CN105413660B - A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof - Google Patents
A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high absorption heavy metal ion chelating agents based on nanometer titanium dioxide silicon structure and preparation method thereof, it is using nano silicon dioxide nanospheres as base material, by atom transferred free radical living polymerization (ATRP) technology in microsphere surface graft polymers, and then to polymer brush chemical modification, dithiocar-bamate (DTC) functional group with strong absorption chelating ability is introduced in its side chain.The suction-operated site enriched in the bigger serface of such materials combine nanometer silicon dioxide material and polymer side chain structure can realize effective adsorbing separation, such as Cu to contents of many kinds of heavy metal ion within a short period of time2+、Cd2+、Ni2+、Pb2+、Hg2+Deng.The Nano type heavy metal chelant that the present invention reports has huge application potential in improvement heavy metal in water ionic soil field.
Description
Technical field
The present invention relates to a kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and its preparation sides
Method belongs to functional high molecule material synthesis field.
Background technology
Since the mankind are increasingly frequent to industrial activities such as exploitation, the smeltings of heavy metal, damage human survival health
Problem of environmental pollution, including heavy metal atmosphere pollution, heavy metal water body pollution, soil pollution by heavy metal etc..Wherein, water pollution
There is big, difficult to control, the easy diffusion in region, and serious harm is made to human body by approach such as food chain concentration or drinking-water.
Heavy metal ion, which enters human body, to be combined with biological enzyme, and then inhibits protein synthesis, inducible protein denaturation, and disturbs nerve
System.The situation is tense for heavy metal water body pollution, becomes one of environmental issue instantly urgently to be resolved hurrily.
In the mask work of heavy metal in water ion, researchers are made that a large amount of trials.Chemiadsorption has
Have the advantages that at low cost, capacity is big, easily implement, is recyclable as the important means for administering heavy metal water body pollution, adsorbent and
The suction-operated of heavy metal ion generally has both the characteristics of physical absorption and chemisorbed.The research and development of high-performance adsorbent are to improve
The key point of heavy metal containing sewage regulation effect.
Chinese patent literature CN103159896A discloses a kind of preparation method of cellulose graft acrylic copolymer, is
Using water as solvent, N, N- methylene-bisacrylamides are crosslinking agent, and azodiisobutyronitrile is initiator, using cellulose as matrix,
Sodium acrylate and n-vinyl pyrrolidone are comonomer, are copolymerized and are obtained using solution polymerization process.The present invention utilizes height
The strong adsorption capacity of the strong sequestering power of molecule chelating agent, carboxyl and amido bond, to the heavy metal ion in waste water and organic sun
Ionic dye has the characteristics that adsorption capacity is strong, adsorption capacity is big, percent of decolourization is high, available for the heavy metal in adsorbing and removing waste water
The organic cation dyes such as ion and methylene blue.The cellulose copolymer of the present invention reaches the removal rate of Cu in waste water ion
95.1%, 99.5% is reached to the removal rate of methylene blue.But the copolymer specific surface area is small, and adsorption site is few, adsorbing and removing
Heavy metal ion ability in waste water is weaker.
The content of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of high absorption heavy metal based on nanometer titanium dioxide silicon structure from
Sub- chelating agent and preparation method thereof.
Summary of the invention
The preparation method of high absorption Nano type heavy metal ion chelating agent of the invention, present invention selection compare table with larger
The Nano-meter SiO_2 of area2Material is base material, first, is prepared for Nano-meter SiO_22- Br, then, by ATRP, (atom transferred free radical gathers
Closing) PGMA is grafted on Nano-meter SiO_2 by living polymerization2- Br surfaces, and then introduce the functional base of a large amount of absorption heavy metal ion
Group, finally, Nano type heavy metal ion chelating agent is prepared for by chemical modification.It is chelated and made by the absorption of functional functional group
With, can to heavy metal ions in sewage carry out quickly and effectively absorption chelate.Have very in heavy metal-polluted water harnessing field
Wide application prospect.
