CN101701042A - Carboxymethyl chitosan thiourea resin and preparation method and application thereof - Google Patents
Carboxymethyl chitosan thiourea resin and preparation method and application thereof Download PDFInfo
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- CN101701042A CN101701042A CN200910020084A CN200910020084A CN101701042A CN 101701042 A CN101701042 A CN 101701042A CN 200910020084 A CN200910020084 A CN 200910020084A CN 200910020084 A CN200910020084 A CN 200910020084A CN 101701042 A CN101701042 A CN 101701042A
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Abstract
The invention relates to a carboxymethyl chitosan thiourea resin and a preparation method and an application thereof, belonging to the technical field of adsorbent resins. The preparation method comprises the following steps: using chitosan with high molecular weight to react with chloroacetic acid and synthesize carboxymethyl chitosan and then perform a series of crosslinking and chemical modification to the carboxymethyl chitosan to prepare carboxymethyl chitosan thiourea resin. The invention relates to the design, synthesis method and adsorption property of carboxymethyl chitosan thiourea resin; the prepared resin through design has good mechanical property, the introduced functional groups have good adsorption to heavy metals, and has excellent adsorption and adsorption selectivity to various heavy metals such as mercury, silver and lead, the synthesis method is simple, and the reaction conditions are relatively mild. The structural formula of the carboxymethyl chitosan chelate resin is shown below, wherein n > 1450.
Description
Technical field
The present invention relates to resin and synthetic method thereof, belong to technical field of adsorbent resins, is a kind of carboxymethyl chitosan thiourea resin, its preparation method and application specifically.
Background technology
Research for resin at present mainly concentrates on fields such as analytical chemistry, thalassochemistry, environment protection, geochemistry, radiological chemistry, catalytic chemistry, medical science, pharmacy, toxicology, hydrometallurgy.Particularly heavy metal ion is serious day by day to the problems such as purifying treatment of the pollution of water quality, chemical industry sewage in recent years, and fields such as geochemistry, environment protection etc. are more and more higher to the demand of resin.Utilize resin to handle to contain the trade effluent of heavy metal ion not only to improve human living environment, simultaneously again can be from industrial waste the useful material of Separation and Recovery, make full use of resource, increase economic efficiency.
Chitosan is present in the crust of crustaceans such as shrimp, crab, and it is extremely extensive to distribute, and is to be only second to cellulosic second largest class natural high moleculer eompound in the world.Chitosan has adsorption to many materials, and amino in its molecule and hydroxyl and many metal ions are (as Cu
2+, Pb
2+Deng) can form stable chelate, can use it for the fields such as separation of metal ion in heavy metal containing wastewater treatment, water purification from the beginning, the hydrometallurgy.In the last few years, used chitosan synthetic resins, and introduce more multi-active base group and increase its absorption property and caused increasing concern.
In the chitosan main chain, introduce carboxymethyl group can improve its to heavy metal ion (as Zn
2+, Pb
2+) adsorptivity, be to study often in recent years, Shengling Sun etc. has synthesized cm-chitosan Pb
2+The trace resin is to Pb
2+High-adsorption-capacity can reach 1.89mmol/g (Shengling Sun, Li Wang, Aiqin Wang.Adsorptionproperties of crosslinked carboxymethyl-chitosan resin withPb (II) as template ions[J] .Jounal of hazardous materials, 2006,136:930.).And introduce sulfydryl in chitosan structure also is the focus of studying in the last few years, can improve the adsorptivity to heavy metal especially precious metal ion, and Li Jian etc. have synthesized the phenylthiourea grafted chitosan, to Cr
6+And Cu
2+Maximum adsorption capacity be respectively 170mg/g and 78mg/g.
Summary of the invention
Problem to be solved by this invention provides a kind of carboxymethyl chitosan thiourea resin and preparation method thereof and application, the present invention not only will introduce carboxymethyl group in the chitosan main chain, and thioureido is advanced in the polymer side chain grafting at cross-linked chitosan, increased the absorption property of resin greatly to some heavy metal ion, make the purposes of this resin more extensive, efficient is higher.
In order to address the above problem, the invention provides the compound of a kind of general formula (I), as follows:
N＞1450 wherein.
