CN108503751A - The preparation and application of the nano-starch composite particulate material of quaternary ammonium polymer modification - Google Patents
The preparation and application of the nano-starch composite particulate material of quaternary ammonium polymer modification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention relates to the preparations and application of a kind of nano-starch particulate composite of quaternary ammonium polymer modification, and the nano-starch of high degree of dispersion is prepared for by acid-catalyzed hydrolysis using cornstarch as raw material；Again using 2 bromine isobutyl acylbromides as initiator, triethylamine is acid binding agent, is prepared for the nano-starch particle of initiator modification；Then using the nano-starch particle that 2 bromo isobutyl acylbromides are modified as initiator, so that DMAEMA is carried out polymerization modification and obtain the nano-starch particle of PDMAEMA modifications；Most afterwards through it is quaternized modify quaternary ammonium polymer modification nano-starch granular materials, which has good dispersibility, pH value and temperature-responsive；The nano-starch composite material of quaternary ammonium polymer modification prepared by the present invention shows preferable absorption property for the chromate in simulation sewage, has a good application prospect in environmental improvement；And using the modified good pH value of nano-starch composite material and temperature-responsive.
Description
Technical field
The invention belongs to high polymer material technologies and field of environmental improvement, and in particular to a kind of modification of quaternary ammonium polymer
The preparation of nano-starch particulate composite；The nano-starch particle that the present invention also relates to quaternary ammonium polymer modification is multiple
Application of the condensation material as adsorbent in handling waste water containing chromate.
Background technology
Cornstarch is a kind of natural reproducible natural macromolecular material, and abundance has good bio-compatibility
And degradability, widely used, safety and environmental protection are easily modified to prepare various environment-friendly materials.The natural height prepared with cornstarch
Molecule nano starch crystallite is compared with inorganic nano reinforcing agent, and source is wide, at low cost, density is low, and surface has many hydroxyls, can
To carry out functional modification by graft copolymerization.
During traditional graft copolymerization, the initiator concentration on starch surface is relatively low, and grafting efficiency is relatively low, how
It is crucial that starch surface, which introduces more active sites,.There is active hydroxyl, this is just to introduce activity to draw on starch polymer chain
Hair agent creates condition.Studies have shown that SI-ATRP is used for the surface grafting polymerization of nano-starch material, can give full play to
The characteristics of " controllable " is with " activity ".Based on this, select it is a kind of contain in carbochain with halogen atom acetyl halide compound as atom
The initiator of transition free radical polymerization reaction (ATRP) passes through active end group in initiator and nano-starch Large molecule active end
Hydroxyl reaction to modify nano-starch surface, to will polymerisation carbon-halogen functional group introduce nano-starch side group,
Further cause vinyl monomer graft polymerization and widens the application field of starch to the surface of starch to improve the performance of starch.
Invention content
The object of the present invention is to provide a kind of preparation sides of the nano-starch particulate composite of quaternary ammonium polymer modification
Method.
The nano-starch particulate composite that purpose of the present invention another object is to provide quaternary ammonium polymer modification exists
Application in adsorption treatment waste water containing chromate.
The technical solution adopted in the present invention is：A kind of nano-starch particulate composite of quaternary ammonium polymer modification
Preparation method comprises the following steps that：
The preparation of step (1) nano-starch particle：Cornstarch after vacuum drying is scattered in 2-4M dilute sulfuric acids,
It is hydrolyzed 8-11 days in 30-40 DEG C of oil bath, high speed centrifugation, it is dry, obtain nano-starch particle；
The preparation of the nano-starch particle of step (2) 2- bromo isobutyl acylbromides modification：Using dichloromethane as solvent, triethylamine
For acid binding agent, 2- bromo isobutyl acylbromides are initiator, under nitrogen protection, stirring, make the nano-starch of above-mentioned steps (1) preparation
After particle carries out modification polymerization 20-24h at room temperature, high speed centrifugation, separation of polymeric product is simultaneously washed with acetone, dry, is obtained
The nano-starch particle of 2- bromo isobutyl acylbromides modification；
The preparation of the nano-starch particle of step (3) PDMAEMA modifications：Using deionized water as solvent, above-mentioned steps (2) system
The nano-starch particle of standby 2- bromo isobutyl acylbromides modification is initiator, and 2,2 '-bipyridyls and cuprous bromide are urged as compound
Agent makes Dimethylaminoethyl Methacrylate carry out modification polymerization in 30-40 DEG C under nitrogen protection, stirring；It waits reacting
After solution becomes uniform blue-tinted transparent solution, high speed centrifugation, the polymerizate after separation is washed with acetone, dry, is obtained
The nano-starch particle of PDMAEMA modifications；
The preparation of the nano-starch granular materials of step (4) quaternary ammonium polymer modification：Using nitromethane as solvent, iodine first
Alkane is quaternizing agent, under nitrogen protection, makes the nano-starch particle of PDMAEMA modifications prepared by above-mentioned steps (3) in room temperature
Under be protected from light 20-24h；Wait for that after reaction, high speed centrifugation, separation product is washed with acetone, it is dry, it obtains quaternized poly-
Close the nano-starch granular materials of object modification.
Preferably, the drying in the step (1) is：It is first freeze-dried 20-24h, is dried in vacuo at 60-70 DEG C
20-24h.
Preferably, in the step (2), the dosage of triethylamine is 0.02-0.03 times of nano-starch quality；Initiator
The dosage of 2- bromo isobutyl acylbromides is 0.05-0.06 times of nano-starch granular mass.
Preferably, in the step (3), the dosage of monomer DMAEMA is the nano-starch of 2- bromo isobutyl acylbromides modification
0.1-0.3 times of grain quality.
Preferably, in the step (3), the molar ratio of 2,2 '-bipyridyl of composite catalyst and cuprous bromide is 1:1-3；
The dosage of composite catalyst is 0.05-0.06 times of monomer DMAEMA moles.
Preferably, in the step (4), the molar ratio of iodomethane and the nano-starch particle of PDMAEMA modifications is 1：
3.0-3.5.
Preferably, in the step (4), nitromethane dosage is 10-15 times of the mole of iodomethane.
Preferably, the drying in the step (2), (3) (4) is that 20-24h is dried in vacuo at 60-70 DEG C.
