CN104592397B - Thioglycolic acid modified cellulose, its preparation method and application - Google Patents
Thioglycolic acid modified cellulose, its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of thioglycolic acid modified cellulose, its preparation method and application.The preparation method, using cellulose powder as parent, thioglycolic acid is part, and the hydroxyl on cellulose powder is modified, comprised the following steps：（1）Cellulose powder is immersed in the distilled water as reaction dissolvent, until cellulose powder is fully swelled；（2）In step（1）Gains in add part thioglycolic acid, under conditions of nitrogen protection, add catalyst, keep 45 DEG C~90 DEG C of reaction temperature stirring reaction 12 hours；（3）Filtration step（2）Gains, obtain filter cake, for the reacted solvent washing of gained filter cake to after colourless, 50 DEG C are dried under vacuum to constant weight, obtain thioglycolic acid modified cellulose.The preparation method technique disclosed by the invention is simple, cost is cheap, and the new thioglycolic acid modified cellulose obtained using the preparation method is to Se in food（IV）Ion has higher selective absorption.
Description
Technical field
The present invention relates to a kind of production method of new modified cellulose, more particularly to it is a kind of to heavy metal Se in food
(IV) ion has good selective absorption, absorption property, the repeatable thioglycolic acid-modified cellulose utilized, its preparation side
Method and application.
Background technology
With recent year expanding economy and growth in the living standard, people are generally no longer satisfied with general food,
The food of the Special Categories such as organic food, functional food progresses into the visual field of people, and the micronutrient levels in food has been made
To evaluate the key of food functionality, therefore the analyzing detecting method of trace trace element in food is established, for safeguarding human body
Effect of the difference trace element to health in health and evaluation food has particularly important meaning.Recently conventional member
Belong to detection method ICP-MS, ICP-AES, HG-AFS etc., possess higher selectivity and sensitivity, but high testing cost limits
Its popularization in middle-size and small-size food enterprise production detection is at home made.Spectrophotometer is a kind of more economical analysis analyzer
Device, the advantage of UV-VIS spectrophotometry are to purchase maintenance cost low, easy to operate.But its instrument detection limit is high, coexists
The shortcomings that ion is big limits its application in Trace Elements in Food detection.The concentration of Trace Elements in Food is mostly trace
Amount, often less than its detection limit, and the element species in food are more；Therefore sample must just be decomposed and preenrichment
The analysis measure could be carried out Deng pre-treatment.The preenrichment of modified cellulose adsorption functional material can eliminate interference, and improve
Trace components content to be measured.Because it has, adsorption capacity is big, enrichment times are high, selectivity is good, easy to operate, modified cellulose is easy
The advantages that regeneration and acid and alkali-resistance, thus have important researching value in analysis detection, resource reclaim etc. and widely should
With advance.
Modified cellulose has high mechanical strength, and heat endurance is good, and price is low, the features such as easily preparation, and contains in macromolecular
There are multiple hydroxyls, can be acted on plurality of reagents, generate a variety of functional groups, so as to which chelating, acid, alkalescence is made
Or the function separation and concentration material of both sexes.
The content of the invention
The present invention provides a kind of preparation method for thioglycolic acid-modified cellulose that technique is simple, cost is cheap and answered
With having higher choosing to Se in food (IV) ion using new thioglycolic acid-modified cellulose that the preparation method obtains
Selecting property is adsorbed.
In order to solve the above-mentioned technical problem, the present invention provides a kind of preparation method of thioglycolic acid-modified cellulose, with
Cellulose powder is parent, and thioglycolic acid is part, and the hydroxyl on cellulose powder is modified, comprised the following steps：
(1) cellulose powder is immersed in the distilled water as reaction dissolvent, until cellulose powder is fully swelled；
(2) part thioglycolic acid is added in the gains of step (1), under conditions of nitrogen protection, adds catalysis
Agent, keeps 45 DEG C~90 DEG C of reaction temperature stirring reaction 12 hours；The thing of the thioglycolic acid and hydroxyl in cellulose powder
The ratio between amount of matter is 2~5：1；
(3) gains of filtration step (2), obtain filter cake, and the reacted solvent washing of gained filter cake is to after colourless, 50 DEG C of vacuum
Dry to constant weight, obtain thioglycolic acid-modified cellulose.
It is preferred that the catalyst is 5% phosphotungstic acid.
It is preferred that in the step (1), the amount ratio of cellulose powder and reaction dissolvent distilled water is：1g cellulose powders/
50ml reaction dissolvent distilled water.
