CN104109256B - Preparation method of thiolated chitosan modified polyurethane foam plastic - Google Patents
Preparation method of thiolated chitosan modified polyurethane foam plastic Download PDFInfo
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Abstract
Thioglycollic acid and chitosan are subjected to an amidation reaction to obtain thiolated chitosan, then the thiolated chitosan is grafted to polyurethane foam plastic by a crosslinking agent glutaraldehyde, and the modified foam plastic can be used to enrich precious metal silver ions. The thiol-modified polyurethane foam plastic has a stronger adsorption ability than that of unmodified polyurethane foam plastic. The saturated adsorption amount of the thiol-modified polyurethane foam plastic can reach 104.8 mg/g according to the linear-regression analysis of the Langmuir adsorption isotherm. The technology is simple, and the thiol-modified polyurethane foam plastic can be used to enrich or recycle precious metal silver ions from industrial sewage or environmental samples.
Description
Technical field
The present invention relates to field of functional materials, is related to a kind of preparation side of Chitosan-Thiolated Polymers modified rigid polyurethane foam
Method, the preparation side of the preparation method of the Chitosan-Thiolated Polymers modified rigid polyurethane foam of more particularly to a kind of enriching noble metals
Method.
Background technology
With the progress and development of science and technology, people are in production and life for noble metal, such as platinum（Pt）, palladium（Pd）, rhodium
（Rh）, ruthenium（Ru）, iridium（Ir）, osmium（Os）The platinum group metal of composition and gold（Au）And silver（Ag）, demand is increasing.For picture
Electroplating wastewater, mirror waste water processed, gold mine waste, smelting wastewater, film-making plant effluent, wash as waste water and film studio's waste water
In, containing noble metal, especially gold, silver, need to recycle them.In the market refinement method has a lot, there is chemistry
Method, physical method etc..These methods are both advantageous and disadvantageous, and different experiment conditions and method have to detached effect
Difference.Further, since noble metal abundance, and from the noble metal sample of different places, have different methods to require again and
Separation and concentration efficiency requirements.
Polyurethane foam plastics can extensively be weighed as the analysis of material of a kind of adsorption and enrichment and separation measured matter
Depending on.In order to widen separation, the enrichment scope of foamed plastics, the selectivity of its absorption is improved, people are modified to foamed plastics,
Extractant, chelating agent and developer even load or combination support type foamed plastics has been made on foam.So, both gram
Take that adsorption capacity is little, the shortcoming of poor selectivity, and the sensitivity of analysis can be improved, reduce detection limit.Ren Ying etc.（Ren Ying, thunder
Middle profit, Zhang Jingyu. the research of foamed plastics dynamic fast separating concentration gold method. analytical chemistry, 1993,21（1）：99～101
）The method that have studied foamed plastics dynamic fast separating concentration gold.And the method to processing foam plastic column has carried out selectivity
Test, first deionized water boils foamed plastics 10min, then boils 10min with 10% hydrochloric acid, and deionized water is washed till neutrality,
Earth Using Adsorption of Polyurethane Foam after processing in this way works well.Yan Junfeng etc.（Yan Junfeng, Chen Mingde, Wang Jisen. chelating foam
The research of plastics separation and concentration noble metal. physical and chemical inspection-chemistry fascicle, 1999,35（5）：211～213）Using chelating technique
Synthesize the novel C PF-V type foamed plastics containing rhenocure CA chelation group, and to CPF-V foamed plastics SEPARATION ENRICHMENT OF GOLD WITHs
Studied with the condition of palladium, the preparation of the Chelate foaming plastics be with resin, isocyanates and rhenocure CA as raw material,
The open-celled flexible foamed plastics containing rhenocure CA chelation group is formed through polycondensation, foaming and after solidifying.Due to CPF-V foams
Plastics are formed by high polymer parent and analytical functional group rhenocure CA chelate group bonding, therefore show high stability
And high selectivity, CPF-V and Au3+And Pd2+Stable inner complex salt can be formed and by earth Using Adsorption of Polyurethane Foam.Yang Zhong equalitys（Yang Zhong
It is flat, Jin Xiaozhu, yellow Hua Luan, Wei Shantao .TNA load polyurethane foam plactics enrichment ICP-MS determine Determination of trace gold in geochemical sample,
Platinum, palladium. assay laboratory, 2006,25（9）：99～102）The strong tri-n-octyl amine of extraction noble metal ability is supported on into polyurethane
On foamed plastics, draft that one easy to operate, quick, the tri-n-octyl amine that concentration coefficient is high（TNA）Load earth Using Adsorption of Polyurethane Foam
Separate ICP- MS methods for measuring.