Preferably, the high speed centrifugation speed in the above-mentioned steps is 10000-12000rpm.
One, the synthetic route of the nano-starch composite material of quaternary ammonium polymer modification is as follows：
The present invention obtains compound 1 (StNP-I) after surface modification using nano-starch as matrix, by initiator, introduces
The active function groups carbon-halogen bond of SI-ATRP polymerisations, so that SI-ATRP reactions can be realized.Initiator modification
Nano-starch particle makes DMAEMA monomers modify nano-starch under the action of CuBr and bpy catalyst, by SI-ATRP reactions
Particle obtains compound 2 (PDMAEMA-StNP), which has coreshell type structure,
So that the surface physico-chemical property of nano-starch changes, to have new function.Since the monomer of graft copolymerization has
Standby tertiary amine functional group, can further obtain compound 3 (QPDMAEMA-StNP) by quaternization reaction, nano-starch is made to answer
The surface property of condensation material is further modified.
Two, the characterization of the nano-starch composite material of quaternary ammonium polymer modification
1, infrared spectrum analysis (FT-IR)
Divided through the characteristic peak of mode study sample using ENSOR 27instrument (Bruker) infrared spectrometer
Resolution is 4cm-1, general 32 times of scanning times.Fig. 1 is starch surface grafting polymerization object (PDMAEMA-StNP) and its raw material
(StNP), the FT-IR spectrograms of intermediate (StNP-I) and derivative (QPDMAEMA-StNP).It can be seen that nano-starch
Grain (StNP) is located at the skeletal vibration peak that the characteristic peak at 537cm-1 is pyranoid form hexatomic ring, and the characteristic peak at 764cm-1 is C-
C stretching vibration peaks, the characteristic peak at 930cm-1 are α-Isosorbide-5-Nitrae glycosidic bond skeletal vibration peak, and the characteristic peak at the places 1067cm-1 is C
(1)-H flexural vibrations peaks, the characteristic peak at 1094cm-1 are C-O-H flexural vibrations peaks, the characteristic peak at the places 1163cm-1 be C-O with
C-C stretching vibration peaks, the characteristic peak at 1415cm-1 are CH2 flexural vibrations peaks and C-O-O stretching vibration peaks, 2800-3000cm-
Characteristic peak at 1 is that CH2 deforms peak, and the characteristic peak at 3000-3600cm-1 is O-H stretching vibration peaks.
There is-C=O at 1730cm-1 after 2- bromo isobutyl acylbromides are surface modified and stretches in nano-starch particle
Contract the absorption peak vibrated, illustrates that esterification has occurred with hydroxyl in starch in 2- bromo isobutyl acylbromides, initiator is successfully modified
Nano-starch particle surface.
The infrared analysis of the PDMAEMA-StNP obtained after graft polymerization the result shows that, the characteristic absorption peak of starch disappears,
Occur NH stretching vibration peaks at 3300-3500cm-1, the middle C-H stretching vibration peaks of 2926cm-1 appearance-CH3 and-CH2-,
C-H stretching vibration peaks in 2855 and 2770cm-1 appearance-N (CH3) 2, due in the polymer chain after starch surface graft modification
Containing a large amount of ester functional groups, so the absorption peak strength of the stretching vibration of the corresponding C=O of 1730cm-1 significantly increases, separately
Corresponding-CH2 flexural vibrations peaks at outer 1459cm-1, corresponding C-N stretching vibration peaks further demonstrate poly- at 1150cm-1
The presence [17] for closing object, shows that nano-starch particle surface is successfully modified by DMAEM polymer.
Infrared analysis after quaternized the result shows that, the middle C-H stretching vibration peaks of-CH2- in situ in 2926cm-1 are to height
Wave number is moved to 3009cm-1, and original corresponds to the suction of the C-H stretching vibration peaks 2855 and 2770cm-1 in tertiary amine groups-N (CH3) 2
It is unimodal at 2955cm-1 to receive peak degeneracy, and the absorption peak of quaternary ammonium group CH2-N+ (CH3) 3 occurs in 951cm-1.Therefore it demonstrate,proves
It is bright to generate QPDMAEMA-StNP nano-starch composite materials.
Infrared analysis result clearly demonstrates that initiator successfully grafts on nano-starch surface, and it is poly- to cause ATRP by surface
It closes, the surface of nano-starch is modified by PDMAEMA, successfully realizes that quaternary ammonium polymer modifies nano-starch after quaternization reaction
The preparation of grain.
2, X-ray diffraction analysis (XRD)
Fig. 2 is the XRD analysis result of starch surface grafting polymerization object and raw material.By comparing it can be found that 2- bromos are different
After butyryl bromide modifies nano-starch particle, the intensity of diffraction maximum slightly reduces, this illustrates in initiator modification, nano-starch
Crystallization degree decrease, but feature is spread out, the shape at peak does not change with position, illustrates that the structure of nano-starch particle does not have
It is destroyed；The diffraction maximum of sample after grafting, copolymerization and modification, starch disappears, and new broad peak occurs at 17.73 °, this
It is the characteristic diffraction peak of starch surface polymer, illustrates that the surface of the starch after graft modification is essentially polymer chain and is covered,
So as to assign nano-starch new surface physico-chemical property.The sample obtained after quaternised modified does not have apparent diffraction
Peak, this illustrates that the sample is impalpable structure.
X-ray diffraction analysis the result shows that, initiator successfully modifies nano-starch surface, nanometer after PDMAEMA grafting is poly-
Starch surface is essentially polymer and is covered, this explanation can be copolymerized anti-using nano-starch as template by surface initiation grafting
It should realize that the preparation of nucleocapsid, quaternised modified rear crystallization degree are substantially change, further expand nano-starch
Application range.
3, x-ray photoelectron spectroscopy (XPS)
Fig. 3 composes the comparison of scanning result for the XPS of different phase product during nano-starch graft modification entirely.By than
Compared with it can be found that nano-starch particle by with after 2- bromo isobutyryl bromine reactions, there is new peak in the surface-element of starch, and
After graft polymerization, due to containing nitrogen in monomer so that there is the characteristic peak of nitrogen in full spectrum scanning figure, and it is quaternized
After processing, due to the introducing of iodine, occurs the characteristic peak of iodine in full spectrogram.The full spectrum scanning result of XPS is further
It demonstrates initiator and successfully modifies nano-starch particle, PDMAEMA modification nano-starch particles and quaternization process.