Detailed description of the invention
Technical scheme is as follows：
A kind of high absorption Nano type heavy metal ion chelating agent, has the structure shown in formula (I)：
In formula (I), 100≤n≤300.
, according to the invention it is preferred to, heavy metal ion chelating agent specific surface area is 130-170m2/ g, grafting rate 55-
94%.
The preparation method of above-mentioned high absorption Nano type heavy metal ion chelating agent is as follows including step：
(1) Nano-meter SiO_22Surface amino groups be modified
By Nano-meter SiO_22Ultrasound is dispersed in absolute ethyl alcohol, adds 3- aminopropyl triethoxysilane coupling agents
(KH550), stir at room temperature, be warming up to 70-90 DEG C, and in N2It flows back, centrifuges in atmosphere, the solids centrifuged is dispersed in
It washs in absolute ethyl alcohol, is then dried in vacuo, obtain Nano-meter SiO_22-NH2；
(2) Nano-meter SiO_22-NH2Bromo is modified
Nano-meter SiO_2 prepared by step (1)2-NH2Ultrasonic disperse adds in triethylamine, is slowly added dropwise under ice bath in toluene
2- bromine isobutyl acylbromides, react at room temperature, and water and absolute ethyl alcohol washing, vacuum drying obtain Nano-meter SiO_22-Br；
(3) Nano-meter SiO_22The preparation of-PGMA
Nano-meter SiO_2 prepared by above-mentioned steps (2)2- Br is dispersed in glycidyl methacrylate (GMA) and different
In the methyl phenyl ethers anisole solution of bromo-butyric acid hydroxyl ethyl ester (HEBIB), liquid nitrogen frozen displacement N2After twice, CuBr is dispersed in system
In, freeze-substitution N is carried out again2；By in the methyl phenyl ethers anisole solution addition system of pentamethyl-diethylenetriamine (PMDETA), at room temperature
It thaws and is coordinated, then system is warming up to 40-60 DEG C of polymerisation 2-8h；It centrifuges, washs, vacuum drying obtains nanometer
SiO2-PGMA；
(4) Nano-meter SiO_22The DTC of-PGMA is modified
By Nano-meter SiO_22- PGMA is scattered in n,N-Dimethylformamide, adds in excessive ethylenediamine (EDA), at room temperature
8-20h is reacted, is centrifuged；Products therefrom is scattered in NaOH aqueous solutions, and CS is added dropwise2, react at room temperature, after centrifugation
Washing is dried in vacuo and adsorbs Nano type heavy metal ion chelating agent to get height.
It is currently preferred, in step (1), Nano-meter SiO_22Grain size for 20-600nm, Nano-meter SiO_22Additive amount with
The mass ratio of KH550 is 10:1-5:1；The mass ratio of nano silicon dioxide and absolute ethyl alcohol is 1:50-1:100.
It is currently preferred, in step (1), it is warming up to 80-85 DEG C, washing times 2-5 times, vacuum drying temperature 35-
45℃。
It is currently preferred, in step (2), Nano-meter SiO_22-NH2The mass ratio of additive amount and 2- bromine isobutyl acylbromides be 10:
1-5:1, the molar feed ratio of triethylamine and 2- bromine isobutyl acylbromides is 2:1-1:1；Nano-meter SiO_22-NH2It is 1 with toluene mass ratio:
50-1:100。
It is currently preferred, in step (2), reaction time 10-30h, it is preferred that reaction time 24-26h.
Currently preferred, in step (3), the molar ratio of different bromo-butyric acid hydroxyl ethyl ester and glycidyl methacrylate is
1：500-1:200, the molar ratio of glycidyl methacrylate (GMA) and CuBr are 400:1-200:1, pentamethyl divinyl
The molar ratio of triamine (PMDETA) and CuBr are 2:1, Nano-meter SiO_22- Br and the mass ratio of glycidyl methacrylate are 1:
2-1:5。
Currently preferred, in step (3), polymeric reaction temperature is 50 DEG C, reaction time 4h, and washing methods is with four
Hydrogen furans dispensing laundry is three times.
