum (in-plane bending vibration of N H) of place's chitosan and acrylamide 1413 cm-1Place；Meanwhile, 1612 cm−1The C=C stretching vibration peak of place AM disappears.The above results proves that CS, PGS, AM react shape Become organic/inorganic copolymer CS/PGS/PAM hydrogel.
4. XRD test
With Rigaku D/max-2400 type X-ray powder diffractometer to raw materials used and prepared answering in preparation method of the present invention The structure of Heshui gel sample is tested, and obtains the XRD figure spectrum shown in Fig. 5, Fig. 6 and Fig. 7.Fig. 5 is the XRD figure of chitosan Spectrum, as seen from Figure 5,2θBe 11.9 ° (d=0.43 nm), 20.18 ° (d=0.34 nm) place is the feature diffraction of chitosan Peak, the characteristic peak of corresponding CS segment crystallization.Fig. 6 is the XRD figure spectrum of Paligorskite, shows, 2 in figureθIt is 8.04 ° of (d=1.10 Nm) place is the characteristic diffraction peak of PGS, and 2θ =20.46 ° (d=0.45 nm) and 26.44 ° of (d=0.34 nm) places are Impurity quartz and the diffraction maximum of dolomite in PGS.The XRD figure spectrum of the composite aquogel made is shown in Fig. 7,2θ20.88 ° (d= 0.43 nm) there is maximum diffraction peak in place, and this peak entirety peak shape broadens, intensity reduce, in mild Qiu Zhuanfeng, this be due to After introducing polyacrylamide (PAM), form amorphous organic/inorganic composite material.It addition, after graft modification, Paligorskite feature The angle of diffraction does not has obvious difference, if composite aquogel is 2θIt is the characteristic diffraction peak having Paligorskite at 8.7 °, but peak subtracts by force Weak, this shows that, under the synthesis condition of composite aquogel, the cladding of chitosan and acrylamide does not change the structure of Paligorskite. In a word, chitosan, Paligorskite and acrylamide form amorphous polymer by graft copolymerization.
5. thermogravimetric test
With PE TG/DTA 6300 type thermogravimetric-differential scanning amount thermal analyzer measure the raw materials used sample of preparation method of the present invention and The heat stability of the composite aquogel sample prepared.Fig. 8 is the thermogravimetric curve figure of chitosan, Paligorskite and composite aquogel.Fig. 8 In curve a be the thermogravimetric curve of chitosan, by this curve it can be seen that the thermal decomposition of chitosan is divided into 2 stages, the first rank Section is that temperature 25 DEG C arrives temperature 148 DEG C, and 6.2% weightlessness in this stage is caused by losing of water；2nd stage was temperature 148 DEG C to temperature 787 DEG C, in this second stage weightless 59.2%, being to be caused by the C-C bond fission of chitosan main chain, maximum heat is decomposed Temperature is 300 DEG C.Curve b in Fig. 8 is the thermogravimetric curve of Paligorskite, by this curve it can be seen that Paligorskite is in temperature 788 Total weightlessness 5.4% before DEG C, this is caused by slowly losing of water.Curve c in Fig. 8 is the thermogravimetric curve of composite aquogel, should Thermogravimetric curve is divided into 3 stages: 11.7% weightlessness of the 1st stage 25～211 DEG C is by a small amount of water absorbed and a small amount of little Molecular organic loses caused；Chitosan and poly-third in 2nd stage 211～340 DEG C of weightlessness 19.2%, mainly graft copolymer Acrylamide loses caused by amido, hydroxyl；3rd stage 340～550 DEG C of weightlessness 16.5%, for the PAM of the crosslinking in graft copolymer Decompose and chitosan ring decomposes caused by dehydration, decarboxylation；550～788 DEG C of weightlessness having 13.3%, this is owing to main chain decomposition ruptures Caused.Three curves in comparison diagram 8 are it can be seen that the weight-loss ratio of composite aquogel is less than the weight-loss ratio of chitosan, and thermogravimetric Curve is significantly different, illustrates that acrylamide is grafted on Paligorskite and chitosan under glow discharge electrolysis plasma causes, Improve the heat stability of composite aquogel.