Fig. 4 is the C1s spectrum swarming results of different phase Product samples during nano-starch graft modification.Fig. 4 a are shown
StNP samples C1s composes swarming result.The result shows that in conjunction with that can be that 283.268eV and 284.695eV corresponds respectively to pyranose ring
Middle C-C chains and-CH2OH side chain carbons peak, in conjunction with can be the carbon peak of 285.592eV corresponding to C-O keys in pyranose ring
Carbon peak, O and C element ratio are 0.52；The nano-starch C1s that Fig. 4 b show initiator modification composes swarming as a result, result
Show in conjunction with can be that 283.268eV and 284.127eV correspond respectively to C-C chains and-CH2OH side chain carbons in pyranose ring
The combination of peak, most strong cutting edge of a knife or a sword can be 285.101eV corresponding to the carbon peak in C-Br keys in initiator, in conjunction with can be 286.899eV
Carbon peak correspond to the carbon peak in-O-C=O keys, O and C element ratio are 0.440874, the table for the nano-starch that compares
Face composition is declined, and is since graft reaction occurs for initiator and nano-starch particle surface, to cause surface composition
Variation；Fig. 4 c show PDMAEMA-StNP samples C1s spectrum swarming results.In conjunction with can be that 281.926eV and 284.002eV distinguish
Corresponding to C element peak in C-C chains, the carbon peak of 284.772eV corresponds to the carbon peak in CO keys, and most strong cutting edge of a knife or a sword combination can be
285.802eV corresponds to the carbon peak in C-N keys.In conjunction with can for 279.609eV carbon peak correspond to quaternary carbon element peak,
In conjunction with that can correspond to the carbon peak in O-C=O keys for the carbon peak of 288.570eV, N and C atomic ratios are about 0.098936,
Close to N in DMAEMA molecules and C atomic ratios 0.125, this illustrates the surface of polymer-modified nano-starch for polymer institute
Cladding, is consistent with the result of IR Characterization above；Fig. 4 d show the C1s spectrum swarmings of QPDMAEMA-StNP samples as a result, knot
It can be that 284.801eV corresponds respectively to C element peak in C-C chains to close, and the carbon peak of 284.953eV corresponds to the carbon member in CO keys
Plain peak, most strong cutting edge of a knife or a sword combination can be that 285.903eV corresponds to the carbon peak in C-N keys, in conjunction with the carbon that can be 288.295eV
Peak corresponds to the carbon peak in-O-C=O keys, and the atomic ratio of carbon and oxygen element is 0.27492, is very close to polymerization
The element ratio of object monomer shows that the surface of nano-starch is essentially polymer and is coated.N and C atomic ratios are about 0.098936, I
With C atomic ratios be about 0.069354, I and N atomic ratios are about 0.7:1, the explanation of nano-starch surface grafting polymerization object is quaternized
Degree is more complete.
Fig. 5 show the surface N element XPS analysis results contrast of modified Nano starch, by analysis it can be found that nanometer
The combination of tertiary N can be 399.22eV in starch particle surface graft polymers, be obtained after quaternized in QPDMAEMA-StNP samples
Season N combination can be 402.1333eV, illustrate that the quaternised modified combination for enabling tertiary N increases, this is because the charge in season N
Increase from caused.
4, nuclear magnetic resonance
Fig. 6 is StNP (a), NMR points of the 1H of StNP-I (b), the QPDMAEMA-StNP (d) of PDMAEMA-StNP (c) sums
As a result, by comparing a and b it can be found that chemical shift 0.9ppm is the proton peak in-OH, 2.14~3.49ppm is starch for analysis
The proton peak of middle C4, C2 and C3,3.9ppm are the proton peaks on C5, and 4.2~4.3.ppm is the proton peak on C1；Two figure Central Plains
Expect that the proton peak shift of nano-starch particle is unchanged, but new proton occurs at chemical shift 0.7ppm and 1.3ppm
Peak illustrates that 2- bromo isobutyl acylbromides are modified into work(, and starch chain does not change；By comparing c and d it can be found that chemistry
Occur the proton peak of monomer at 1.2,1.9,2.1,2.3,2.5,3.3,3.6 and 4.6ppm of displacement, nano-starch particle
Proton peak is obviously reduced, and illustrates that the nano-starch particle surface success graft polymers after initiator modification, monomer are successfully grafted
In nano-starch particle surface.QPDMAEMA-StNP proton peaks after quaternized are due to foring quaternary ammonium functional group so that
The chemical shift of tertiary amine functional group proton peak increases to 3.3ppm by 2.5ppm in PDMAEMA-StNP so that the peak is significantly wide
Change, illustrates quaternised modified success.
5, transmission electron microscope (TEM)
Fig. 7 show the cornstarch tem analysis result by 3.16mol/L sulfuric acid treatments.By analysis it can be found that
After sulfuric acid treatment, the particle diameter distribution of cornstarch is more uniform, and average grain diameter is about in 10-15nm.This illustrates acid catalysis
Hydrolysis process can prepare the nano-starch of high degree of dispersion.
Fig. 8 show the tem analysis result of initiator modification nano-starch particle (StNP-I).It can send out by analysis
Existing, surface is modified, and the particle diameter distribution of nano-starch particle is more concentrated and relatively uniform, and average grain diameter is about in 12-20nm.
Grain size becomes smaller, and is that hydrogen bond weakens between nano-starch granulin molecule after introducing small molecule initiator, dispersibility improves, further subtracts
The reason of having lacked nano-starch particle agglomeration.
Fig. 9 and Figure 10 show starch surface grafting polymerization object (PDMAEMA-StNP) and quaternized starch surface grafting is poly-
Close the tem analysis result of object (QPDMAEMA-StNP).Analyze the grain it can be found that the nano-starch particle after PDMAEMA modifications
Diameter significantly increases one times to 20-30nm, and particle diameter distribution is wider, compared with hereinbefore tem analysis result, is connect by surface
Nano-starch grain diameter after branch copolymerization dramatically increases, and is polymer-modified result.Nano-starch particle after quaternized
Grain size increases further to 110-130nm, is the group that starch surface grafting polymerization object nano-particle is caused in quaternization process
It is poly-.