It is currently preferred, in step (4), Nano-meter SiO_22The mass ratio of-PGMA and ethylenediamine (EDA) is 1:1-1:2, CS2
The molar ratio of dripping quantity and ethylenediamine (EDA) be 1:1；N,N-dimethylformamide and Nano-meter SiO_22The mass ratio of-PGMA is
10:1-5:1, the concentration of NaOH solution is 2mol/L.
Currently preferred, in step (4), the room temperature reaction time is for 24 hours, to wash to wash three with water and methanol successively
It is secondary.
The preparation principle of the present invention：
It is described based on Nano-meter SiO_22The high absorption heavy metal ion chelating agent of structure is with Nano-meter SiO_22Material is base material, tool
There is the high-specific surface area characteristic of nano material.By ATRP activity polymerizating technologies in Nano-meter SiO_22Material surface situ-formed graft is a large amount of
PGMA polymer brush, and then open loop modification is carried out to the epoxy base side chain of PGMA, dithiocarbamates is introduced in its structural unit
Formates functional group.Therefore, heavy metal ion chelating agent of the present invention is heavy metal ion adsorbed with what is extremely enriched
Active site.
The excellent results of the present invention are as follows：
1st, the present invention is with Nano-meter SiO_22For base material, there is larger specific surface area, heavy metal ion chelating agent specific surface area
For 130-170m2/ g, grafting rate 55-94% are conducive to improve the rate of adsorption.
2. the present invention is by atom transfer (ATRRP) activity polymerizating technology, in nanosized SiO_2 surface grafting number of polymers
Brush, and abundant active adsorption sites are introduced in its structural unit, structure design is conducive to improve adsorption capacity.
3. the recyclable heavy metal ion of the present invention, and realize the recycling of chelating agent, use cost can be greatly reduced.
4. raw material of the present invention is easy to get, preparation process is simple, and chemical stability is high, and exploitativeness is higher in practical application.
5. the present invention has boundless application prospect in heavy metal-polluted water harnessing field.
Description of the drawings
Fig. 1 is the infrared spectrogram of Nano type heavy metal ion chelating agent prepared by embodiment 1.
Fig. 2 be embodiment 1 prepare Nano type heavy metal ion chelating agent at 25 DEG C to Cu2+、Pb2+、Cd2+Deng a huge sum of money
Belong to the curve of adsorption kinetics of ion.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of preparation method of high absorption Nano type heavy metal ion chelating agent, step are as follows：
Step (1) Nano-meter SiO_22Surface amino groups be modified
By the Nano-meter SiO_2 of 2g grain sizes 30nm2It is dispersed in 80mL absolute ethyl alcohols, adds in three second of 0.4g 3- aminopropyls
Oxysilane coupling agent (KH550), stirs 2h at room temperature, is warming up to 85 DEG C in N2Flow back 1h in atmosphere.It centrifuges, is dispersed in
It is washed in absolute ethyl alcohol three times, vacuum drying obtains Nano-meter SiO_22-NH2。
Step (2) Nano-meter SiO_22-NH2Bromo is modified
By 1.8g Nano-meter SiO_2s2-NH2Ultrasonic disperse is uniform in 100mL toluene, addition 0.13g triethylamines, under additional ice bath
0.3g 2- bromine isobutyl acylbromides are slowly added dropwise, react 30h at room temperature, second alcohol and water is dried in vacuo after alternately washing twice and is received
Rice SiO2-Br。
Step (3) Nano-meter SiO_22The preparation of-PGMA
By 2g Nano-meter SiO_2s2- Br is dispersed in the methyl phenyl ethers anisole solution of 5g GMA and 20mg HEBIB, and liquid nitrogen frozen is put
Change N2Afterwards, 15mg CuBr are dispersed in system, carry out freeze-substitution N again2.The methyl phenyl ethers anisole of 18mg PMDETA is molten
Liquid injects above-mentioned system, coordination of thawing at room temperature, and then system is warming up to 50 DEG C of polymerization 4h.The SiO that will be obtained2- PGMA is centrifuged
Separation, tetrahydrofuran wash three times, vacuum drying.