Generally speaking, the exploratory development for polyurethane foam plastics enriching noble metals is mainly entered in terms of following two
OK：1. the pretreatment to foamed plastics and the absorption of foamed plastics are tried and process is freed being improved, to reach foamed plastics
The purpose of selective absorption.2. by improving foamed plastics and selective reagent, by some extractants, chelating agent and developer etc.
Load on foamed plastics, to form Chelate foaming plastics, ion exchange foam plastics and the life of high adsorption rate and high selectivity
Color foamed plastics etc., so as to widen the range of application of foamed plastics separation and concentration.But see on the whole, for how further
Improve the selectivity of earth Using Adsorption of Polyurethane Foam；Adsorption rate how is improved, reduces loss when eluting to improve the rate of recovery；How to know
Which kind of material is loaded on foamed plastics, will become the adsorbent of which kind of ion or organic matter, and specifically how reduces cost is incited somebody to action
It is applied to curbs environmental pollution medium, needs discussion, synthesis and the practice of system, exists further to improve foamed plastics
Use value in scientific research and production practices.
Sulfydryl, as soft base, is good electronq donor, has stronger complexing to make with the precious metal ion as soft acid
With, it is incorporated on chelating resin, shitosan, the new adsorbent of a class is obtained.River and mountain are won bright et al.（Ping XiaoFei, Me Enyun. use
In separation, the chelating resin Recent Advances of enriching noble metals. ion exchange and absorption, 1992,8（6）：532～537）Synthesize
Thiol resin RGS-TGA and RGA-TSH with poly epihydric alcohol base methacrylate as skeleton：Both resins have strong resisting
It is atmospheric oxidising, to Au（）And Ag（）There is preferable adsorption effect, the sulfydryl ammonia type chelating resin with polystyrene as skeleton
To Au（）Adsorption capacity it is also very strong.Hu Huiling etc.（Hu Huiling, Su Mingang, Xu Jiangping. the preparation of modification of chitosan and right
Cu2+, Pb2+Absorption research. ion exchange with absorption, 2007,23 (3)：274～281）Shitosan is modified, is selected
The condition of sulfhydrylation is selected.Experiment shows that in concentration is for the copper solution of 188mg/L, the maximum adsorption rate of CTS-SH reaches
More than 90.3%, adsorption capacity is 27.76mg/g, in concentration is for the lead solution of 203mg/L, the maximum adsorption rate of lead is reached
More than 99%, in concentration in the lead solution of 1.015g/L, maximum adsorption rate is up to 95.5%.Adsorption capacity now is 97.4
Mg/g, adsorption rate when adsorption capacity is more than 147.2mg/g is 36.3%.Zhang Min etc.（Zhang Min, evergreen, Wang Jinxi, Wang Juan. it is high
Molecule heavy metal flocculant MAC removes Cu2+Go turbid performance. ACTA Scientiae Circumstantiae 2007,27（12）：1994～1999）It is poly- with shell
Sugar, TGA etc. are a kind of novel high polymer heavy metal flocculant mercaptoacetyl shitosan of Material synthesis（MAC）, have studied
Its copper removal with go turbid mechanism.When MAC and H PAM is compounded, effect is better than exclusive use MAC, Cu2+Clearance is up to 98%
More than.Cu is processed with MAC2+During the system coexisted with turbidity, the heavy metal ion and cause absurd creature matter in waste water can be played mutually
Promote the effect for removing.
Polyurethane foam plastics is as there is greatly value on concentration of precious metal, but price domestic at present is relatively held high
It is expensive, therefore develop inexpensive and the good polyurethane foam carrier of effect is imperative.Shitosan raw material is easy to get, and cost is more female than other
Body is cheap, and good separating effect.But, chitosan derivative species adsorbent is generally in powder, and the later stage separates separating process complexity,
Power consumption is high.
The content of the invention
The technical problem to be solved：Inferior separating effect, enrichment narrow range when conventional foamed plastics is used to adsorb noble metal,
The selectivity of absorption is low, adsorption rate is low, it is an object of the invention to provide a kind of Chitosan-Thiolated Polymers of enriching noble metals are modified
The preparation method of polyurethane foam plastics, for solving the problems of the prior art.