It is preferred that in the step (2), the ratio between the thioglycolic acid and amount of material of hydroxyl in cellulose powder are
3：1.
It is preferred that in the step (2), the reaction temperature is 60 DEG C.
The present invention also provides a kind of thioglycolic acid-modified cellulose, prepared by the above method provided by the present invention.
The present invention also provides the application of thioglycolic acid-modified cellulose, comprises the following steps：
(1) thioglycolic acid-modified cellulose is inserted in pH=1.5 cushioning liquid and soaked 24 hours；
(2) in the gains of step (1) add selenite radical ion standard liquid, in temperature be 25 DEG C, rotating speed be
Vibrated in 100r/min constant temperature oscillator；The dosage of thioglycolic acid-modified cellulose and selenite radical ion standard liquid
Than for 5:1；
(3) saturated adsorption capacity of the thioglycolic acid-modified cellulose to plasma selenium is determined after balance to be adsorbed.
The present invention also provides the application of thioglycolic acid-modified cellulose, comprises the following steps：
(1) testing sample pre-treatment：Testing sample is obtained containing selenous to be measured molten after repeatedly acidifying, heating, cooling
Liquid；
(2) separation and preconcentration of thioglycolic acid-modified cellulose：Power is placed in after solution to be measured is adjusted to pH=1.5
Profit requires in the dynamic adsorption post of the 6 thioglycolic acid-modified celluloses that coutroi velocity is 1.0ml/min by the way that dynamic is inhaled
After attached end, strippant is added, is desorbed with 0.5ml/min flow velocity by the dynamic adsorption post, and it is molten to detect outflow
Liquid concentration.
It is preferred that the strippant is 25mL 3.0mol/L HCl and 2% potassium chlorate.The testing sample is purple
Potato.
New thioglycolic acid-the modified cellulose (hereinafter referred to as TGAC) being prepared using the inventive method, is entered
The following experiment of row：
First, heavy metal ion adsorbed experiment
After 50 DEG C of vacuum drying, the drying TGAC for accurately weighing a certain amount of (being, for example, 200.0mg) is placed in 100mL iodine
In measuring bottle, add the distilled water of a certain amount of (being, for example, 25mL) and soaked 24 hours after accurately adjusting pH to 1.5, then add one
The selenous acid solution of quantitative (such as 5ml), to be not added with thioglycolic acid-modified cellulose as control group, on constant temperature oscillator
Vibrate at a certain temperature, remaining selenite radical ion in Accurate Determining solution fully after absorption (such as 48 hours) to balance
Concentration, adsorbance Q, Sorption ratio D is calculated as follows.
C in above formulaoFor metal ion initial concentration (mg/mL)；CeFor (mg/mL) after concentration of metal ions-adsorption equilibrium, Q
For saturated extent of adsorption-static state (mg/g)；M is TGAC quality (g)；V is liquor capacity (mL), refers to heavy metal ion titer
With volume of buffer solution sum.
2nd, desorption experiment
Modified adsorbent (TGAC) after adsorption saturation for several times and is filtered out with distillation water washing, one is added after 50 DEG C of drying
Determine the eluant, eluent of volume, after 25 DEG C of constant temperature oscillations balance, determine the concentration of selenite radical ion in solution, the desorption efficiency of adsorbent
E (%) is calculated as follows：
C in formuladFor the concentration (mg/mL) of selenite radical ion in solution；VdFor stripping liquid volume (mL), CoAnd CeRespectively
For the initial concentration (mgmL of metal ion in aqueous phase-1) and equilibrium concentration (mgmL-1)；V is liquid phase volume (mL).
The present invention has the advantage that relative to prior art：
1st, the chemical property of cellulose powder is stable, not soluble in water and common organic solvents, non-toxic to human body, has higher
Mechanical strength and physical stability wide material sources, it is cheap, there is obvious economic benefit, moreover, cellulose compares surface
Greatly, its special physical aspect makes it have larger contact area with adsorbate, and the resistance very little of convection body, diffusion admittance is short,
Cation exchange groups can fully react, and the parent as modified adsorbent has very big potentiality, compared to other fertile materials, have more
Superior dynamic absorption characteristic, absorption is fast, and elution is easy, moreover it is possible to more kinds of structure type with process；
2nd, cellulose powder is modified by the present invention using chemical graft, makes it have larger chemical stability, and enhance
The ability and its adsorption capacity of resistance acid, alkali and organic solvent；
3rd, the new modified adsorbent that the present invention uses has higher selective absorption to Se (IV), and adsorbance is big, absorption
Speed is fast；
4th, adsorption function thioglycolic acid-modified cellulose chemical stability produced by the present invention is good, easily elution, only needs
Want HCl and KClO3Mixed liquor can elutes completely, reduces secondary pollution, has more excellent regeneration and reusability
Energy；
5th, the preparation method of new thioglycolic acid-modified cellulose of the invention is easy to operate, and yield is high.
