CN103464124B - Spongy emergency adsorbing material and preparation method thereof - Google Patents
Spongy emergency adsorbing material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 46
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 46
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 230000008961 swelling Effects 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 125000003277 amino group Chemical class 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229950004959 sorbitan oleate Drugs 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- -1 polyoxyethylene oleic acid Polymers 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 9
- 150000002500 ions Chemical class 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 239000011133 lead Substances 0.000 abstract description 2
- 239000008239 natural water Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 2
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000008236 heating water Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical class OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BNECGDCGGVACFF-UHFFFAOYSA-N 2,2-diethylbutanenitrile Chemical compound CCC(CC)(CC)C#N BNECGDCGGVACFF-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001702 transmitter Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a spongy emergency adsorbing material and a preparation method thereof, and belongs to the field of environment material synthesis and application. Artificially-synthesized high molecular materials are adopted as a matrix, according to graft polymerization and a nucleophilic substitution reaction of amine derivatives, a polyvinyl alcohol sponge is used as a skeleton, a grafting reaction and modified synthesis are carried out on the surface, and the spongy emergency adsorbing material is obtained. The preparation method is simple and low in raw material price, the obtained spongy adsorbing material is large in toughness, is provided with pore passages and surfaces with the high hydrophilic performance and can rapidly and efficiently remove various heavy metal ions in water under the group action of the pore passages and the surfaces, the time for equilibrium adsorption of the heavy metal ions such as nickel, copper and lead is only about 10min, and the absorbed sponge is easily recycled and reused after being reproduced. The spongy emergency adsorbing material is particularly suitable for the emergency disposal of an emergency heavy metal water contamination accident which happens in natural water such as a riverway and a lake.
Description
Technical field:
The invention discloses a kind of emergent sorbing material and preparation method thereof, is a kind of spongy emergent sorbing material and preparation method thereof in particular.
Background technology:
In recent years, environment suddenly accident happens occasionally, and the water pollutions accident especially caused because of heavy metal pollution takes place frequently.How fast, in efficient removal water, heavy metal ion becomes the hot issue in Study on Water Pollution Control field.Resin type adsorbent based on macromolecule polymer material has that adsorption capacity is large, structure controllable, be easy to the advantages such as regeneration and be widely used in field of waste water treatment.But there is following deficiency when processing burst water pollution accident in traditional particulate resin: 1) particulate resins needs to contact with contaminated water body in adsorption column or blending tank, is difficult at the purifying polluted water body of the river course situ that The turbulent river crashes its way through, water surface disturbance is violent; 2) rate of adsorption of particulate resins is relatively low, is difficult to a large amount of contaminated water body of process in the short time.Fiber is adopted to cause the attention of people at present as the disposal that sorbing material is applied to burst mode tra nsmitter.But use in water body at fibrous material and need set, otherwise be easily mutually wound around and broken up loss by current, reduce its utilization rate.
Summary of the invention:
1, the technical problem that will solve is invented
For existing fibrous sorbing material, set is needed for actual water body emergency processing, be difficult to sprawl on a large scale and the limitation brought, the invention provides a kind of emergent absorption sponge and preparation method thereof, simple method is adopted to carry out pretreatment to polyvinyl alcohol (PVA) sponge, by the nucleophilic substitution of graft reaction and amine derivative, the obtained novel spongy containing hydroxamic acid structure is met an urgent need sorbing material.It is extremely low that the sponge matrix that this invention adopts does not have aromatic structure, bio-toxicity, high level PVA sponge even can be medical, this novel spongy meets an urgent need sorbing material synthesis step simply in addition, has very high hydrophily, can remove heavy metal ion in water fast and efficiently.
2, technical scheme
Spongy emergent sorbing material provided by the present invention adopts PVA sponge to prepare through the nucleophilic substitution of glycerol polymerization and amine derivative.