The preparation method of this carboxymethyl chitosan thiourea resin is as follows:
Reacted 6-9 hour down at 20-40 ℃ by chitosan and Mono Chloro Acetic Acid, then reaction soln suction filtration, dissolving, deposition and purification are got cm-chitosan; Re-use glutaraldehyde and thiocarbamide at 40-80 ℃ of following hybrid reaction 3-6 hour, the mix products and the above-mentioned cm-chitosan that obtain were reacted 6-8 hour down at 50-80 ℃, the product that obtains uses the sodium hydroxide solution, distilled water of 1mol/L and acetone rinsing 5-6 time successively, vacuum-drying then obtains carboxymethyl chitosan thiourea resin; Use resin to Pb then
2+, Zn
2+, Cu
2+, Ag
+, Hg
2+, Ni
2+And Cd
2+Carry out the variation that adsorptive capacity was tested and measured with ICP-OES to adsorptivity respectively.
Among the preparation method of the present invention, chitosan needs the 20-30h that alkalizes earlier in NaOH solution; Chitosan and chloroacetic mol ratio are 1: 1-1: 5; The mol ratio of glutaraldehyde and thiocarbamide is 1: 1-1: 5, and the reaction times is 3-6 hour.The mol ratio of cm-chitosan and mix products is 1: 3-1: 6; Obtaining the used precipitation agent of cm-chitosan is dehydrated alcohol; The dissolving solvent for use is distilled water or weak acid, and wherein the scope of weak acid pH is pH5.5-6.5.
Have prior art to compare, the present invention has following advantage:
(1) experimental technique of the present invention is easy, the synthesis condition gentleness, and it is less to react the material toxicity that produces in required reagent and the building-up process, and environmental pollution is little.
(2) carboxymethyl chitosan thiourea resin of the present invention is water insoluble, have favorable mechanical performance and resistance to acids and bases, introducing carboxyl, sulfydryl etc. has the functional group of favourable absorption to heavy metal, contents of many kinds of heavy metal ion such as mercury, silver, lead are all had very excellent absorption property and adsorption selectivity, can be applied to multiple field.
(3) the present invention not only will introduce carboxymethyl group in the chitosan main chain, and advances thioureido in the polymer side chain grafting of cross-linked chitosan, has increased the absorption property of resin to some heavy metal ion greatly, makes the purposes of this resin more extensive, and efficient is higher.
Description of drawings
Fig. 1 is the infrared spectrogram of chitosan; Its characteristic infrared (cm
-1): 3446.20,2873.02,1580.13,1420.35,1089.16,664.32.
Fig. 2 is the infrared spectrogram of sulfated chitosan; Its characteristic infrared (cm
-1): 3412.32,2929.73,1657.08,1548.11,1404.11,1065.51.
Embodiment
Embodiments of the invention further specify as follows in conjunction with the accompanying drawings, and protection scope of the present invention not only is confined in following examples.
Embodiment 1:
The 2g chitosan is swelling alkalization 24h in 50% the NaOH solution in the 25ml mass percent, the 5g Mono Chloro Acetic Acid is dissolved in the 25ml Virahol drips, 20 ℃ are reacted 6h down, suction filtration, product is dissolved in the 100ml distilled water, regulates pH to 7, use 400ml dehydrated alcohol precipitated product again, use dehydrated alcohol repeatedly to wash the final vacuum drying precipitated product, obtain cm-chitosan.The 3g thiocarbamide is dissolved in the 100ml distilled water, and adding 12ml mass percent is glutaraldehyde reaction 3h under 40 ℃ of 25%, adds the aqueous solution 30ml that is dissolved with the 2g cm-chitosan then, reacts 8h down at 50 ℃ and obtains product.Products therefrom is used 1mol/L sodium hydroxide solution, distilled water and acetone rinsing 5-6 time successively, and vacuum-drying then obtains carboxymethyl chitosan thiourea resin.
The 2g chitosan is swelling alkalization 24h in 50% the NaOH solution in the 25ml mass percent, the 5g Mono Chloro Acetic Acid is dissolved in the 25ml Virahol drips, 30 ℃ are reacted 8h down, suction filtration, product is dissolved in the 100ml distilled water, regulates pH to 7, use 400ml dehydrated alcohol precipitated product again, use dehydrated alcohol repeatedly to wash the final vacuum drying precipitated product, obtain cm-chitosan.The 3g thiocarbamide is dissolved in the 100ml distilled water, and adding 6ml mass percent is glutaraldehyde reaction 3h under 50 ℃ of 25%, adds the aqueous solution 30ml that is dissolved with the 1.5g cm-chitosan then, reacts 6h down at 70 ℃ and obtains product.Products therefrom is used 1mol/L sodium hydroxide solution, distilled water and acetone rinsing 5-6 time successively, and vacuum-drying then obtains carboxymethyl chitosan thiourea resin.