6. sem test
With the pattern of sample after JSM-5600LV scanning electron microscopic observation metal spraying.Fig. 9 and Figure 10 is respectively Paligorskite and compound water congealing The scanning electron microscope (SEM) of glue.From fig. 9, it can be seen that Paligorskite is club shaped structure, the diameter of nanometer palygorskite about 40～60 nm, A length of 400～800 nm of nanometer rods.After forming composite aquogel, from fig. 10 it can be seen that composite aquogel presents loose Loose structure, bar-shaped Paligorskite structure disappears, and granule boundary obscures, and inorganic organic biphase compatibility is preferable, show CS, PGS and AM is compound preferably.Owing to the structure of composite aquogel has bigger specific surface area than smooth particle, when hydrogel runs into During heavy metal ion solution, increase and the contact area of heavy metal ion solution, be effectively improved hydrogel heavy metal The rate of adsorption of ion and adsorbance.
7. the absorption of composite aquogel heavy metal ion
Preparation mass body volume concentrations is the Pb of 1000 mg/L2+Solution, under room temperature, accurately weighs 0.030 g and uses system of the present invention The composite aquogel that Preparation Method prepares is put in 100mL vial, is subsequently adding this Pb2+ Solution 100mL, is placed on agitator After velocity fluctuation 4 h of 100 r/min, filter, measure the concentration of solution before and after adsorbing with plasma emission spectrometer, inhale Attached amount is calculated as follows:
In formula,qFor adsorbance unit, mg/g；C 0For Pb in solution before absorption2+Concentration, unit mg/L；CFor in solution after absorption Pb2+Concentration, unit mg/L；VFor liquor capacity, unit L；mFor the quality of composite aquogel used, unit g.
According to measuring Pb2+The method of adsorbance, measures the composite aquogel pair using preparation method of the present invention to prepare respectively Ni2+、Cd2+And Cu2+Adsorbance, obtain the adsorbance rectangular histogram of this composite aquogel heavy metal ion shown in Figure 11.Can To find out, this composite aquogel Pb (II), Cd (II), Cu (II), the adsorbance of Ni (II) are respectively 156.7 mg/g, 96.6 Mg/g, 108.3 mg/g, 51.7 mg/g, illustrate this composite aquogel can from waste water enriching and recovering heavy metal ion.Table 1 Give the adsorbance of the hydrogel heavy metal that this patent prepares and the comparison of other hydrogel adsorbances.It can be seen that use The hydrogel that preparation method of the present invention prepares can adsorb contents of many kinds of heavy metal ion, and the adsorbance of some heavy metal ion is higher than The adsorbance of hydrogel prepared by other method.This is because the HO that glow discharge electrolysis plasma produces adds to polymerization In thing chain, causing-OH group and heavy metal ion coordination, adsorbance increases.
Relevant CS material prepared by table 1 distinct methods is to Pb2+、Cd2+、Cu2+And Ni2+Adsorbance compare
Embodiment 1
Na2SO4Solution adds acetic acid, is acidified, Na must be acidified2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4 Quality be 1g, the quality of acetic acid is this acidifying Na2SO4The 1% of solution quality；It is chitosan mass 60 that chitosan adds quality Acidifying Na again2SO4In solution；With the rotating speed of 120 r/min at a temperature of 60 DEG C, stir 30 min, make chitosan dissolve, so Rear addition quality is the Paligorskite of chitosan mass 0.1 times, continues stirring 20 min and makes Paligorskite be uniformly dispersed；It is added followed by Acrylamide and N, N'-methylene-bisacrylamide, the quality of acrylamide used is 5 times of chitosan mass, N used, N'- The quality of methylene-bisacrylamide is the 1% of acrylamide quality used, continues stirring 10 min, forms finely dispersed liquid Body；Inserting two electrodes in this finely dispersed liquid, discharge under the voltage of 650 V 10 min, and finely dispersed liquid becomes For thick, at a temperature of 60 DEG C, stir 5 h, be cooled to room temperature, obtain product；After repeatedly washing with water, dry at 50 DEG C Dry, pulverize, obtain chitosan/Paligorskite/polyacrylamide composite aquogel.
The performance of the composite aquogel prepared: during 90 min, absorption reaches saturated, to Pb (II), Cd (II), Cu (II), Ni (II) adsorbance is respectively 156.7 mg/g, 96.6 mg/g, 108.3 mg/g, 51.7 mg/g.