Brief description of the drawings
Fig. 1 is the reaction principle figure of the present invention；
Fig. 2 is the influence for reacting mol ratio to thioglycolic acid-modified cellulose function base conversion ratio；
Fig. 3 is influences of the TGAC to metal ion Se (IV) adsorption capacity under different pH value；
Fig. 4 is influences of the TGAC to Se (IV) ionic adsorption amount under different anions；
Fig. 5 is the linear relationship between absorbance and Se concentration；
Fig. 6 is influence of the adsorption flow rate to enrichment percentage；
Fig. 7 is influence of the elution flow rate to the rate of recovery.
Embodiment
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.Wherein, following examples
In washing be to be washed with distilled water.
Embodiment 1
1) 1.0g cellulose powders, at room temperature, are accurately weighed in 100ml three-necked bottle, add the distillation of 50ml reaction dissolvents
Water soaks 12 hours, cellulose powder is fully swelled；
2) part thioglycolic acid, the thing of thioglycolic acid and hydroxyl on cellulose powder, are added in the gains of step 1)
The ratio between amount of matter is 3：1, under conditions of nitrogen protection, the phosphotungstic acid for adding 5% is used as catalyst, 60 DEG C of reaction temperature of holding
Degree stirring (rotating speed 100r/min) is reacted 12 hours；
3), reaction is filtered the gains of step 2) after terminating, the filter cake of gained with reaction dissolvent washing by soaking 3~
4 times (each dosage is 40ml), then wash 3 times (dosage of each distilled water is 40ml) repeatedly with distilled water successively；50
DEG C constant weight is dried under vacuum to, obtains thioglycolic acid-modified cellulose.
With infrared technique method, by thioglycolic acid-modified cellulose after cellulose powder, part and synthesis
Comparative analysis, draw the response path and thioglycolic acid-modified cellulose knot of thioglycolic acid-modified cellulose synthetic reaction
Structure, as shown in Figure 1.
Comparative example 1
Ligand mercapto glycolic in the step 2) of embodiment 1 is changed to mercaptonicotinic acid, sulfydryl salicylic acid, remaining is the same as embodiment 1
It is identical；Gained modified cellulose is respectively modified cellulose I, modified cellulose II, thioglycolic acid-modification of itself and the present invention
Cellulose adsorbent TGAC comparing result is as shown in table 1.
Sulfur content and adsorbance of the modified cellulose of the different ligands of table 1 synthesis to Se (IV) metal ion
Comparative example 2
Temperature 60 C in the step 2) of embodiment 1 is changed to be stirred under conditions of 45 DEG C, 75 DEG C, 90 DEG C, remaining is complete
Entirely with embodiment 1 the step of, is identical, so as to inquire into reaction temperature to synthesizing thioglycolic acid-modified cellulose function base conversion ratio
Influence.
From solvent of the water as this experiment, in view of the boiling point of water at ambient pressure is 100 DEG C, to avoid solvent from evaporating rapidly
And boiling influence to caused by reaction system, this experiment choose 45 DEG C, 60 DEG C, 75 DEG C, 90 DEG C and are used as experimental group.Gained contains
Sulfur content S% is respectively 3.912%, 4.852%, 3.757%, 3.530%, it can be seen that temperature have impact on to a certain extent
The grafting of part, the optimum temperature for preparing thioglycolic acid-modified cellulose are 60 DEG C, higher than sulfur content after this temperature all
Decline.
Comparative example 3
Part in the step 2) of embodiment 1 and parent are reacted into mol ratio by 3:1 makes 2 into respectively:Isosorbide-5-Nitrae:1,5:1, reaction temperature
Spend for 60 DEG C of optimum temperature, the step of remaining is completely with embodiment 1.Thioglycolic acid-the modified cellulose synthesized as shown in Figure 2
It is 3 in mol ratio:Sulfur content highest when 1, its sulfur content are 4.897%.