Tem analysis the result shows that, starch acid-catalyzed hydrolysis prepares nano-starch particle, and hydrolysis time is to nano-starch particle
Size Distribution it is larger；The nano-starch particle size distribution of initiator modification is more uniform, and grain size becomes smaller.PDMAEMA
Due to the coating function of macromolecule polyalcohol, grain size significantly increases the nano-starch particle of modification, quaternized so that grain size is into one
Step increases.But before and after surface modification treatment, significant change does not occur for the surface topography of nano-starch, basic to keep more advising
Whole chondritic.
Three, the performance of the nano-starch composite material of quaternary ammonium polymer modification is surveyed
1, to the sensibility of temperature and pH value
DMAEMA is a kind of macromolecule with temperature and pH-sensitivity.Hydrophily is existed simultaneously in its molecular structure unit
Tertiary amine groups, carbonyl and hydrophobic alkyl group, two class groups match each other on space structure.The present invention is for quaternized
Front and back starch surface grafting polymerization object investigates the sensibility of temperature and pH value.
Figure 11 show influences of the pH for PDMAEM-StNP dispersibilities.A concentration of 2mg/mL (a) pH=4.0, (b) pH
=10.0, by analysis it can be found that the dispersibility of PDMAEM-StNP declines with the increase of pH, illustrate that surface grafting is total
Poly- modified nano-starch has preferable pH sensitive properties.
Figure 12 show influences of the pH to QPDMAEMA-StNP absorbances.By analysis it can be found that being 4-8 models in pH
In enclosing, the absorbance of QPDMAEMA-StNP is increased slightly with the increase of pH, illustrates the modified nano-starch of surface graft copolymerization
PH sensitive properties it is relatively low.But when pH increases to 12 by 8, absorbance dramatically increases, and illustrates in higher pH value range, surface
Nano-starch after grafting, copolymerization and modification has preferable pH sensitive properties.
Figure 13 is shown in the buffer solution of pH=9.18, influence of the temperature for PDMAEM-StNP swellbilitys.Through excessive
Analysis illustrates that surface graft copolymerization is modified it can be found that PDMAEM-StNP swellbilitys are gradually reduced as the temperature increases
Nano-starch has preferable temperature sensitivity energy.
Figure 14 nano-starch before modified after in methylene chloride dispersibility relatively (30min).(a) StNP, (b) StNP-
I, (c) PDMAEMA-StNP, (d) QPDMAEMA-StNP.By analysis it can be found that point of nano-starch in methylene chloride
It is relatively low to dissipate property, localized precipitation phenomenon occurs.The dispersibility of the nano-starch (StNP-I) of initiator modification in methylene chloride
Little, nano-starch surface grafting polymerization object (PDMAEM-StNP) and quaternized surface grafting polymerization object can be changed
(QPDMAEMA-StNP) dispersibility in methylene chloride significantly improves, and deposit-free matter occurs, and illustrates that surface graft copolymerization changes
Starch after property also can be evenly dispersed in the smaller solvent of polarity.Dispersibility of the nano-starch in nonpolar solvent itself
It is relatively low, and the nano-starch grain diameter after initiator modification is smaller, shows certain nano effect, dispersion performance has centainly
The raising of degree, by polymer-modified nano-starch surface to be coated with amphiphilic polymer, to show
It is a degree of amphipathic.
2, absorption property
Figure 15 show the starch after graft modification for potassium chromate solution equilibrium adsorption capacity with concentration change curve.
Through comparison it can be found that PDMAEMA-StNP for the chromate in solution equilibrium adsorption capacity when concentration is relatively low, with
The increase of concentration and quickly increase, when the concentration of potassium chromate continues growing, equilibrium adsorption capacity tends to be flat with the variation of concentration
Smooth, maximum equilibrium adsorption capacity is about 260mg/g.The equilibrium adsorption of QPDMAEMA-StNP samples after quaternised modified
Amount almost linearly increases within the scope of experimental concentration with the increase of concentration, when the concentration of potassium chromate is less than 3000mg/L,
Its equilibrium adsorption capacity is less than the equilibrium adsorption capacity of PDMAEMA-StNP, and when the concentration of potassium chromate is more than the concentration, balance is inhaled
Attached amount is higher than the equilibrium adsorption capacity of PDMAEMA-StNP.The reason of causing the phenomenon is the difference due to the adsorption mechanism of the two.
For PDMAEMA-StNP samples, suction-operated mainly relies on the three-dimensional effect for the polymer for being grafted on starch surface, and
Larger raising is obtained for the hydrophilicity of the QPDMAEMA-StNP polyelectrolyte samples after quaternised modified, is polymerize
Object chain has a degree of ion-exchange capacity, and when chromic acid potassium concn is relatively low, ion-exchange capacity is relatively low, for solution
The absorption of middle chromate plays a major role, and simple physical absorption ability is less than the polymer without quaternized processing, because
, when the concentration of chromate continues growing, ion-exchange capacity increases so that its equilibrium adsorption capacity reaches even higher than for this
The equilibrium adsorption capacity of PDMAEMA-StNP.
Nano-starch after graft modification shows that the surface grafting in nano-starch changes to the Adsorption experimental results of chromate
Property after, surface physico-chemical property significantly improves, for heavy metal in toxic wastewater removal have preferable effect.Relatively low dense
The nano-starch of the lower graft modification of degree has larger equilibrium adsorption capacities, adsorbance solidifying higher than PDMAEMA reported in the literature
The equilibrium adsorption capacity of glue material, at higher concentrations QPDMAEMA-StNP have larger equilibrium adsorption capacities, absolutely prove
Before polymer-modified nano-starch composite material has preferable application in terms of the processing containing toxic effluent containing heavy metal ions
Scape.