Embodiment 2
Na2SO4Solution adds acetic acid, is acidified, Na must be acidified2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4 Quality be 1g, the quality of acetic acid is this acidifying Na2SO4The 1% of solution quality；It is chitosan mass that chitosan adds quality The acidifying Na of 100 times2SO4In solution；With the rotating speed of 90 r/min at a temperature of 80 DEG C, stir 60 min, make chitosan dissolve, It is subsequently adding the Paligorskite that quality is chitosan mass 1 times, continues stirring 40 min and make Paligorskite be uniformly dispersed；It is added followed by Acrylamide and N, N'-methylene-bisacrylamide, the quality of acrylamide used is 12 times of chitosan mass, N used, The quality of N'-methylene-bisacrylamide is the 5% of acrylamide quality used, continues stirring 20 min, is formed finely dispersed Liquid；Inserting two electrodes in this finely dispersed liquid, discharge under the voltage of 720 V 1 min, and finely dispersed liquid becomes For thick, at a temperature of 80 DEG C, stir 2 h, be cooled to room temperature, obtain product；After repeatedly washing with water, 70 DEG C of temperature Under dry, pulverize, obtain chitosan/Paligorskite/polyacrylamide composite aquogel.
The performance indications of the composite aquogel prepared: during 90 min, absorption reaches saturated, to Pb (II), Cd (II), Cu substantially (II), the adsorbance of Ni (II) is respectively 123.3 mg/g, 103.3 mg/g, 106.7 mg/g, 55 mg/g.
Embodiment 3
Na2SO4Solution adds acetic acid, is acidified, Na must be acidified2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4 Quality be 1g, the quality of acetic acid is this acidifying Na2SO4The 1% of solution quality；It is chitosan mass 80 that chitosan adds quality Acidifying Na again2SO4In solution；With the rotating speed of 105 r/min at a temperature of 70 DEG C, stir 45 min, make chitosan dissolve, so Rear addition quality is the Paligorskite of chitosan mass 0.55 times, continues stirring 30 min and makes Paligorskite be uniformly dispersed；Add the most again Entering acrylamide and N, N'-methylene-bisacrylamide, the quality of acrylamide used is 8.5 times of chitosan mass, used The quality of N, N'-methylene-bisacrylamide is the 3% of acrylamide quality used, continues stirring 15 min, and formation is uniformly dispersed Liquid；Inserting two electrodes in this finely dispersed liquid, discharge under the voltage of 685 V 6 min, finely dispersed liquid Become thick, at a temperature of 70 DEG C, stir 3.5h, be cooled to room temperature, obtain product；After repeatedly washing with water, 60 DEG C of temperature Under dry, pulverize, obtain chitosan/Paligorskite/polyacrylamide composite aquogel.
The performance indications of the composite aquogel prepared: during 90min, absorption reaches saturated, to Pb (II), Cd (II), Cu substantially (II), the adsorbance of Ni (II) is respectively 128.3mg/g, 71.7mg/g, 33.3mg/g, 61.7mg/g.

Claims (3)

1. the preparation method of chitosan/Paligorskite/polyacrylamide compound hydrogel material, it is characterised in that this is prepared Method specifically sequentially includes the following steps:
Step 1:Na2SO4Solution adds acetic acid, Na must be acidified2SO4Solution, every liter of this acidifying Na2SO4Na in solution2SO4Matter Amount is 1g, and the quality of acetic acid is this acidifying Na2SO4The 1% of solution quality；
Step 2: chitosan is added the acidifying Na that quality is chitosan mass 60～100 times2SO4In solution；At 60～80 DEG C At a temperature of stir 30～60 min, being subsequently adding quality is chitosan mass 0.1～the Paligorskite of 1 times, continue stirring；The most again Add acrylamide and N, N'-methylene-bisacrylamide, stirring, form finely dispersed mixing liquid；
Step 3: continuously stirred, inserts two electrodes in finely dispersed liquid, under the voltage of 650～720 V discharge 1～ 10min, stirs 2～5h at a temperature of 60～80 DEG C, is cooled to room temperature, obtains product；Wash this product, dry, pulverize, obtain Chitosan/Paligorskite/polyacrylamide composite aquogel.