Technical scheme：The present invention adopts waste and old polyurethane foam plastics as concentration of precious metal carrier, by sulfhydrylation
Chitin modified carrier material, the sulfydryl having using chitosan derivatives, amino active group are chelated to the special efficacy of noble metal
Effect, obtains the cost-efficiently polyurethane-base functional material for enriching noble metals.
For achieving the above object and other related purposes, the present invention provides a kind of Chitosan-Thiolated Polymers of enriching noble metals and changes
The preparation method of property polyurethane foam plastics, comprises the steps：
（1）TGA 16ml, acetic anhydride 8ml are separately added in reaction bulb, the 4 drop concentrated sulfuric acids are added dropwise in vibration, fully
After vibration cooling, shitosan 2g is added, make it react 1h at room temperature under stirring, then stood overnight in dark place；
（2）200mL is prepared, 2mol/LNaOH solution in being added to above-mentioned reactant liquor, is put in 70 DEG C of baking ovens and stands 12h
Afterwards, original precipitation dissolving in solution, then stirs lower regulation and adds NaOH, determines the pH value of solution, adjusts pH value, fruit occurs
Freeze the purplish red color substance of shape, suction filtration is embathed except alkali is neutral up to filtrate repeatedly with distilled water, and filter cake is vacuum dried at 50 DEG C
12h, obtained Chitosan-Thiolated Polymers are placed in brown bottle and keep in dark place；
（3）The obtained Chitosan-Thiolated Polymers for taking 1 ~ 2g are dissolved in 100mL 2wt% acetums, take 15 ~ 25cm3It is poly-
In urethane foamed plastics immersion 50mL Chitosan-Thiolated Polymers solution, vacuumize, make in foamed plastics full of solution, then pipette leaching
Not in 50mL, in the glutaraldehyde solution of 0.25wt%, react after 4h at room temperature, being embathed repeatedly with distilled water makes foam in neutrality,
It is placed in baking oven and is dried overnight at 75 DEG C.
Preferably, the step（2）In, stirring is lower to add 1 ~ 10mgNaOH, and it is 9 ~ 10 to adjust reacting liquid pH value.
Preferably, the step（3）In, take obtained Chitosan-Thiolated Polymers 1.0g or 1.5g or 2.0g and be dissolved in 100mL
In 2wt% acetums.
Preferably, the step（3）In, preferably take 18 10mm × 10mm × 10mm small cubes polyurethane foam modeling
Material.
With developing rapidly for polyurethane industrial, substantial amounts of polyurethane foam plastics needs recycling, improves product
Added value.TGA is organic compounds containing sulfur, and according to the hsab theory of Person definition, it belongs to soft base, can and
The each metal ion species for belonging to soft acid form stable chelate, be also commonly used as in alkaline medium the metals such as copper, silver, zinc from
The screening agent of son.Sulfydryl has good combination to noble metal, so being changed as Material synthesis with shitosan and TGA
Property shitosan has significant advantage for enriching noble metals.The present invention not merely with the big specific surface of polyurethane foam plastics, easily
The characteristics such as absorption improve the stability of chitosan absorbent, and using the dual structure feature containing sulfydryl and amino shitosan and
The selective adsorption capacity improved to precious metal ion, the chitin modified polyurethane-base functional material of sulfur-bearing of exploitation can be used to inhale
Precious metal ion in the environmental samples such as attached industrial wastewater, moreover it can be used to gathering and measuring noble metal.
Beneficial effect：Present invention process is simple, and operating procedure is convenient, can obtain the chitin modified polyurethane foam modeling of sulfur-bearing
Material, for the enrichment that noble metal is particularly silver ion.Economic worth of the present invention is higher, efficient, the cheap function carrier of exploitation
Material is used for concentration of precious metal, has the advantages that simple to operate, good stability, reagent cost be low, good separating effect.It is applicable to
Adsorb the precious metal ion in the environmental samples such as industrial wastewater and recycled, and the separation and concentration of precious metal ion is surveyed
It is fixed.
Description of the drawings
Fig. 1 is the infrared spectrum of thiolated modified shitosan product；
Fig. 2 is the infrared spectrum of Chitosan-Thiolated Polymers modified rigid polyurethane foam；
Fig. 3 is the adsorption curve that blank polyurethane foam modeling processes variable concentrations silver ion solution；
Fig. 4 processes the adsorption curve of variable concentrations silver ion solution for the modified polyurethane foam modeling of embodiment 1.