A kind of spongy emergent sorbing material, it is by with polyvinyl alcohol ((polyvinyl alcohol, English name is abbreviated as PVA, No. CAS: 9002-89-5, average degree of polymerization 2000-3000) sponge is skeleton, surface is by graft reaction and modify synthesis, and its basic structure formula is as follows:
{ bracket ' [] ' represents high molecular polymer structural units, x is polyvinyl alcohol average degree of polymerization (2000-3000), the average of the methyl acrylate units of a representation unit polyvinyl alcohol structures unit grafting, with polymerization single polymerization monomer percent grafting about (in the present invention, the value of a is between 1.5-2) }.
Described emergent sorbing material is spongy, and skeleton and surface have the functional group of quick heavy-metal ion removal.A kind of spongy emergent sorbing material, its synthesis flow and basic structure formula as follows:
(1) PVA sponge pretreatment
(a) extracting: by the organic solvent extractant extracting 8 ~ 12 hours in Soxhlet extractor of PVA sponge, then at room temperature dry;
B () is swelling: will be placed in three-neck flask through the dried PVA sponge of extracting, adds distilled water swelling 1 ~ 2 hour.The mass ratio of distilled water and sponge is 50 ~ 100:1, and swelling temperature is room temperature;
The organic solvent used in step (1-a) is acetone, benzene or benzinum.
(2) preparation reaction emulsion
Grafted monomers, dispersant and water are mixed, wherein the proportioning of grafted monomers, dispersant and water is as follows: 11.1 ~ 18.3mL:1g:100 ~ 151.7mL;
The grafted monomers used in step (2) is methyl acrylate; The dispersant used is gelatin, polyvinyl alcohol or Tissuemat E.
(3) graft reaction
Initator is added after being mixed with emulsion by PVA sponge, PVA sponge (extracting dry after quality) is 5g:1 ~ 2g:500mL or 5g:1 ~ 2mL:500mL with the ratio of initator, emulsion, react 8 ~ 12 hours at 85 ~ 95 DEG C, obtain grafting sponge, the rear 50 DEG C of vacuum drying of acetone cleaning, percent grafting=(grafting sponge quality-PVA sponge quality)/PVA sponge quality;
The initator used in step (3) is benzoyl peroxide, di-t-butyl peroxide or acyl azo diethyl butyronitrile.
(4) nucleophilic substitution of amine derivative
A alkali, liquid amine derivative or solid amine derivative, emulsifying agent and distilled water are mixed with reactant liquor by (), its configuration proportion is 2 ~ 3g:2 ~ 3mL:1mL:100mL or 2 ~ 3g:2 ~ 3g:1mL:100mL;
B grafting sponge mixes with above-mentioned reactant liquor by () after, wherein in grafting sponge and step 4-a, ratio that is solid-state or liquid amine derivative is 1g:1 ~ 1.5g or 1g:1 ~ 1.5mL, 45 ~ 60 DEG C of reactions 12 ~ 20 hours, obtain spongy emergent sorbing material (being called for short PVA-G-N), the rear 50 DEG C of vacuum drying of distilled water cleaning.
The alkali used in step (4-a) is NaOH or potassium hydroxide; The amine derivative used elects 50% (mass percent mark) aqueous hydroxylamine solution, hydroxylamine hydrochloride or HAS as; The emulsifying agent used is polyethenoxy sorbitan oleate, polyoxyethylene oleic acid ester or diglycerol polypropylene glycol ether.
3, beneficial effect
The invention provides a kind of preparation method of spongy emergent sorbing material, nontoxic PVA sponge is adopted to be matrix, upper hydroxamic acid structure is modified by grafting, nucleophilic substitution, its cheaper starting materials is easy to get, synthesis technique step is simple, the emergent absorption sponge that the present invention obtains can remove heavy metal ion in water by quick adsorption, both particulate resin fixed bed pattern can have been adopted to adsorb, mesh bag can be loaded again and in the natural water bodies such as river, river, lake, carry out original position absorption for environmental pollution emergency processing, and easily reclaiming, avoids secondary pollution.The present invention is not only applicable to complicated water environment conditions, and is convenient to be separated from water after absorption, can reuse, can be widely used in the emergency disposal of heavy metal ion in burst water contamination accident with after acid solution regeneration.