The preparation method of chitosan/Paligorskite/polyacrylamide compound hydrogel material the most according to claim 1, its Being characterised by, in described step 2, chitosan adds acidifying Na2SO4In solution, the rotating speed with 90～120 r/min stirs.
The preparation method of chitosan/Paligorskite/polyacrylamide compound hydrogel material the most according to claim 1, its It is characterised by, in step 2 quality is chitosan mass 5～12 times of acrylamide used, N used, N'-methylene bisacrylamide The quality of amide is the 1～5% of acrylamide quality used.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915803A (en) * 2017-10-23 2018-04-17 昆明理工大学 It is a kind of to prepare the method for removing cadmic nano-composite gel in waste water
CN115558301A (en) * 2022-09-28 2023-01-03 闽江学院 Anti-freezing hydrogel with high flexibility and high ionic conductivity and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644590A (en) * 2004-12-17 2005-07-27 西北师范大学 Method for synthesizing super-strong water absorbing agent induced by contacting glow plasma
CN102690535A (en) * 2012-06-07 2012-09-26 复旦大学 Organic modified nano-attapulgite particles and preparation method thereof
CN102977271A (en) * 2012-12-14 2013-03-20 西北师范大学 Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma
US20140219973A1 (en) * 2011-08-23 2014-08-07 Victoria L. Boyes Composite Hydrogel-Clay Particles
CN105709704A (en) * 2016-02-03 2016-06-29 西北师范大学 Preparation of chitosan-based adsorption agent and application of chitosan-based adsorption agent to heavy metal ion wastewater treatment

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644590A (en) * 2004-12-17 2005-07-27 西北师范大学 Method for synthesizing super-strong water absorbing agent induced by contacting glow plasma
US20140219973A1 (en) * 2011-08-23 2014-08-07 Victoria L. Boyes Composite Hydrogel-Clay Particles
CN102690535A (en) * 2012-06-07 2012-09-26 复旦大学 Organic modified nano-attapulgite particles and preparation method thereof
CN102977271A (en) * 2012-12-14 2013-03-20 西北师范大学 Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma
CN105709704A (en) * 2016-02-03 2016-06-29 西北师范大学 Preparation of chitosan-based adsorption agent and application of chitosan-based adsorption agent to heavy metal ion wastewater treatment

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
JUNPING ZHANG ET AL.: "Synthesis and characterization of chitosan-g-poly(acrylic acid)/attapulgite superabsorbent composites", 《CARBOHYDRATE POLYMERS》 *
XIAOHUAN WANG ET AL.: "Fast removal of copper ions from aqueous solution by chitosan-g-poly(acrylic acid)/attapulgite composites", 《JOURNAL OF HAZARDOUS MATERIALS》 *
俞洁等: "CS/P(AMPS-co-AM)水凝胶吸附Pb2+性能研究", 《水处理技术》 *
常春雨等: "《新型纤维素、甲壳素水凝胶的构建、结构和性能》", 31 October 2015 *
张文明等: "辉光放电电解等离子体引发纤维素基水凝胶的制备及其多重响应行为", 《高电压技术》 *
朱婉萍等: "《甲壳素及其衍生物的研究与应用》", 30 November 2014 *
赵睿等: "新型吸附剂的制备及其对亚甲基蓝吸附的研究", 《化工新型材料》 *
陆泉芳等: "辉光放电电解等离子体制备聚丙烯酸/蒙脱土水凝胶及性能测试", 《化工新型材料》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915803A (en) * 2017-10-23 2018-04-17 昆明理工大学 It is a kind of to prepare the method for removing cadmic nano-composite gel in waste water
CN107915803B (en) * 2017-10-23 2020-02-07 昆明理工大学 Method for preparing nano composite gel for removing divalent cadmium in wastewater
CN115558301A (en) * 2022-09-28 2023-01-03 闽江学院 Anti-freezing hydrogel with high flexibility and high ionic conductivity and preparation method thereof
CN115558301B (en) * 2022-09-28 2023-09-15 闽江学院 High-flexibility high-ionic-conductivity anti-freezing hydrogel and preparation method thereof

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