Specific embodiment
Embodiments of the present invention are illustrated below by way of specific instantiation.The present invention can also be by different in addition
Specific embodiment is carried out or applies, and the every details in this specification can also not had based on different viewpoints and application
Have carries out various modifications and changes under the spirit of the present invention.
Embodiment 1
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
TGA 16ml, acetic anhydride 8ml are separately added in reaction bulb, the 4 drop concentrated sulfuric acids, fully vibration are added dropwise in vibration
After cooling, 2g shitosans, stirring so as to react 1h at room temperature are added.Then stand overnight in dark place.Add 200mL,
2mol/LNaOH solution, is put in baking oven and dries（70℃）, original precipitation dissolving in solution after 12h, now pH is 7.Add 1mg
NaOH, it is stirring while adding, when measure pH value is 9, there is the purplish red color substance of g., jelly-like, suction filtration is embathed except alkali repeatedly with distilled water,
So that filtrate is about neutrality.Filter cake is vacuum dried 12h at 50 DEG C, and obtained Chitosan-Thiolated Polymers are placed on lucifuge in brown bottle
Preserve.
Take obtained Chitosan-Thiolated Polymers 1.0g to be dissolved in 100mL2wt% acetums.Take 18 10mm × 10mm ×
In 10mm small cubes polyurethane foam plastics immersion 50mL Chitosan-Thiolated Polymers solution, vacuumize, make in foam full of solution.
Take out foam and be immersed in 50mL, the glutaraldehyde solution of 0.25w%（I.e. shitosan and the mol ratio of glutaraldehyde are 10：1）In, in room
After the lower reaction 4h of temperature, being embathed repeatedly with distilled water makes foam in neutrality, and with distilled water the acid on surface is washed away, and foam surface is presented
Neutrality, is placed in baking oven and is dried overnight at 75 DEG C.
The reactivity of various functional groups such as the modified hydroxyl mainly used on strand, the amino of shitosan, passes through
Graft reaction is incorporated into sugar chain, polypeptide chain, polyester chain, alkyl chain etc. in chitosan molecule, the different shitosan of forming properties
Derivative.TGA is organic compounds containing sulfur, is that daily cosmetics are cold for making the catalyst of epoxy resin, bisphenol-A
Scald the primary raw material of essence and hair remover.The reaction of TGA modification of chitosan is mainly the reaction of carboxyl and amino, certainly
The reaction with hydroxyl is not excluded for, because many, the reaction with hydroxyl more active than the hydrogen on hydroxyl of the activity of the hydrogen on amino
Lack.The product of 2.6750g should be obtained in experimentation in theory, and actually obtain the product of about 2.4900g, yield is about
For 93.1%.Its main cause is the loss that can all have portion of product in operating process such as to filter, dry.
Fig. 1 is the FT-IR collection of illustrative plates of thiolated modified shitosan.Characteristic peak in the infrared spectrum of shitosan is：3400cm-1
The broad peak of left and right is the multi-absorption peak that the stretching vibration absworption peak of O-H is overlapped to form with the stretching vibration absworption peak of N-H；
2853cm-1And 2923cm-1It is the C-H stretching vibration peaks of methyl on shitosan ring and methine；1531-1637cm-1It is
By the acid amides I of shitosan（C=O）, acid amides II（N-H）And-NH2（1590cm-1）Constituted one of deformation vibration peak compared with
Wide blended absorbent bands of a spectrum.The infrared spectrum of the thiolated modified shitosans of contrast Fig. 1, in 3400cm-1The intensity at the peak of left and right subtracts
It is weak, it is the reaction consumption due to-NH groups.In 2850-2890cm-1There is a very strong new peak-SH stretching vibration peak in place,
Consistent with the infrared signature frequency of the S-H stretching vibrations of organic sulfur compound, this explanation Chitosan-Thiolated Polymers is generated.And
1740-1750cm-1Place, particularly 1300cm-1There are the flexible peaks of stronger amide-type C=O in place, shows to be made by amidation process
TGA is connected on shitosan.Chitosan-Thiolated Polymers before modified after elementary analysis result understand, before modified S contents are zero
0, modified S contents are up to 11.478%, it was demonstrated that TGA is combined with chitosan reaction.