Accompanying drawing explanation
Fig. 1 is ftir analysis (FT-IR) collection of illustrative plates of the spongy emergent sorbing material that embodiment of the present invention 1-5 prepares.According to bibliography (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p184).
(abscissa represents chemical shift to the 13C NMR collection of illustrative plates of the spongy emergent sorbing material that Fig. 2 (a) prepares for embodiment of the present invention 1-5, unit is ppm), Fig. 2 (b) is structure chart corresponding to Fig. 2 (a) characteristic peak, its characteristic peak δ 186.63, δ 73.28, δ 64.64, δ 52.15, structure corresponding to δ 41.34 are listed in Fig. 2 (b), according to bibliography (organic chemistry), association reaction raw material, the reaction mechanism mechanism of reaction, and the infared spectrum of product, characteristic peak positions in nuclear magnetic resonance map, the structure determining material can be identified.According to bibliography (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p216).
Fig. 3 is the structure chart of spongy emergent sorbing material.
Fig. 4-1, Fig. 4-2, Fig. 4-3, Fig. 4-4 and Fig. 4-5 is respectively the scanning electron microscope (SEM) photograph of the spongy emergent sorbing material that embodiment of the present invention 1-5 prepares, after graft reaction and chemical modification, sponge is inner and surperficial defines coarse fold, the group with hydroxamic acid that these folds are modified can fast and heavy metal ion chelating, makes sponge can heavy-metal ion removal fast.
Detailed description of the invention
Embodiment 1
A kind of spongy emergent sorbing material its preparation methods steps is:
(1) PVA sponge pretreatment
(a) extracting: by the 200mL benzinum extracting 11 hours in Soxhlet extractor of 5gPVA sponge, room temperature is dried;
B () is swelling: the PVA sponge of drying is placed in three-neck flask, and add 500mL distilled water swelling 1 hour, swelling temperature is room temperature, is outwelled by water afterwards.
(2) preparation reaction emulsion
By 50mL methyl acrylate, 4.5g gelatin, the mixing of 450mL distilled water, fully stir.
(3) graft reaction
Reaction emulsion is poured in the three-neck flask that PVA sponge is housed, add 1.5g benzoyl peroxide, 88 DEG C of heating water baths, and with the rotating speed stirring reaction 11 hours of 60r/min, reaction gained grafting sponge is carried out Separation of Solid and Liquid, after acetone cleaning, 50 DEG C of vacuum drying, the percent grafting of gained grafting sponge is 380%, a value is 1.9.
(4) nucleophilic substitution of amine derivative
A () gets 10g NaOH, 15g HAS, 5mL polyethenoxy sorbitan oleate, 500mL distilled water are made into reaction solution;
B () gets the dried grafting sponge of 10g, add in reactant liquor, and with the rotating speed stirring reaction 18 hours of 60r/min at 48 DEG C, product is vacuum drying at 50 DEG C after distilled water cleaning, obtains spongy emergent sorbing material finished product.Its physicochemical property is as follows:
By to the infrared spectrum analysis of spongy emergent sorbing material as shown in Figure 1, after graft reaction, amine derivative nucleophilic substitution, there is amido and carbonyl characteristic peak at δ 1581.8, δ 1737 place in spongy emergent sorbing material.Carbon-13 nmr spectra is analyzed as shown in Fig. 2 (a) He Fig. 2 (b), and comprehensive infrared spectrum analysis and nuclear magnetic resonance spectroscopy, spongy emergent sorbing material structure as shown in Figure 3
carry out sem observation to obtained spongy emergent sorbing material, result is as shown in Fig. 4-1.
Embodiment 2
A kind of spongy emergent sorbing material its preparation methods steps is:
(1) PVA pretreatment
(a) extracting: by the 200mL benzene extracting 9 hours in Soxhlet extractor of 5gPVA sponge, room temperature is dried;
B () is swelling: the PVA sponge of drying is placed in three-neck flask, adds 350mL distilled water swelling 1.5 hours, is outwelled by water afterwards.