Starch after graft modification is reversible the absorption of chromate, in order to explore the sample after adsorption equilibrium again
Generation method has attempted soda acid immersion treatment, electrolyte solution exchange and the method for changing solution polarity, still during the experiment
It was found that only leaning on a kind of single method, it is difficult to prove effective.By exploration repeatedly, it is found that the sample after adsorption equilibrium passes through
Several minutes of 0.1mol/L salt acid soak, after being then centrifuged for separation, is changed to acetone soak, can realize sample after adsorption experiment rapidly
Regeneration.The adsorption capacity of sample after regeneration can be restored to original level.Acetone is easy to implement complete with potassium chromate
Separation, so that the metal ion realization in simulated wastewater is totally separated from.This is because sample is in acidity after graft modification
There is preferable dispersibility in solution, be conducive to the desorption of adsorption sample.
The present invention is prepared for the nano-starch of high degree of dispersion by acid-catalyzed hydrolysis using cornstarch as raw material；Again with 2-
Bromine isobutyl acylbromide is initiator, and triethylamine is acid binding agent, is prepared for the nano-starch of initiator modification；Then with 2- bromo isobutyls
The nano-starch particle of acylbromide modification makes DMAEMA carry out polymerization modification and obtains the nanometer shallow lake of PDMAEMA modifications as initiator
Powder particles composite material PDMAEMA-StNP；Target product QPDMAEMA-StNP is most modified to obtain through quaternized afterwards, which has
Good dispersibility, pH value and temperature-responsive.XRD, XPS, NMR and TEM characterization result show nano-starch graft polymers
It is based on surface is caused, it is nucleocapsid that the nano-starch composite material of preparation, which is that nano-starch surface polymer coated,
Structure；It is further it is quaternised modified after nano-starch polymer architecture and surface topography significant change does not occur.
Beneficial effects of the present invention are：The product has good dispersibility, pH value and temperature-responsive.XRD、XPS、
NMR and TEM characterization results show that nano-starch graft polymers is based on surface is caused, and the nano-starch of preparation is multiple
It is nucleocapsid that condensation material, which is that nano-starch surface polymer coated,；It is further it is quaternised modified after nano-starch it is poly-
It closes object structure and significant change does not occur for surface topography；The nano-starch of quaternary ammonium polymer modification prepared by the present invention is multiple
Condensation material shows preferable absorption property for the chromate in simulation sewage, before having good application in environmental improvement
Scape；And using the modified good pH value of nano-starch composite material and temperature-responsive, continue probing polymer modification
Nano-starch expands answering for nano-starch in the application in the fields such as bactericidal property of drug controlled release, quaternary ammonium type polyelectrolyte
Use field.
Description of the drawings
Fig. 1 is the infrared spectrogram of starch surface grafting polymerization object and raw material；
Fig. 2 is the XRD analysis result figure of starch surface grafting polymerization object and raw material；
Fig. 3 is the variation diagram of the surface composition of starch surface grafting polymerization object and raw material；
Fig. 4 is the C1s spectrum swarming result figures of different phase Product samples during nano-starch graft modification；
Fig. 5 starch surface grafting polymerization objects surface N1s element XPS analysis results contrast figures；
Fig. 6 is the 1H NMR analyses of StNP (a), StNP-I (b), PDMAEMA-StNP (c) and QPDMAEMA-StNP (d)
Result figure；
Fig. 7 hydrolyzes the tem analysis result figure after 11d；
Fig. 8 is the tem analysis result figure of StNP-I；
The tem analysis result figure of Fig. 9 PDMAEMA-StNP；
Figure 10 is the tem analysis result figure of QPDMAEMA-StNP；
Figure 11 is influence diagram of the different pH value for PDMAEMA-StNP dispersibilities；
Figure 12 is influence diagram of the different pH value for QPDMAEMA-StNP absorbances；
Figure 13 is influence diagram of the temperature to PDMAEMA-StNP swellbilitys；.
Figure 14 be nano-starch before modified after dispersed comparison figure in methylene chloride；
Figure 15 is the equilibrium adsorption capacity of graft modified starch with the variation diagram of concentration.
In figure：StNP-nano-starch particle；The nano-starch particle of StNP-I -2- bromo isobutyl acylbromides modification；
The nano-starch particle of PDMAEMA-StNP-PDMAEMA modifications；The nanometer of QPDMAEMA-StNP-quaternary ammonium polymer modification
Starch granules material.
Specific implementation mode
The preparation for the nano-starch granular materials that quaternary ammonium polymer of the present invention is modified below by embodiment and performance
It is described further.
Embodiment 1
(1) preparation of nano-starch particle
The dilute sulfuric acid of the accurate 3.16mol/L for measuring 200mL is in the three-necked flask of 250mL；Weighing 40.64g vacuum is dry
Former cornstarch after dry, and be added into three-necked flask, it is hydrolyzed respectively in 30 DEG C of oil baths 8 days, then at 10000rpm
After high speed centrifugation, then freeze-dried 20h is dried in vacuo 20h at a temperature of 60 DEG C, obtain nano-starch particle (StNP).
Tem analysis finds that after 11d, the particle diameter distribution of starch is more uniform, and average grain diameter is about in 10nm, and yield is 20%.
(2) preparation of the nano-starch particle of 2- bromos isobutyl acylbromide modification
Above-mentioned obtained nano-starch 80mg is taken, is added in 100mL three-necked flasks, 20mL dichloromethane is then added, is used
High pure nitrogen is purged and is sealed with rubber stopper after replacing the air in flask, opens magnetic stirring apparatus, is slowly dripped with injection tolerance
Add the triethylamine of 2.8mL；After 10min, the 2- bromo isobutyl acylbromides of 2.4mL are slowly injected by rubber stopper with syringe,
Polymerization is surface modified at 25 DEG C of room temperature for 24 hours, then the high speed centrifugation at 10000rpm, is then washed and centrifuged with acetone
Three times, the nano-starch for obtaining initiator modification for 24 hours is dried in vacuo after being air-dried in centrifuge tube at a temperature of 60 DEG C
(StNP-I).Tem analysis it can be found that surface is modified, more concentrate and relatively uniform by the particle diameter distribution of nano-starch particle,
Its average grain diameter is about in 12nm.Grain size becomes smaller, and is that hydrogen bond weakens between nano particle molecule after introducing small molecule initiator, dispersion
The reason of property improves, further reduces nanoparticle agglomerates.