Shitosan after will be thiolated modified carries out glutaraldehyde cross-linking and is modified with polyurethane foam plastics, and accompanying drawing 2 is modified
The FT-IR collection of illustrative plates of polyurethane foam plastics.As seen from the figure, in 3138cm-1The spectral peak at place is significantly increased, and this is because shitosan is handed over
Connection is modified to introduce hydroxyl, the amino-NH also not reacted completely on shitosan2Impact because penta 2 in cross-linking reaction
Aldehyde is only reacted with the part amino on chitosan molecule ring.2335.5cm-1Place produced by peak intensity it is very high, this be because
For the stretching vibration of C=N groups, show-the NH on glutaraldehyde carbonyl group and polyurethane, shitosan2Between there occurs
Schiff is reacted.In 2850cm-1There is a new peak-SH stretching vibration peak in place, and the intensity at peak is not very strong, with organic sulfur
The infrared signature frequency of the S-H stretching vibrations of compound is consistent, and this explanation Chitosan-Thiolated Polymers there occurs with polyurethane, glutaraldehyde
Crosslinking association reaction.
As it can be seen from table 1 when 1% Chitosan-Thiolated Polymers solution is 10 with the mol ratio of glutaraldehyde consumption：When 1, it is modified
Polyurethane foam plastics afterwards, various performance parameters are significantly changed, and aperture reaches 1.4mm, and water holding multiplying power reaches 31.3 times, hole
Rate reaches 96.4%.After modified, density polyurethane foam increase, from 30 kg/ m3Increase to 35 kg/ m3, this is
Because the crosslinked action of shitosan is so as to increased the weight of polymer.Thiolated modified rear polyurethane foam aperture increases are bright
It is aobvious, increase to 1.4mm from 1.0mm.The porosity and water holding multiplying power of polyurethane foam has larger change after before modification
Change, from 80% or so 96% or so is increased to.This is primarily due to chemical modification and makes the senses such as hydroxyl, amino, sulfydryl on foam
The total amount of group is improved.
The change of polyurethane foam plastics performance parameter afterwards before modified of the Chitosan-Thiolated Polymers of table 1
Knowable to elementary analysis result before and after Chitosan-Thiolated Polymers modified rigid polyurethane foam, unmodified polyurethane foam
Plastics S contents are 00, and modified S contents show that Chitosan-Thiolated Polymers are introduced in polyurethane foam plastics up to 3.625%.It is logical
Cross electron-microscope scanning to learn, polyurethane foam internal structure is hole pattern connected one by one, these hole patterns are to prepare polyurethane foam
Foaming during foam is formed, in foaming process, the film rupture in the middle of some hole patterns, but still deposit in the middle of many hole patterns
In uncracked pore membrane.Relatively unmodified front foam cellular structure, after cross-linked chitosan in polyurethane foam cellular structure
Film is reduced, but is changed in polyurethane prismatic surface pattern, is because the chitosan film that surface combines causes.
Embodiment 2
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
TGA 16ml, acetic anhydride 8ml are separately added in reaction bulb, the 4 drop concentrated sulfuric acids, fully vibration are added dropwise in vibration
After cooling, 2g shitosans, stirring so as to react 1h at room temperature are added.Then stand overnight in dark place.Add 200mL,
2mol/LNaOH solution, is put in baking oven and dries（70℃）, original precipitation dissolving in solution after 12h, now pH is 7.Add
10mg NaOH, it is stirring while adding, when measure pH value is 10, there is the purplish red color substance of g., jelly-like, suction filtration is soaked repeatedly with distilled water
Remove alkali so that filtrate is about neutrality.Filter cake is vacuum dried 12h at 50 DEG C, and obtained Chitosan-Thiolated Polymers are placed on brown bottle
In keep in dark place.
Take obtained Chitosan-Thiolated Polymers 1.5g to be dissolved in 100mL2wt% acetums.Take 15 10mm × 10mm ×
In 10mm small cubes polyurethane foam plastics immersion 50mL Chitosan-Thiolated Polymers solution, vacuumize, make in foam full of solution.
Take out foam and be immersed in 50mL, the glutaraldehyde solution of 0.25w%（I.e. shitosan and the mol ratio of glutaraldehyde are 10：1）In, in room
After the lower reaction 4h of temperature, being embathed repeatedly with distilled water makes foam in neutrality, and with distilled water the acid on surface is washed away, and foam surface is presented
Neutrality, is placed in baking oven and is dried overnight at 75 DEG C.