(2) preparation reaction emulsion
By 50mL methyl acrylate, 3g Tissuemat E, the mixing of 450mL distilled water, fully stir.
(3) graft reaction
Reaction emulsion is poured in the three-neck flask that PVA sponge is housed, add 2g azodiisobutyronitrile, 92 DEG C of heating water baths, and with the rotating speed stirring reaction 9 hours of 60r/min, reaction gained grafting sponge is carried out Separation of Solid and Liquid, after acetone cleaning, 50 DEG C of vacuum drying, the percent grafting of gained grafting sponge is 298%, a value is 1.5.
(4) nucleophilic substitution of amine derivative
A () gets 12g potassium hydroxide, 8mL50% (mass fraction) aqueous hydroxylamine solution, 4mL diglycerol glycol ether, 400mL distilled water are made into reaction solution;
B () gets the dried grafting sponge of 7g, add in reactant liquor, and with the rotating speed stirring reaction 14 hours of 60r/min at 55 DEG C, product is vacuum drying at 50 DEG C after distilled water cleaning, obtains spongy emergent sorbing material finished product.Its physicochemical property is as follows:
By to the infrared spectrum analysis of spongy emergent sorbing material as shown in Figure 1, after graft reaction, amine derivative nucleophilic substitution, there is amido and carbonyl characteristic peak at δ 1581.8, δ 1737 place in spongy emergent sorbing material.Carbon-13 nmr spectra is analyzed as shown in Fig. 2 (a) He Fig. 2 (b), comprehensive infrared spectrum analysis and nuclear magnetic resonance spectroscopy, as shown in Figure 3, carry out sem observation to obtained spongy emergent sorbing material, result as shown in the Fig. 4-2 for spongy emergent sorbing material structure.
Embodiment 3
A kind of spongy emergent sorbing material its preparation methods steps is:
(1) PVA pretreatment
(a) extracting: by the 200mL benzinum extracting 12 hours in Soxhlet extractor of 5g PVA sponge, room temperature is dried;
B () is swelling: the PVA sponge of drying is placed in three-neck flask, adds 400mL distilled water swelling 1.5 hours, is outwelled by water afterwards.
(2) preparation reaction emulsion
By 55mL methyl acrylate, 3g polyvinyl alcohol, the mixing of 445mL distilled water, fully stir.
(3) graft reaction
Reaction emulsion is poured in the three-neck flask that PVA sponge is housed, add 1.0mL di-t-butyl peroxide, 85 DEG C of heating water baths, and with the rotating speed stirring reaction 12 hours of 60r/min, reaction gained grafting sponge is carried out Separation of Solid and Liquid, after acetone cleaning, 50 DEG C of vacuum drying, the percent grafting of gained grafting sponge is that 307%, a value is about 1.6.
(4) nucleophilic substitution of amine derivative
A () gets 11g potassium hydroxide, 12mL50% (mass fraction) aqueous hydroxylamine solution, 4.5mL diglycerol glycol ether, 450mL distilled water are made into reaction solution;
B () gets the dried grafting sponge of 12g, add in reactant liquor, and with the rotating speed stirring reaction 16 hours of 60r/min at 50 DEG C, product is vacuum drying at 50 DEG C after distilled water cleaning, obtains spongy emergent sorbing material finished product.Its physicochemical property is as follows:
By to the infrared spectrum analysis of spongy emergent sorbing material as shown in Figure 1, after graft reaction, amine derivative nucleophilic substitution, there is amido and carbonyl characteristic peak at δ 1581.8, δ 1737 place in spongy emergent sorbing material.Carbon-13 nmr spectra is analyzed as shown in Fig. 2 (a) He Fig. 2 (b), comprehensive infrared spectrum analysis and nuclear magnetic resonance spectroscopy, as shown in Figure 3, carry out sem observation to obtained spongy emergent sorbing material, result is as shown in Fig. 4-3 for spongy emergent sorbing material structure.