(3) preparation of the nano-starch particle of PDMAEMA modifications
It is accurate to measure 30mL deionized waters and be added into tool test tube, it is sealed with rubber stopper, is purged by high pure nitrogen
After displaced air, after adjusting water temperature to experimental temperature, 4mL DMAEMA (dimethylaminoethyl second is pipetted with syringe
Ester) and be slowly injected in tool test tube, be then respectively adding 90mg2,2 '-bipyridyls and cuprous bromide (2,2 '-bipyridyls and
The molar ratio of cuprous bromide is 1:2)；Add every time after reagent with high pure nitrogen purging simultaneously, wait for solid reagent dissolving completely at
After uniform brown solution, the nano-starch particle (StNP-I) of the initiator modification of 80mg is added, reaction to solution becomes
After uniform blue-tinted transparent solution under 10000rpm rotating speeds high speed centrifugation, separation of polymeric product washed repeatedly with acetone and from
The heart, to remove polymerizate, until white or water white transparency.Polymerizate air-dries at room temperature, then at a temperature of 60 DEG C
After being dried in vacuo 20h, the nano-starch product (PDMAEMA-StNP) of the modifications of the PDMAEMA after surface graft copolymerization is obtained.TEM points
Analysis as a result, it has been found that, the grain size of nano-starch after PDMAEMA modifications significantly increases one times to 20nm, and particle diameter distribution is wider,
Compared with hereinbefore tem analysis result, the nano-starch grain size after surface graft copolymerization dramatically increases, and is that polymer is repaiied
The result of decorations.
(4) preparation of the nano-starch granular materials of quaternary ammonium polymer modification
It is accurate to measure 5mL nitromethanes and be added into tool test tube, it then passes to high pure nitrogen and purges and replace test tube
In air, be added 1mL iodomethane, it is to be mixed uniformly after, the PDMAEMA-StNP samples of 20mg are added, are protected in room temperature and nitrogen
It is protected from light 20h under the conditions of shield, waits for that after reaction, the high speed centrifugation under 10000rpm rotating speeds, separation product is washed with acetone
And centrifuge three times, after being dried in vacuo 20h at a temperature of 60 DEG C after air-drying at room temperature, the modification of obtained quaternary ammonium polymer
Nano-starch particle (QPDMAEMA-StNP).Tem analysis as a result, it has been found that, it is quaternized after nano-starch particle (QPDMAEMA-
StNP) grain size increases further to 110nm, is the group that starch surface grafting polymerization object nano-particle is caused in quaternization process
It is poly-.
Adsorption test shows that QPDMAEMA-StNP is about 320mg/g for the maximum equilibrium adsorption capacity of chromate.
Embodiment 2
(1) preparation of nano-starch particle
The dilute sulfuric acid of the accurate 3.16mol/L for measuring 100mL is in the three-necked flask of 250mL；Weighing 20.32g vacuum is dry
Former cornstarch after dry, and be added into three-necked flask, it is hydrolyzed respectively in 35 DEG C of oil baths 10 days, then at 11000rpm
After high speed centrifugation, then freeze-dried 22h is dried in vacuo 22h at a temperature of 70 DEG C, obtain nano-starch particle (StNP).
Tem analysis finds that after 11d, the particle diameter distribution of starch is more uniform, and average grain diameter is about in 12nm, and yield is 25%.
(2) preparation of the nano-starch particle of 2- bromos isobutyl acylbromide modification
Above-mentioned obtained nano-starch 40mg is taken, is added in 100mL three-necked flasks, 10mL dichloromethane is then added, is used
High pure nitrogen is purged and is sealed with rubber stopper after replacing the air in flask, opens magnetic stirring apparatus.It is slowly dripped with injection tolerance
Add the triethylamine of 1.4mL.After 10min, the 2- bromo isobutyl acylbromides of 1.2mL are slowly injected by rubber stopper with syringe,
Polymerization is surface modified at 25 DEG C of room temperature for 24 hours, then the high speed centrifugation at 11000rpm, is then washed and centrifuged with acetone
Three times, it is dried in vacuo 22h at a temperature of 65 DEG C after being air-dried in centrifuge tube, obtains the nano-starch of initiator modification
(StNP-I).Tem analysis it can be found that surface is modified, more concentrate and relatively uniform by the particle diameter distribution of nano-starch particle,
Its average grain diameter is about in 15nm.Grain size becomes smaller, it may be possible to introduce after small molecule initiator that hydrogen bond weakens between nano particle molecule,
Dispersibility improves, the reason of further reducing nanoparticle agglomerates.
(3) preparation of the nano-starch particle of PDMAEMA modifications
It is accurate to measure 15mL deionized waters and be added into tool test tube, it is sealed with rubber stopper, is purged by high pure nitrogen
After displaced air, after adjusting water temperature to experimental temperature, 2mL DMAEMA (dimethylaminoethyl second is pipetted with syringe
Ester) and be slowly injected in tool test tube, being then respectively adding 45mg, (molar ratio of 2,2 '-bipyridyls and cuprous bromide is 1:
2).It is purged simultaneously with high pure nitrogen after adding reagent every time, after solid reagent dissolving goes completely into uniform brown solution, is added
Enter the nano-starch (StNP-I) of the initiator modification of 40mg.Reaction to solution become uniform blue-tinted transparent solution after
High speed centrifugation under 12000rpm rotating speeds, separation of polymeric product is washed and is centrifuged repeatedly with acetone, to remove polymerizate, until being in
White or water white transparency.Polymerizate air-dries at room temperature, after being then dried in vacuo for 24 hours at a temperature of 60 DEG C, obtains surface grafting
The nano-starch product (PDMAEMA-StNP) of PDMAEMA modifications after copolymerization.Tem analysis as a result, it has been found that, PDMAEMA modification after
The grain size of nano-starch significantly increase one times to 25nm or so, and particle diameter distribution is wider, with hereinbefore tem analysis result phase
Compare, the nano-starch grain size after surface graft copolymerization dramatically increases, it may be possible to polymer-modified result.