Embodiment 3
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
TGA 16ml, acetic anhydride 8ml are separately added in reaction bulb, the 4 drop concentrated sulfuric acids, fully vibration are added dropwise in vibration
After cooling, 2g shitosans, stirring so as to react 1h at room temperature are added.Then stand overnight in dark place.Add 200mL,
2mol/LNaOH solution, is put in baking oven and dries（70℃）, original precipitation dissolving in solution after 12h, now pH is 7.Add 6mg
NaOH, it is stirring while adding, when measure pH value is 9, there is the purplish red color substance of g., jelly-like, suction filtration is embathed except alkali repeatedly with distilled water,
So that filtrate is about neutrality.Filter cake is vacuum dried 12h at 50 DEG C, and obtained Chitosan-Thiolated Polymers are placed on lucifuge in brown bottle
Preserve.
Take obtained Chitosan-Thiolated Polymers 2.0g to be dissolved in 100mL2wt% acetums.Take 25 10mm × 10mm ×
In 10mm small cubes polyurethane foam plastics immersion 50mL Chitosan-Thiolated Polymers solution, vacuumize, make in foam full of solution.
Take out foam and be immersed in 50mL, the glutaraldehyde solution of 0.25w%（I.e. shitosan and the mol ratio of glutaraldehyde are 10：1）In, in room
After the lower reaction 4h of temperature, being embathed repeatedly with distilled water makes foam in neutrality, and with distilled water the acid on surface is washed away, and foam surface is presented
Neutrality, is placed in baking oven and is dried overnight at 75 DEG C.
The quantitative contrast experiment of silver ion absorption
The preparation of silver nitrate solution：The pure silver nitrate of required quality is weighed, the salpeter solution of 10% concentration is dissolved in
In, and be stirred continuously dissolves it in the dark.During the volumetric flask of 1L is proceeded to after to be dissolved, shady place guarantor is placed it at once
Deposit.
Determine silver ion concentration of standard solution and absorbance curve：50mg/L silver nitrate solutiones are prepared, by the nitre prepared
Sour silver solution is diluted to respectively 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, uses atomic absorption spectrophotometry
（Atomic Absorption Spectrophotometer, AAS, atomic absorption spectrophotometer best operating condition：Absorb
Line wavelength 328.1nm, lamp current 2mA, air mass flow 5L/min, acetylene throughput 0.5L/min, burner position：6-7mm, light
Spectrum passband：0.2nm）The absorbance corresponding to respective concentration is determined, the curve of silver ion concentration of standard solution and absorbance is drawn.
Gained equation is A=0.1491c-0.0383, R2=0.9993, it is as a result substantially linear, meet absorbance and concentration relationship.
Modified rigid polyurethane foam adsorbs silver ion in different periods：50mg/L silver nitrate solutiones are prepared, will be prepared
Silver nitrate solution fall 100mL respectively in 6 identical beakers, the embodiment 1 to 3 of equal number is placed in each beaker
Modified rigid polyurethane foam, respectively at 30min, 60min, 90min, 120min, 150min, 180min determines concentration of silver ions
Change.Analysis above adsorption test result, modified rigid polyurethane foam reached adsorption saturation value at 3 hours or so.
In Comparative and Quantitative Analysis experiment, can directly determine with modified polyurethane foam plastics absorption 50mg/L's
AgNO3Solution, and can determine its saturated extent of adsorption at 3 hours or so.The silver ion standard liquid of configuration 50mg/L, at three
Equipped with same volume（50mL）Put 2 10mm × 10mm × 10mm small cubes in the beaker of silver nitrate solution respectively to be matched somebody with somebody by difference
Than modified rigid polyurethane foam obtained in Chitosan-Thiolated Polymers.After standing 3-4 hours, surveyed by atomic absorption spectrophotometry
Go out the absorbance of each of which, be converted into adsorbance and adsorption rate is as shown in table 2.
By contrast experiment it can be found that：The modified rigid polyurethane foam that the reaction of embodiment 1 is obtained, satisfies to silver ion
All it is best with adsorbance, adsorption rate.Analysis increases with Chitosan-Thiolated Polymers acetic acid solution concentration, saturated extent of adsorption, absorption
The reason for rate declines, it may be possible to which, because concentration proportioning is bigger, Chitosan-Thiolated Polymers acetic acid solution viscosity increases, cross-linking modified poly- ammonia
During ester foamed plastic, be easily filled in polyurethane foam gap, forming pore membrane after solvent volatilization will affect mass transfer effect, when after
When continuous addition glutaraldehyde solution crosslinks reaction, decline reaction efficiency, affect the effect of Chitosan-Thiolated Polymers modified polyurethane
Really.