Embodiment 4
A kind of spongy emergent sorbing material its preparation methods steps is:
(1) PVA pretreatment
(a) extracting: by the 200mL benzene extracting 8 hours in Soxhlet extractor of 5gPVA sponge, room temperature is dried;
B () is swelling: the PVA sponge of drying is placed in three-neck flask, adds 250mL distilled water swelling 2 hours, is outwelled by water afterwards.
(2) preparation reaction emulsion
By 45mL methyl acrylate, 3g gelatin, the mixing of 455mL distilled water, fully stir.
(3) graft reaction
Reaction emulsion is poured in the three-neck flask that PVA sponge is housed, add 1g benzoyl peroxide, 95 DEG C of heating water baths, and with the rotating speed stirring reaction 8 hours of 60r/min, reaction gained grafting sponge is carried out Separation of Solid and Liquid, after acetone cleaning, 50 DEG C of vacuum drying, the percent grafting of gained grafting sponge is that 325%, a value is about 1.7.
(4) nucleophilic substitution of amine derivative
A () gets 11g NaOH, 10g hydroxylamine hydrochloride, 4mL polyethenoxy sorbitan oleate, 400mL distilled water are made into reaction solution;
B () gets the dried grafting sponge of 8g, add in reactant liquor, and with the rotating speed stirring reaction 20 hours of 60r/min at 45 DEG C, product is vacuum drying at 50 DEG C after distilled water cleaning, obtains spongy emergent sorbing material finished product.Its physicochemical property is as follows:
By to the infrared spectrum analysis of spongy emergent sorbing material as shown in Figure 1, after graft reaction, amine derivative nucleophilic substitution, there is amido and carbonyl characteristic peak at δ 1581.8, δ 1737 place in spongy emergent sorbing material.Carbon-13 nmr spectra is analyzed as shown in Fig. 2 (a) He Fig. 2 (b), comprehensive infrared spectrum analysis and nuclear magnetic resonance spectroscopy, as shown in Figure 3, carry out sem observation to obtained spongy emergent sorbing material, result is as shown in Fig. 4-4 for spongy emergent sorbing material structure.
Embodiment 5
A kind of spongy emergent sorbing material its preparation methods steps is:
(1) PVA pretreatment
(a) extracting: by the 200mL acetone extracting 10 hours in Soxhlet extractor of 5gPVA sponge, room temperature is dried;
B () is swelling: the PVA sponge of drying is placed in three-neck flask, adds 450mL distilled water swelling 1 hour, is outwelled by water afterwards.
(2) preparation reaction emulsion
By 60mL methyl acrylate, 4g polyvinyl alcohol, the mixing of 440mL distilled water, fully stir.
(3) graft reaction
Reaction emulsion is poured in the three-neck flask that PVA sponge is housed, add 1.5mL di-t-butyl peroxide, 90 DEG C of heating water baths, and with the rotating speed stirring reaction 10 hours of 60r/min, reaction gained grafting sponge is carried out Separation of Solid and Liquid, after acetone cleaning, 50 DEG C of vacuum drying, the percent grafting of gained grafting sponge is that 355%, a value is about 1.8.
(4) nucleophilic substitution of amine derivative
A () gets 12g potassium hydroxide, 12g HAS, 5mL polyoxyethylene oleic acid ester, 500mL distilled water are made into reaction solution;
B () gets the dried grafting sponge of 8g, add in reactant liquor, and with the rotating speed stirring reaction 12 hours of 60r/min at 60 DEG C, product is vacuum drying at 50 DEG C after distilled water cleaning, obtains spongy emergent sorbing material finished product.Its physicochemical property is as follows:
By to the infrared spectrum analysis of spongy emergent sorbing material as shown in Figure 1, after graft reaction, amine derivative nucleophilic substitution, there is amido and carbonyl characteristic peak at δ 1581.8, δ 1737 place in spongy emergent sorbing material.Carbon-13 nmr spectra is analyzed as shown in Fig. 2 (a) He Fig. 2 (b), comprehensive infrared spectrum analysis and nuclear magnetic resonance spectroscopy, as shown in Figure 3, carry out sem observation to obtained spongy emergent sorbing material, result as illustrated in figures 4-5 for spongy emergent sorbing material structure.