(4) preparation of the nano-starch granular materials of quaternary ammonium polymer modification
It is accurate to measure 2.5mL nitromethanes and be added into tool test tube, it then passes to high pure nitrogen and purges and replace examination
Air in pipe, be added 0.5mL iodomethane, it is to be mixed uniformly after, the PDMAEMA-StNP samples of 10mg are added, in room temperature and nitrogen
It is protected from light for 24 hours under the conditions of gas shielded.It waits for after reaction, the high speed centrifugation under 12000rpm rotating speeds, separation product acetone
It washs and centrifuges three times, after being dried in vacuo 22h at a temperature of 65 DEG C after air-drying at room temperature, obtained quaternary ammonium polymer is repaiied
The nano-starch particle (QPDMAEMA-StNP) of decorations.Tem analysis as a result, it has been found that, it is quaternized after nano-starch particle
(QPDMAEMA-StNP) grain size increases further to 120nm, it may be possible to starch surface grafting polymerization is caused in quaternization process
The reunion of object nano-particle.
Adsorption test shows that QPDMAEMA-StNP is about 340mg/g for the maximum equilibrium adsorption capacity of chromate.
Embodiment 3
(1) preparation of nano-starch particle
The dilute sulfuric acid of the accurate 3.16mol/L for measuring 250mL is in the three-necked flask of 500mL；Weighing 50.8g vacuum drying
Former cornstarch afterwards, and be added into three-necked flask, it is hydrolyzed respectively in 40 DEG C of oil baths 11 days, it is then high at 12000rpm
It is freeze-dried to be then dried in vacuo for 24 hours at a temperature of 70 DEG C for 24 hours after speed centrifugation, obtain nano-starch particle (StNP).TEM
Analysis is found, after 11d, the particle diameter distribution of starch is more uniform, and average grain diameter is about in 15nm, and yield is 26%.
(2) preparation of the nano-starch particle of 2- bromos isobutyl acylbromide modification
Above-mentioned obtained nano-starch 100mg is taken, is added in 250mL three-necked flasks, 25mL dichloromethane is then added, is used
High pure nitrogen is purged and is sealed with rubber stopper after replacing the air in flask, opens magnetic stirring apparatus.It is slowly dripped with injection tolerance
Add the triethylamine of 3.5mL.After 10min, the 2- bromo isobutyl acylbromides of 3.0mL are slowly injected by rubber stopper with syringe,
Polymerization is surface modified at 25 DEG C of room temperature for 24 hours, then the high speed centrifugation at 12000rpm, is then washed and centrifuged with acetone
Three times, the nano-starch for obtaining initiator modification for 24 hours is dried in vacuo after being air-dried in centrifuge tube at a temperature of 70 DEG C
(StNP-I).Tem analysis it can be found that surface is modified, more concentrate and relatively uniform by the particle diameter distribution of nano-starch particle,
Its average grain diameter is about in 20nm.Grain size becomes smaller, it may be possible to introduce after small molecule initiator that hydrogen bond weakens between nano particle molecule,
Dispersibility improves, the reason of further reducing nanoparticle agglomerates.
(3) preparation of the nano-starch particle of PDMAEMA modifications
It is accurate to measure 37.5mL deionized waters and be added into tool test tube, it is sealed with rubber stopper, by High Purity Nitrogen air-blowing
After sweeping displaced air, after adjusting water temperature to experimental temperature, 5.0mL DMAEMA (dimethylaminoethyls are pipetted with syringe
Ethyl ester) and be slowly injected in tool test tube, it is then respectively adding the 112.5mg (molar ratios of 2,2 '-bipyridyls and cuprous bromide
It is 1:2).It is purged simultaneously with high pure nitrogen after adding reagent every time, waits for that solid reagent dissolving goes completely into uniform brown solution
Afterwards, the nano-starch particle (StNP-I) of the initiator modification of 100mg is added.It is molten that reaction to solution becomes uniform blue-tinted transparent
After liquid under 12000rpm rotating speeds high speed centrifugation, separation of polymeric product is washed and is centrifuged repeatedly with acetone, to remove polymerizate,
Until white or water white transparency.Polymerizate air-dries at room temperature, after being then dried in vacuo for 24 hours at a temperature of 70 DEG C, obtains table
The nano-starch product (PDMAEMA-StNP) of PDMAEMA modifications after the graft copolymerization of face.Tem analysis as a result, it has been found that, PDMAEMA
The grain size of nano-starch after modification significantly increases one times to 30nm, and particle diameter distribution is wider, with hereinbefore tem analysis result
It compares, the nano-starch grain size after surface graft copolymerization dramatically increases, and is polymer-modified result.
(4) preparation of the nano-starch granular materials of quaternary ammonium polymer modification
It is accurate to measure 6.25mL nitromethanes and be added into tool test tube, it then passes to high pure nitrogen and purges and replace examination
Air in pipe, is added 1.25mL iodomethane, it is to be mixed uniformly after, the PDMAEMA-StNP samples of 25mg are added, in room temperature and
It is protected from light for 24 hours under the conditions of nitrogen protection.It waits for after reaction, the high speed centrifugation under 12000rpm rotating speeds, separation product is with third
Ketone is washed and is centrifuged three times, after being dried in vacuo for 24 hours at a temperature of 70 DEG C after air-drying at room temperature, obtained quaternary ammonium polymer
The nano-starch particle (QPDMAEMA-StNP) of modification.Tem analysis as a result, it has been found that, it is quaternized after nano-starch particle
(QPDMAEMA-StNP) grain size increases further to 130nm, it may be possible to starch surface grafting polymerization is caused in quaternization process
The reunion of object nano-particle.
Adsorption test shows that QPDMAEMA-StNP is about 350mg/g for the maximum equilibrium adsorption capacity of chromate.