Adsorbance and adsorption rate of the different ratio Chitosan-Thiolated Polymers acetic acid solution modified polyurethane of table 2 to silver ion
Analysis thio chitosan modified polyurethane adsorbs the mechanism of silver ion, due to being to use TGA modification of chitosan again
Polyurethane foam plastics surface is cross-linked to, the leading ion chelation group of introducing is-SH.The reaction of metal ion and-SH, one
As be metal ion and H+Exchange： Ag++-SH- SAg+H+.And the combination between them is very firm
Gu.Additionally, substantial amounts of amino, oh group in shitosan, and shitosan and thioglycolic acid amidation, the structure of esterification
Factor is very beneficial for the adsorption process to precious metal ion, thus the present invention is changed for adsorbing the preferable polyurethane of noble metal
Property measure.
The Chitosan-Thiolated Polymers modified rigid polyurethane foam enrichment Adsorption For Ag ion experiment of embodiment 1
Different periods adsorb the measure of silver ion：50mg/L silver nitrate solutiones are prepared, by the silver nitrate solution prepared point
Not Dao 100mL in 6 identical beakers, in each beaker place equal number the modified rigid polyurethane foam of embodiment 1,
Respectively at 30min, 60min, 90min, 120min, 150min, 180min determines the change of concentration of silver ions.Prepare respectively again
100mg/L, 150mg/L, 200mg/L, 250mg/L silver nitrate solution, repeats above experimental procedure, determines the change of concentration of silver ions
Change.
Research using embodiment 1 10g/L Chitosan-Thiolated Polymers modified rigid polyurethane foams, be placed in 50mg/L,
100mg/L, 150mg/L, 200mg/L, 250mg/L variable concentrations silver ion solution, the efficiency of enrichment absorption silver ion.By dividing
Time period absorbs enrichment, dilution metering, conversion value, show that different time sections absorb the quality of silver ion, and for adsorbing
The adsorbance of variable concentrations silver ion solution, and contrast with blank polyurethane foam plastics is adopted.
Fig. 3 and accompanying drawing 4 are respectively blank polyurethane foam plastics, the modified rigid polyurethane foam of embodiment 1 adsorbs not
With the adsorption curve of concentration silver ion solution.Contrast accompanying drawing 3 and 4 can be seen that：The modified polyurethane foam modeling of embodiment 1
Expect there is the more preferable rich absorbent to silver ion than blank polyurethane foam plastics, polyurethane foam plastics is to carry well
Body, can load sulfydryl so as to be firmly carried in above polyurethane foam plastics, and blank polyurethane foam plastics is also right
Silver ion also has certain absorption enrichment.AgNO of the blank polyurethane foam plastics to variable concentrations3There is identical to adsorb
Amount, but the AgNO larger for concentration3Solution, adsorption rate is more hurried up.Comparatively speaking, blank polyurethane foam plastics pair
When the silver ion of variable concentrations is absorbed, its adsorption efficiency is substantially the same, some difference only above adsorption time, empty
White polyurethane foam plastics is shorter for silver ion solution saturated adsorption time.For modified polyurethane foam plastics, its
Adsorption efficiency comparatively, the silver ion solution of 50mg/L its bioaccumulation efficiency more high point.
Modified polyurethane foam plastics has to silver ion than blank polyurethane foam plastics and separate well absorption
Effect.Modified polyurethane foam plastics, the AgNO for 50mg/L3Solution adsorbance is maximum.Modified polyurethane is to Ag+'s
Adsorbance（Qt）Calculate as follows：
Qt=V（ρ0- ρt）/m
In formula：Qt--- the adsorbance of modified polyurethane（mg/g）；ρ0--- mass concentration in initial soln（mg/L）；
ρt--- mass concentration in absorption t solution（mg/L）；The volume of V --- solution（L）；M --- adsorbent mass.
Data measured is fitted with Freundlich and Langmuir adsorption isotherms.
Freundlich isotherm formulas：lgQ=（1/n）lgρe +lgKf
In formula：Q --- adsorbance（mg/g）；Kf, 1/n --- characteristic constant；ρe--- mass concentration during adsorption equilibrium（mg/
L）.
Langmuir adsorption isotherms：ρe/Q=ρe/Qmax+1/Qmaxb
In formula：Q --- adsorbance（mg/g）；B --- characteristic constant；Qmax--- maximal absorptive capacity；ρe--- adsorption equilibrium
When mass concentration（mg/L）.