Embodiment 1-5 obtains spongy emergent sorbing material, preparation method is simple, low in raw material price, prepared sponge sorbing material toughness is large, have high-hydrophilic duct and surface, contents of many kinds of heavy metal ion in water can be removed fast and efficiently by the group effect on duct and surface, about 10 minutes are only to the equilibrium adsorption time of the heavy metal ion such as nickel, copper, lead, and the sponge after absorption is easy to reclaim, and reuses after renewable.
Claims (7)
1. a spongy emergent sorbing material, is characterized in that, it is by taking polyvinylalcohol sponge as skeleton, and surface is by graft reaction and modify synthesis, and its basic structure formula is as follows:
X is polyvinyl alcohol average degree of polymerization, the average of the methyl acrylate units of grafting on x=2000-3000, a representation unit polyvinyl alcohol structures unit, a=1.5-2.
2. spongy emergent sorbing material according to claim 1, is characterized in that, described sorbing material is spongy, and its skeleton and surface have the functional group of quick heavy-metal ion removal.
3. a preparation method for spongy emergent sorbing material, the steps include:
(1) PVA pretreatment
A. extracting: by the organic solvent extracting 8 ~ 12 hours in Soxhlet extractor of PVA sponge, then at room temperature dry;
B. swelling: will be placed in three-neck flask through the dried PVA sponge of extracting, and add distilled water swelling 1 ~ 2 hour, the mass ratio of distilled water and sponge is 50 ~ 100:1, and swelling temperature is room temperature;
(2) preparation reaction emulsion
Grafted monomers, dispersant and water are mixed, wherein the proportioning of grafted monomers, dispersant and water is 11.1 ~ 18.3mL:1g:100 ~ 151.7mL;
(3) graft reaction
Initator is added after the reaction emulsion that PVA sponge and step (2) are prepared being mixed, the ratio of PVA sponge when extracting is dried, initator and reaction emulsion is 5g:1 ~ 2g:500mL or 5g:1 ~ 2mL:500mL, react 8 ~ 12 hours at 85 ~ 95 DEG C, obtain grafting sponge, the rear 50 DEG C of vacuum drying of acetone cleaning;
(4) nucleophilic substitution of amine derivative
A. alkali, liquid amine derivative or solid amine derivative, emulsifying agent and distilled water are mixed with reactant liquor, its configuration proportion is 2 ~ 3g:2 ~ 3mL:1mL:100mL or 2 ~ 3g:2 ~ 3g:1mL:100mL;
B. after grafting sponge being mixed with above-mentioned reactant liquor, wherein in grafting sponge and step (4)-a, ratio that is solid-state or liquid amine derivative is 1g:1 ~ 1.5g or 1g:1 ~ 1.5mL, 45 ~ 60 DEG C of reactions 12 ~ 20 hours, obtain spongy emergent sorbing material, the rear 50 DEG C of vacuum drying of distilled water cleaning.
4. the preparation method of a kind of spongy emergent sorbing material according to claim 3, is characterized in that, the grafted monomers of described step (2) is methyl acrylate; Dispersant is gelatin, polyvinyl alcohol or Tissuemat E.
5. the preparation method of the spongy emergent sorbing material according to claim 3 or 4, is characterized in that, the initator of described step (3) is benzoyl peroxide, di-t-butyl peroxide or azodiisobutyronitrile.
6. the preparation method of spongy emergent sorbing material according to claim 3, is characterized in that, the alkali of described step (4) is potassium hydroxide or NaOH; Amine derivative to be mass fraction be 50% aqueous hydroxylamine solution, hydroxylamine hydrochloride or HAS; Emulsifying agent is polyethenoxy sorbitan oleate, polyoxyethylene oleic acid ester or diglycerol polypropylene glycol ether.
7. the preparation method of the spongy emergent sorbing material according to claim 3 or 4, is characterized in that, the organic solvent extractant used in described step (1)-a is acetone, benzene or benzinum.
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