Comparative example 4
The phosphotungstic acid of catalyst 5% in the step 2) of embodiment 1 is made to 1% concentrated sulfuric acid into, remaining is completely the same as embodiment 1
The step of, thioglycolic acid-modified cellulose sulfur content of synthesis is 4.052%.The concentrated sulfuric acid has necessarily as catalyst
Advantage：It is inexpensive, be easy to get, technical maturity.And it is relative, it has high corrosivity, strong dehydration energy in use
Power, serious chemical burn can be caused with skin contact, very major injury is caused to human body.In contrast, using phosphotungstic acid, environment
Close friend, catalytic activity is high, and higher using the sulfur content of thioglycolic acid-modified cellulose obtained by phosphotungstic acid.
In summary, the synthesis optimum condition for thioglycolic acid-modified cellulose (TGAC) that the present invention synthesizes is：Reaction
Temperature 60 C, react mol ratio 3:1, catalyst is 5% phosphotungstic acid.
Experiment 1
The accurate 200.0mg dryings adsorbent TGAC that weighs is placed in 100mL iodine flasks, is added 45ml distilled water and is adjusted to difference
Soaked 24 hours after pH, add 5mL 8mg/mL selenite radical solion, vibrated in 25 DEG C of constant temperature oscillator, turned
Fast 100r/min.At interval of a period of time, the concentration of residual metallic ion in solution is determined, can determine whether to inhale until concentration is constant
It is attached to reach balance.Adsorbance when detecting and recording adsorption equilibrium, substitute into formula (1) and calculate adsorbent the static state of metal ion is satisfied
And adsorbance, so as to study the relation between resin adsorption performance and pH value.
Can clearly be found out by Fig. 3, last division into new thioglycolic acid-modified cellulose adsorbent (TGAC)
The tremendous influence of absorption to Se (IV) by pH value in absorption system., can be with by the adjustment (scope 1.5~11.5) to pH
See the increase with pH, the static saturated adsorption capacity of thioglycolic acid-modified cellulose drops to from 95.47mg/g
56.53mg/g, it can be seen that relatively low pH is to being adsorbed with facilitation.Now optimal pH is 1.5.
Experiment 2
In order to determine under the conditions of food samples complex process, thioglycolic acid-modified cellulose adsorbent is to selenous acid
The anti-anion interference performance of the absorption of root, modified adsorbent is mixed into certain density common acid ion (CL-、NO3 -) in,
Absorption is shown in experiment 1 with detection method, and the static saturations of Se (IV) calculated under the anion interference of variety classes, various concentrations are inhaled
Attached amount.As shown in Figure 4, CL-、NO3 -To thioglycolic acid-modified cellulose adsorbent to the Adsorption Effect of selenite radical compared with
Small, static saturated adsorption capacity is almost unchanged.
Experiment 3
200.0mg adsorbents accurately are weighed, after being soaked 24 hours in distilled water, it is Φ 3mm × 30cm's to load specification
In dynamic adsorption post, to prevent absorbent powder outflow performance chromatographic column, clogged in the bottom of post with degreasing cotton.PH will be adjusted to
Se (IV) solution control of=1.5 various concentrations is different in flow rate, crosses post respectively, and time segment collects certain volume (10mL)
Efflux is into colorimetric cylinder, sequentially determining outflow concentration Ci, until Ci=C0(showing adsorbent saturation).With trickle
Product (V) is used as abscissa, using efflux and the ratio of influent as ordinate, draws Dynamic Adsorption curve.Dynamic is calculated to inhale
Attached amount, the dynamic saturated extent of adsorption 95.9mg/g of metal ion
Experiment 4
Modified adsorbent after adsorption saturation is distilled into water washing for several times and filtered out, certain volume is added after 50 DEG C of drying
Eluant, eluent, after 25 DEG C of constant temperature oscillations balance, determine the concentration of selenite radical ion in solution.Calculate the desorption efficiency of adsorbent.
The various adsorbents of this experimental selection various concentrations desorb to absorption, dried adsorbent, variety classes and concentration solution
Influence of the vapor to eluting rate is as shown in table 2.