By Ag+Isothermal adsorption result of the test substitutes into respectively Langmuir adsorption isotherms and Freundlich isotherm formulas and carries out
Linear regression analysis.Langmuir adsorption isotherms equation is ρe/Q=0.0017ρe+ 0.003, wherein QmaxFor 104.8mg/g,
B is 3.18, linear correlation degree R2=0.9996.Freundlich isotherm formula linear correlation degree R2=0.9546, thus the absorption is more
Meet Langmuir isothermal adsorptions.When Chitosan-Thiolated Polymers and acetic acid proportioning are 10g/L, according to Langmuir adsorption isotherms
Linear fit, either adsorbance or adsorption efficiency are all best to its modified polyurethane foam plastics.Its saturation is inhaled
Attached amount can reach 104.8mg/g.
Modified polyurethane foam plastics is experimentally confirmed to Ag+Absorption to mould apparently higher than blank polyurethane foam
Material is to Ag+Absorption, modified rigid polyurethane foam is to Ag+Absorption better conform to Langmuir isotherm formulas, illustrate modified poly-
Urethane foamed plastics is to Ag+There is preferably absorption property, modified rigid polyurethane foam is to Ag+Carry out physical absorption and chemistry
Absorption.TGA and chitosan reaction generate Chitosan-Thiolated Polymers, then obtain sulfhydrylation by glutaraldehyde cross-linking polyurethane and gather
Urethane, can be used to precious metal ion in the environmental samples such as trade effluent（Ag+）Enrichment or recovery.
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle and its effect of above-described embodiment only illustrative present invention, it is of the invention not for limiting.Affiliated skill
Equivalent modification or change that personage in art field is completed under without departing from disclosed spirit and technological thought, still
Should be covered by the claim of the present invention.
Claims (1)
1. a kind of preparation method of Chitosan-Thiolated Polymers modified rigid polyurethane foam, it is characterised in that comprise the steps：
（1）TGA 16ml, acetic anhydride 8ml are separately added in reaction bulb, the 4 drop concentrated sulfuric acids, fully vibration are added dropwise in vibration
After cooling, shitosan 2g is added, make it react 1h at room temperature under stirring, then stood overnight in dark place；
（2）200mL is prepared, 2mol/LNaOH solution in being added to above-mentioned reactant liquor, is put in 70 DEG C of baking ovens and stands after 12h, molten
Original precipitation dissolving in liquid, then stirs lower regulation and adds NaOH, determines the pH value of solution, adjusts pH value, g., jelly-like occurs
Purplish red color substance, suction filtration is embathed except alkali is neutral up to filtrate repeatedly with distilled water, and filter cake is vacuum dried 12h at 50 DEG C, makes
The Chitosan-Thiolated Polymers for obtaining are placed in brown bottle and keep in dark place；
（3）The obtained Chitosan-Thiolated Polymers for taking 1 ~ 2g are dissolved in 100mL 2wt% acetums, take 15 ~ 25cm3Polyurethane foam
In foam plastics immersion 50mL Chitosan-Thiolated Polymers solution, vacuumize, make in foamed plastics full of solution, then pipette and be immersed in
In the glutaraldehyde solution of 50mL, 0.25wt%, react after 4h at room temperature, being embathed repeatedly with distilled water makes foam in neutrality, is placed in
It is dried overnight at 75 DEG C in baking oven；
The step（2）In, stirring is lower to add 1 ~ 10mgNaOH；
The step（2）In, it is 9 ~ 10 to adjust reacting liquid pH value；
The step（3）In, taking obtained Chitosan-Thiolated Polymers 1.0g or 1.5g or 2.0g, to be dissolved in 100mL 2wt% acetic acid molten
In liquid；
The step（3）In, take 18 10mm × 10mm × 10mm small cubes polyurethane foam plastics.
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| CN109821516A (en) * | 2019-04-02 | 2019-05-31 | 陕西科技大学 | A kind of preparation method of carboxymethyl chitosan modified polyurethane foam |
| CN112409633B (en) * | 2020-11-16 | 2022-05-13 | 广东顺德同程新材料科技有限公司 | Preparation method of sulfydryl grafted modified polyurethane foam plastic |
| CN114749155B (en) * | 2022-05-10 | 2023-08-11 | 中南大学 | Sulfhydryl modified chitosan material, preparation method thereof and application thereof in adsorbing mercury ions in wastewater |
| CN116515072B (en) * | 2023-03-23 | 2023-10-20 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | Environment-friendly porous material with noble metal enrichment function, and preparation method and application thereof |
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