The present invention is not limited to above-mentioned preferred forms, anyone can show that other are various under the inspiration of the present invention
The product of form, however, make any variation in its shape or structure, it is every that there is skill identical or similar to the present application
Art scheme, is within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification, it is characterised in that including following
Step：
The preparation of step (1) nano-starch particle：Cornstarch after vacuum drying is scattered in 2-4M dilute sulfuric acids,
It is hydrolyzed 8-11 days in 30-40 DEG C of oil bath, high speed centrifugation, it is dry, obtain nano-starch particle；
The preparation of the nano-starch particle of step (2) 2- bromo isobutyl acylbromides modification：Using dichloromethane as solvent, triethylamine is to tie up
Sour agent, 2- bromo isobutyl acylbromides are initiator, under nitrogen protection, stirring, make the nano-starch particle of above-mentioned steps (1) preparation
After carrying out modification polymerization 20-24h at room temperature, high speed centrifugation, separation of polymeric product is simultaneously washed with acetone, dry, obtains 2- bromines
For the nano-starch particle of isobutyl acylbromide modification；
The preparation of the nano-starch particle of step (3) PDMAEMA modifications：Using deionized water as solvent, prepared by above-mentioned steps (2)
The nano-starch particle of 2- bromo isobutyl acylbromides modification is initiator, 2,2 '-bipyridyls and cuprous bromide as composite catalyst,
Under nitrogen protection, stirring, dimethylaminoethyl methacrylate is made to carry out modification polymerization in 30-40 DEG C；Wait for reaction solution at
After uniform blue-tinted transparent solution, high speed centrifugation, the polymerizate after separation is washed with acetone, dry, is obtained PDMAEMA and is repaiied
The nano-starch particle of decorations；
The preparation of the nano-starch granular materials of step (4) quaternary ammonium polymer modification：Using nitromethane as solvent, iodomethane is
Quaternizing agent under nitrogen protection, makes the nano-starch particle of PDMAEMA modifications prepared by above-mentioned steps (3) keep away at room temperature
Light reaction 20-24h；Wait for that after reaction, high speed centrifugation, separation product is washed with acetone, it is dry, obtain quaternary ammonium polymer
The nano-starch granular materials of modification.
2. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：Drying in the step (1) is：It is first freeze-dried 20-24h, 20-24h is dried in vacuo at 60-70 DEG C.
3. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：In the step (2), the dosage of triethylamine is 0.02-0.03 times of nano-starch granular mass；Initiator 2- bromines
Dosage for isobutyl acylbromide is 0.05-0.06 times of nano-starch granular mass.
4. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：In the step (3), the dosage of monomer DMAEMA is the nano-starch quality of 2- bromo isobutyl acylbromides modification
0.1-0.3 times.
5. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：In the composite catalyst of the step (3), the molar ratio of 2,2 '-bipyridyls and cuprous bromide is 1:1-3；It is compound to urge
The dosage of agent is 0.05-0.06 times of monomer DMAEMA moles.
6. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：In the step (4), the molar ratio of iodomethane and the nano-starch particle of PDMAEMA modifications is 1：3.0-3.5.
7. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：In the step (4), nitromethane dosage is 10-15 times of the mole of iodomethane.
8. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：Drying in the step (2), (3), (4) is that 20-24h is dried in vacuo at 60-70 DEG C.
9. the preparation method of the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1, special
Sign is：High speed centrifugation speed in each step is 10000-12000rpm.
10. the nano-starch particulate composite of quaternary ammonium polymer modification as described in claim 1 contains chromium in adsorption treatment
Application in acid group waste water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317121A (en) * | 2018-10-31 | 2019-02-12 | 天津工业大学 | A kind of ion blotting fiber and preparation method thereof orienting extracting and enriching hexavalent chromium |
| CN117343372A (en) * | 2023-10-27 | 2024-01-05 | 无锡德泰纳维高新材料有限公司 | Antibacterial plastic and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0326336A (en) * | 1989-06-23 | 1991-02-04 | Sumitomo Chem Co Ltd | Absorbent for iron and cobalt ion and method for absorbing iron and cobalt ion using same |
| US6103839A (en) * | 1998-05-11 | 2000-08-15 | Nalco Chemical Company | Horizontally flowing continuous free radical polymerization process for manufacturing water-soluble polymers from monomers in aqueous solution |
| CN1510063A (en) * | 2002-12-24 | 2004-07-07 | 北京嘉乐康环保技术有限公司 | Natural polymer modified compound, preparing method and application thereof |
| CN102250291A (en) * | 2011-05-25 | 2011-11-23 | 何善媛 | Ampholytic modified grafted starch flocculant |
| JP2013103161A (en) * | 2011-11-11 | 2013-05-30 | Nissin Electric Co Ltd | Method for adsorbing noble metal and noble metal adsorbent |
| CN103342787A (en) * | 2013-06-28 | 2013-10-09 | 中北大学 | Preparation method of chromate adsorbing material |
| CN103613709A (en) * | 2013-09-30 | 2014-03-05 | 内蒙古大学 | Method for synthesizing special heavy metal absorption ion resin by using potato starch xanthate as raw material |
| CN106279543A (en) * | 2016-08-07 | 2017-01-04 | 福建农林大学 | A kind of preparation method of cellulose base hydrophobic material |
-
2018
- 2018-02-08 CN CN201810129735.2A patent/CN108503751B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0326336A (en) * | 1989-06-23 | 1991-02-04 | Sumitomo Chem Co Ltd | Absorbent for iron and cobalt ion and method for absorbing iron and cobalt ion using same |
| US6103839A (en) * | 1998-05-11 | 2000-08-15 | Nalco Chemical Company | Horizontally flowing continuous free radical polymerization process for manufacturing water-soluble polymers from monomers in aqueous solution |
| CN1510063A (en) * | 2002-12-24 | 2004-07-07 | 北京嘉乐康环保技术有限公司 | Natural polymer modified compound, preparing method and application thereof |
| CN102250291A (en) * | 2011-05-25 | 2011-11-23 | 何善媛 | Ampholytic modified grafted starch flocculant |
| JP2013103161A (en) * | 2011-11-11 | 2013-05-30 | Nissin Electric Co Ltd | Method for adsorbing noble metal and noble metal adsorbent |
| CN103342787A (en) * | 2013-06-28 | 2013-10-09 | 中北大学 | Preparation method of chromate adsorbing material |
| CN103613709A (en) * | 2013-09-30 | 2014-03-05 | 内蒙古大学 | Method for synthesizing special heavy metal absorption ion resin by using potato starch xanthate as raw material |
| CN106279543A (en) * | 2016-08-07 | 2017-01-04 | 福建农林大学 | A kind of preparation method of cellulose base hydrophobic material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317121A (en) * | 2018-10-31 | 2019-02-12 | 天津工业大学 | A kind of ion blotting fiber and preparation method thereof orienting extracting and enriching hexavalent chromium |
| CN117343372A (en) * | 2023-10-27 | 2024-01-05 | 无锡德泰纳维高新材料有限公司 | Antibacterial plastic and preparation method thereof |
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