2 different strippants of table adsorb Se (IV) desorption efficiency to thioglycolic acid-modified cellulose
As seen from the above table, conventional eluant, eluent (NaOH, HCl etc.) is for the fine desorption of the thioglycolic acid after absorption-modification
Effect is undesirable, the maximum elution 20.1% of thioglycolic acid-modified cellulose during using NaOH as eluant, eluent, and makes
When being eluted with HCl and KCl solution, Se (IV) is not detected by eluent, it is believed that the SeO of adsorption3 2-It is not desorbed.Make
With the ammoniacal liquor of various concentrations, (ammoniacal liquor is another conventional strippant of absorbent-type selenium, sub- suitable for the absorbent-type of desorption swage, calcium type
Selenic acid ion) preferable result is not obtained yet when being desorbed.Brand-new concentrated hydrochloric acid (HCl) and potassium chlorate (KClO3) mixed solution
It is the common agents for handling sulfide, the selenium sulfide for being usually used in separating in soil in soil test is measured, this experiment
Finally being desorbed using this mix reagent, significant effect, after HCl concentration reaches 3mol/L, desorption efficiency can reach 100%,
Therefore strippant is defined as brand-new 3mol/L HCl and 0.2g KClO3Mixed liquor.
In summary, the optimal adsorption condition for thioglycolic acid-modified cellulose adsorbent (TGAC) that the present invention synthesizes
For：Optimal adsorption pH is 1.5；Optimal strippant is 3mol/L HCl and 0.2g KClO3Mixed liquor.
Experiment 5：The detection of selenium element in purple potato
1) sample pre-treatments (purple potato)：By commercially available purple potato with originally water-washing away top layer soil, then with deionized water clean number
It is secondary, agricultural chemicals and pollutant on surface are removed, drying 72 hours in 50 DEG C of thermostatic drying chambers is put into after being cut to 2mm thin slice, does
Crush after dry, dried 2 hours in 80 DEG C of thermostatic drying chambers.20g (being accurate to 0.001g) sample is weighed, is placed in digestion bottle,
Add 100.0mL mixed acid (nitric acid：Perchloric acid=9：1) and several beades, cold digestion are stayed overnight.Next day in being heated on electric hot plate,
And nitric acid is added in time.When solution is changed into Clear colourless and during with white cigarette, it is further continued for being heated to residual volume 2mL or so, cuts
It can not be evaporated.Cooling, then add 5.0mL hydrochloric acid (6mol/L), continues to be heated to solution to be changed into Clear colourless and with white cigarette occur,
Hexavalent selenium is reduced into tetravalence selenium.Cooling, constant volume in 50mL volumetric flasks is transferred to, mixing is standby while prepares blank sample.
2) separation and preconcentration of thioglycolic acid-modified cellulose (TGAC)：Accurately pipette containing a certain amount of Se (IV)
Solution, it is placed in after adjusting to pH=1.5 in TGAC dynamic adsorption posts, coutroi velocity is 1.0ml/min by the way that Dynamic Adsorption terminates
Afterwards, strippant 25mL 3.0mol/L HCl and 2% potassium chlorate is added, TGAC Dynamic Adsorptions are passed through with 0.5ml/min flow velocity
Post is desorbed, and detects outflow solution concentration.
3) prepare liquid adds 5%EDTA-2Na solution 5ml after taking 10.00ml dilutions, adjusts pH to 2 with hydrochloric acid, adds 1% adjacent benzene two
Amide hydrochloride 3ml, shaking, 50 DEG C of water-baths 30 minutes.Add toluene 10ml and shake extraction in 5 minutes, take toluene layer in 335nm
Place determines its absorbance.
4) standard working curve：Draw 2.5ml selenium stock solution (200 μ g/mL SeO3 2-Solution) it is diluted to 500ml
It is made into 1 μ g/mL SeO3 2Ion titer.0ml, 3.2mL, 6.4mL, 9.6mL 1ug/mL SeO are drawn respectively3 2Ion mark
Quasi- liquid storing solution is diluted to 10mL and detected with reference to method in step 3) in 25ml colorimetric cylinder.Standard working curve is such as
Shown in Fig. 5, in the range of 0~9.6 μ g/mL, absorbance has good linear relationship with mass concentration：Y=0.0448x+
0.0078, R2=0.998.
Contrast experiment 5-1
Make the modified cellulose TGAC tested in 5 into mercaptonicotinic acids-modified cellulose (MNAR), sulfydryl salicylic acid-to change
Property cellulose (TSAC), remaining with experiment 5, the Se content for measuring purple potato is as shown in table 3.
3 different modified celluloses of table measure the Se content of purple potato
Wherein, the preparation of cross-linked chitosan is with reference to periodical《Spectrographic laboratory》Delivered on the 2nd phase of volume 28 in 2011《Hand over
Join the selenium (1V) and selenium (VI) in the spectrophotometry environmental water sample of chitosan concentration and separation one》(author：Dai Jun, Ren Fenglian,
Tao Chunyuan, Wu Chuanbao；The start-stop page number：915-921).