Step (4) Nano-meter SiO_22The DTC of-PGMA is modified
Nano-meter SiO_2 prepared by 2g2- PGMA is dispersed in n,N-Dimethylformamide, adds in 2g ethylenediamines (EDA), room
The lower reaction 12h of temperature, centrifuges.Products therefrom is dispersed in the NaOH aqueous solutions of 2mol/L, and 2.5g CS are added dropwise2, at room temperature instead
It should be washed three times to get Nano type metal-chelator with water and ethyl alcohol successively after centrifugation for 24 hours.
Heavy metal ion chelating agent manufactured in the present embodiment is to Cu2+Adsorption capacity be 2.108mmol/g；To Cd2+Suction
Attached capacity is 1.077mmol/g；To Pb2+Adsorption capacity be 1.195mmol/g.
It is desorbed after prepared heavy metal ion chelating agent adsorption saturation with the sodium ethylene diamine tetracetate of 0.2mol/L
It is attached, then to Cu in the environment of pH=52+、Pb2+、Cd2+Heavy metal ion is adsorbed, to Cu2+Adsorption capacity be
2.056mmol/g；To Cd2+Adsorption capacity be 1.015mmol/g；To Pb2+Adsorption capacity be 1.109mmol/g.The present invention
Heavy metal ion chelating agent can realize the recycling recycled and to heavy metal ion, application cost can be greatly reduced.
The adsorption capacity of Nano type heavy metal ion chelating agent measures as follows：Precise certain mass (m)
Nano type heavy metal ion chelating agent, add in a series of same volumes (V) various concentration (C0) pH=5 heavy metal ion
In solution.It fully adsorbs in constant temperature oscillation shaking table at 25 DEG C, after effect, is separated by filtration.It is sent out with inductance linking atom
Penetrate the equilibrium concentration (C that spectrum (ICP-AES) measures heavy metal ion in solutione).Equilibrium adsorption capacities (Qe) count as follows
It calculates：
Qe=(C0-Ce)V/m
Embodiment 2
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step
(1) grain size of nano silicon dioxide used in is 400nm, and the nano-silica surface grafting rate of preparation is 57.30%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be
1.593mmol/g；To Cd2+Adsorption capacity be 0.672mmol/g；To Pb2+Adsorption capacity be 0.886mmol/g.
Embodiment 3
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step
(2) the room temperature reaction time is 10h in, and prepared nano-silica surface grafting rate is 72.85%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be
1.775mmol/g；To Cd2+Adsorption capacity be 0.695mmol/g；To Pb2+Adsorption capacity be 0.962mmol/g.
Embodiment 4
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step
(3) addition of HEBIB used in is 38mg, and prepared nano-silica surface grafting rate is 75.86%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be
1.905mmol/g；To Cd2+Adsorption capacity be 0.861mmol/g；To Pb2+Adsorption capacity be 1.037mmol/g.
Embodiment 5
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step
(3) addition of CuBr used in and PMDETA is respectively 25mg and 30mg, and prepared nano-silica surface grafting rate is
93.52%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be
2.351mmol/g；To Cd2+Adsorption capacity be 1.183mmol/g；To Pb2+Adsorption capacity be 1.336mmol/g.
Embodiment 6
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step
(4) EDA used in and Nano-meter SiO_22The mass ratio of-PGMA is 2:1, CS used2Molar ratio with EDA is 1:1.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be
2.253mmol/g；To Cd2+Adsorption capacity be 1.160mmol/g；To Pb2+Adsorption capacity be 1.258mmol/g.