Embodiment 3
The 2g chitosan is swelling alkalization 24h in 50% the NaOH solution in the 25ml mass percent, the 5g Mono Chloro Acetic Acid is dissolved in the 25ml Virahol drips, 40 ℃ are reacted 9h down, suction filtration, product is dissolved in the 100ml distilled water, regulates pH to 7, use 400ml dehydrated alcohol precipitated product again, use dehydrated alcohol repeatedly to wash the final vacuum drying precipitated product, obtain cm-chitosan.The 3g thiocarbamide is dissolved in the 100ml distilled water, and adding 4ml mass percent is glutaraldehyde reaction 3h under 50 ℃ of 25%, adds the aqueous solution 30ml that is dissolved with the 1.5g cm-chitosan then, reacts 6h down at 80 ℃ and obtains product.Products therefrom is used 1mol/L sodium hydroxide solution, distilled water and acetone rinsing 5-6 time successively, and vacuum-drying then obtains carboxymethyl chitosan thiourea resin.
The Infrared spectroscopy of gained resin shows that carboxymethyl chitosan thiourea resin (Fig. 2) is compared with chitosan (Fig. 1), appearance 1657.08,1548.11,1404.11 and 1065.51cm
-1Four new absorption peaks, 1657.08cm
-1And 1548.11cm
-1The symmetrical stretching vibration absorption peak of C=N key and the stretching vibration absorption peak of the C-N key in the thiourea group in the corresponding schiff base groups of difference, and 1404.11cm
-1Corresponding COO
-The symmetrical stretching vibration absorption peak, 1065.51cm
-1The stretching vibration absorption peak of corresponding C-O key, in addition, at 1720cm
-1The place is the charateristic avsorption band of free glutaraldehyde not, proves the formation of target compound.
Embodiment 4
Accurately the resin 0.1000g of weighing embodiment 1 preparation places 100ml tool plug Erlenmeyer flask, adds certain density heavy metal ion solution, the 24h that vibrates in constant temperature oscillator (absorption Ag
+The time wrap up in the bottle lucifuge with black paper bag), with the variation that ICP-OES measures concentration of heavy metal ion before and after the absorption, calculate loading capacity according to following formula:
Q＝(C
0-C)V/W
Q is loading capacity (mmol/g) in the formula, C
0Be the concentration (mol/L) of metal ion before adsorbing, C is the concentration (mol/L) of absorption back metal ion, and W is sorbent material dry weight (g), and V is liquor capacity (ml).
The loading capacity of table one resin (mmol/g)
As seen from the above table, carboxymethyl chitosan thiourea resin is to Ag
+And Hg
2+Have extraordinary adsorption effect, loading capacity reaches 5.99mmol/g and 6.29mmol/g respectively, to Pb
2+Loading capacity is 1.50mmol/g.
Claims (9)
1. carboxymethyl chitosan thiourea resin, its structure is as follows:
Wherein, n＞1450.
2. the preparation method of carboxymethyl chitosan thiourea resin as claimed in claim 1 is characterized in that: reacted 6-9 hour down at 20-40 ℃ by chitosan and Mono Chloro Acetic Acid, then reaction soln suction filtration, dissolving, deposition and purification are got cm-chitosan; Re-use glutaraldehyde and thiocarbamide at 40-80 ℃ of following hybrid reaction 3-6 hour, mix products and the reaction under 50-80 ℃ of above-mentioned cm-chitosan that obtains obtained carboxymethyl chitosan thiourea resin in 6-8 hour.
3. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: chitosan and chloroacetic mol ratio are 1: 1-1: 5.
4. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: the mol ratio of glutaraldehyde and thiocarbamide is 1: 1-1: 5.
5. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: the mol ratio of cm-chitosan and mix products is 1: 3-1: 6.
6. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: the used solvent of above-mentioned dissolving is distilled water or weak acid.
7. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: the used precipitation agent of deposition and purification cm-chitosan is a dehydrated alcohol.
8. according to the preparation method of the described carboxymethyl chitosan thiourea resin of claim 2, it is characterized in that: chitosan reaction is preceding through NaOH solution alkalization 20-30h.
9. the application of carboxymethyl chitosan thiourea resin as claimed in claim 1 in Adsorption of Heavy Metal Ions.
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