Contrast experiment 5-2
By completely with experiment 5 purple potato checked according to ICP-AES direct measuring methods, as a result for：54.51ug.kg-1。
Contrast experiment 5-3
The rate of adsorption tested in 5 steps 2) is made into 0.2mL/min, 0.6mL/min by 1mL/min；Remaining is the same as experiment
5.It will be appreciated from fig. 6 that when the rate of adsorption is 0.2mL/min, 0.6mL/min, enrichment percentage is 98%, 97% respectively, and it is deposited
The defects of be：Because adsorption time is grown, efficiency is low.
Contrast experiment 5-4
By test 5 steps 2) in the rate of adsorption by 1mL/min make into 1.5mL/min, 2.0mL/min, 3.0mL/min,
4.0mL/min；Remaining is the same as experiment 5.It will be appreciated from fig. 6 that when the rate of adsorption be 1.5mL/min, 2.0mL/min, 3.0mL/min,
During 4.0mL/min, enrichment percentage reduces with the increase of the rate of adsorption, and respectively less than 95%.The defects of it is present：Adsorbate with
It is insufficient contact between adsorbent, it is unfavorable for fully adsorbing
In summary, it will be appreciated from fig. 6 that when adsorption flow rate is not higher than 1.0mL/min, enrichment percentage is more than 95%, exceedes
During 1.0mL/min, enrichment percentage substantially reduces, and to ensure absorption result and improving application efficiency, selects 1.0mL/min conducts
It is enriched with flow velocity.
Contrast experiment 5-5
The elution rate tested in 5 steps 2) is made into 0.2mL/min by 0.5mL/min, remaining is the same as experiment 5.Can by Fig. 7
Know, when elution rate is 0.2mL/min, to be 98%, the defects of it is present is the rate of recovery：Due to the extension of elution time,
Cause the defects of detection time is long be present.
Contrast experiment 5-6
The elution rate tested in 5 steps 2) is made into 1.0mL/min, 1.5mL/min, 2.0mL/ by 0.5mL/min
Min, remaining is the same as experiment 5.As shown in Figure 7, when the rate of adsorption is 1.0mL/min, 1.5mL/min, 2.0mL/min, the rate of recovery
Reduced with the increase of elution rate.The accuracy of this method substantially reduces.
In summary, as shown in Figure 7, when being eluted with 5mL eluent with 0.5mL/min flow velocity, the rate of recovery can
Up to 97.8%, best results are eluted.
Above-described embodiment is not limit the invention in any way, every to be obtained by the way of equivalent substitution or equivalent transformation
Technical scheme all fall within protection scope of the present invention.
Claims (3)
- A kind of 1. preparation method of thioglycolic acid-modified cellulose, it is characterised in that using cellulose powder as parent, thio second Alkyd is part, and the hydroxyl on cellulose powder is modified, comprised the following steps：（1）Cellulose powder is immersed in the distilled water as reaction dissolvent, until cellulose powder is fully swelled；Cellulose powder with The amount ratio of reaction dissolvent distilled water is：1g cellulose powders/50ml reaction dissolvent distilled water；（2）In step（1）Gains in add part thioglycolic acid, nitrogen protection under conditions of, add 5% phosphorus tungsten Acid, keeps 60 DEG C of reaction temperature stirring reaction 12 hours；The amount of the thioglycolic acid and the material of hydroxyl in cellulose powder The ratio between be 3：1；（3）Filtration step（2）Gains, obtain filter cake, the reacted solvent washing of gained filter cake is to after colourless, 50 DEG C of vacuum drying To constant weight, thioglycolic acid-modified cellulose is obtained.
- 2. a kind of thioglycolic acid-modified cellulose, it is characterised in that prepared by the method for claim 1.
- 3. the application of thioglycolic acid-modified cellulose described in claim 2, it is characterised in that comprise the following steps：（1）Testing sample pre-treatment：Testing sample obtains containing selenous solution to be measured after repeatedly acidifying, heating, cooling；（2）The separation and preconcentration of thioglycolic acid-modified cellulose：Claim is placed in after solution to be measured is adjusted to pH=1.5 In the dynamic adsorption post of the 2 thioglycolic acid-modified celluloses, coutroi velocity is 1.0ml/min by the way that Dynamic Adsorption terminates Afterwards, the mol/L of 25mL 3.0 HCl and 2% potassium chlorate strippant is added, is inhaled with 0.5ml/min flow velocity by the dynamic Attached column is desorbed, and detects outflow solution concentration；The testing sample is purple potato.
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