Claims (7)
1. a kind of preparation method of high absorption Nano type heavy metal ion chelating agent, as follows including step：
(1) Nano-meter SiO_22Surface amino groups be modified
By Nano-meter SiO_22Ultrasound is dispersed in absolute ethyl alcohol, adds 3- aminopropyl triethoxysilane coupling agent KH550, room temperature
Lower stirring, is warming up to 70-90 DEG C, and in N2It flows back, centrifuges, the solids centrifuged, which is dispersed in absolute ethyl alcohol, to be washed in atmosphere
It washs, is then dried in vacuo, obtain Nano-meter SiO_22-NH2；
(2) Nano-meter SiO_22-NH2Bromo is modified
By step（1）The Nano-meter SiO_2 of preparation2-NH2Ultrasonic disperse adds in triethylamine, 2- bromines is slowly added dropwise under ice bath in toluene
Isobutyl acylbromide, reacts at room temperature, and water and absolute ethyl alcohol washing, vacuum drying obtain Nano-meter SiO_22-Br；
(3) Nano-meter SiO_22The preparation of-PGMA
By above-mentioned steps（2）The Nano-meter SiO_2 of preparation2- Br is dispersed in glycidyl methacrylate GMA and different bromo-butyric acid
In the methyl phenyl ethers anisole solution of hydroxyl ethyl ester, liquid nitrogen frozen displacement N2After twice, CuBr is dispersed in system, is freezed again
Replace N2；By coordination of in the methyl phenyl ethers anisole solution addition system of pentamethyl-diethylenetriamine PMDETA, thawing at room temperature, Ran Houti
System is warming up to 40-60 DEG C of polymerisation 2-8 h；It centrifuges, washs, vacuum drying obtains Nano-meter SiO_22-PGMA；Different bromine fourth
The molar ratio of sour hydroxyl ethyl ester and glycidyl methacrylate is 1：500-1:200, glycidyl methacrylate GMA
Molar ratio with CuBr is 400:1-200:1, the molar ratio of pentamethyl-diethylenetriamine PMDETA and CuBr are 2:1, nanometer
SiO2- Br and the mass ratio of glycidyl methacrylate are 1:2-1:5；
(4) Nano-meter SiO_22The DTC of-PGMA is modified
By Nano-meter SiO_22- PGMA is scattered in n,N-Dimethylformamide, is added in excessive ethylenediamine EDA, is reacted 8- at room temperature
20 h are centrifuged；Products therefrom is scattered in NaOH aqueous solutions, and CS is added dropwise2, react at room temperature, after centrifugation successively
It is washed three times with water and methanol, is dried in vacuo and adsorbs Nano type heavy metal ion chelating agent to get height；Nano-meter SiO_22- PGMA with
The mass ratio of ethylenediamine EDA is 1:1-1:2, CS2The molar ratio of dripping quantity and ethylenediamine EDA be 1:1；N, N- dimethyl
Formamide and Nano-meter SiO_22The mass ratio of-PGMA is 10:1-5:1, the concentration of NaOH solution is 2 mol/L, reacts at room temperature the time
For 24 h.
2. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step
Suddenly（1）In, Nano-meter SiO_22Grain size for 20-600 nm, Nano-meter SiO_22Additive amount and KH550 mass ratio be 10:1-5:1；It receives
Rice SiO2Mass ratio with absolute ethyl alcohol is 1:50-1:100.
3. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step
Suddenly（1）In, 80-85 DEG C is warming up to, washing times 2-5 times, vacuum drying temperature is 35-45 DEG C.
4. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step
Suddenly（2）In, Nano-meter SiO_22-NH2The mass ratio of additive amount and 2- bromine isobutyl acylbromides be 10:1-5:1, triethylamine and 2- bromine isobutyls
The molar feed ratio of acylbromide is 2:1-1:1；Nano-meter SiO_22-NH2It is 1 with toluene mass ratio:50-1:100.
5. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step
Suddenly（2）In, the reaction time is 10-30 h.
6. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step
Suddenly（3）In, polymeric reaction temperature be 50 DEG C, the reaction time be 4 h, washing methods be with tetrahydrofuran dispensing laundry three times.
7. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that weight
Metal ion chelation agent specific surface area is 130-170 m2/ g, grafting rate 55-94%.
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