CN107129543A - A kind of thiocarbamide modification of chitosan and its preparation method and application - Google Patents
A kind of thiocarbamide modification of chitosan and its preparation method and application Download PDFInfo
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- CN107129543A CN107129543A CN201710165560.6A CN201710165560A CN107129543A CN 107129543 A CN107129543 A CN 107129543A CN 201710165560 A CN201710165560 A CN 201710165560A CN 107129543 A CN107129543 A CN 107129543A
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Abstract
The invention discloses a kind of thiocarbamide modification of chitosan, its preparation method includes：(1) dissolve the chitosan in acetic acid solution, add glutaraldehyde water solution, cross-linking modified chitosan is reacted to obtain under microwave radiation；(2) the cross-linking modified chitosan for obtaining step (1) is soaked in the NaOH aqueous solution, adds monoxone, monoxone modification of chitosan is reacted to obtain under microwave radiation；Thiocarbamide is subsequently added, 0.5~1.5h is reacted under microwave radiation, the thiocarbamide modification of chitosan is obtained after suction filtration, washing.The present invention is using chitosan as parent, reacted with part thiocarbamide, the thiocarbamide modification of chitosan with high function base conversion ratio can be obtained under microwave action, gained thiocarbamide modification of chitosan has good selective absorption performance to food synthetic pigment, can apply to the analysis detection field of amaranth in beverage.
Description
Technical field
The invention belongs to edible synthesized coloring matter absorption detection field, and in particular to a kind of thiocarbamide modification of chitosan and its preparation
Methods and applications.
Background technology
Food coloring can be divided into edible natural pigment and secondary colour as the food additives of sensory quality of food are improved
Element.Edible natural pigment is extracted from animal and plant, generally relatively safety, harmless, but it is poor to there is dyeing capacity, composition
Complexity, less stable is easy to change, the shortcomings of cost is higher, limits its application in the food industry.Edible synthesized coloring matter
Synthesis processing is carried out by Organic Chemicals to obtain, high with tinting strength, tinting power, bright in colour, impurity is less, and stability is higher, easily
Storage, the advantages of price is relatively low is widely used in food.But edible synthesized coloring matter has certain toxic action, mainly
It is due to heavy metal therein (lead, copper, arsenic), ether, phenol, aniline, chloride and sulfate etc., different journeys is caused to human body
The harm of degree.
In recent years, China's edible synthesized coloring matter consumption is in cumulative year after year, and criminal is in the case where interests are driven, and breakthrough allows to make
Kind, quantity and scope, abuse edible synthesized coloring matter so that food security violation event frequently occurs, and threaten consumption
Person's is healthy, and food security faces the challenge.The measure of so edible synthesized coloring matter has become the pass for ensureing food security
Key.
There are high performance liquid chromatography, high performance capillary electrophoresis to the detection method that edible synthesized coloring matter is commonly used at present, divide
Light photometry, fluorescent spectrometry, thin-layered chromatography etc..High performance liquid chromatography sensitivity is high, and precision is high, good separating effect,
Amount of samples is less, and test limit is relatively low, but the method pretreatment process is cumbersome, and mobile phase is with toxic organic solvents, and to need many
Plant solvent and make mobile phase, easily cause environmental pollution, experiment process is slower, operation requires higher, and solvent.Equipment is costly.
And high performance capillary electrophoresis is simple to operate, separating rate is fast, and reagent consumption is less, and what environment was produced is of reduced contamination, but point
Weaker from ability, the requirement to pH value is higher.Polarography is applied widely, the scope that can determine constituent content is wide, the degree of accuracy is high,
Sensitivity height, good precision, favorable reproducibility, selectivity are strong, can carry out METHOD FOR CONTINUOUS DETERMINATION, but it prepares trouble, dropping-mercury electrode requirement
Strictly, mercury is volatile and mercury vapour is poisonous, is not yet popularized in inspection body of basic unit.So, edible synthesized coloring matter in food
There is instrument and equipment costliness in determination method, cost is high, is easily disturbed, applicable food narrow range, cumbersome etc. mostly
Shortcoming.
Chitosan has good biocompatibility and an adsorptivity, and because with nontoxic, chemical property is stable, can be biological
The characteristics such as degraded, are widely used in the fields such as biotechnology, chemical industry, light and textile industries, food industry.Modification of chitosan can be made
For a kind of high absorption, the adsorbent of low cost, it is of wide application in terms of adsorpting pigment, dyestuff general.
Microwave is one kind of electromagnetic wave, between shortwave and far infrared, and wavelength is from 1mm-1m, referred to as microwave, its frequency
About in 300MHz to being widely used between 300GHz in medical treatment, scientific research, industrial or agricultural and daily life.Microwave spoke
Method is penetrated, is compared with conventional heating methods, its mode of heating heats to be internal, it is not necessary to which media conduct heat, fast with aggregate velocity, instead
Short, simple operation and other advantages between seasonable.Therefore, microwave heating technique has before good application development in the field of chemical synthesis
Scape.
Microwave heating is modified to chitosan, the progress of synthetic reaction is more beneficial for, and with reaction speed it is fast and
Homogeneous heating, efficient energy-saving, it is easy to control, the advantages of environmental pollution is less.The method can be obtained more for advantageous property
Modification of chitosan.
The content of the invention
The purpose of invention is that solve above-mentioned technology present in prior art and Cost Problems is modified there is provided a kind of thiocarbamide
Chitosan and its preparation method and application, the present invention is reacted using cross-linked chitosan as parent with part thiocarbamide, is made in microwave
The thiocarbamide modification of chitosan with higher functionality base conversion ratio is resulted under, gained thiocarbamide modification of chitosan is synthesized to food
Pigment has good selective absorption performance, can apply to the analysis detection field of amaranth in beverage.
To solve above-mentioned technical barrier, the present invention uses following technical scheme：
A kind of thiocarbamide modification of chitosan, with the structure as shown in formula (I)：
In formula, n=1,2,3 ...；
The thiocarbamide modification of chitosan by chitosan is through glutaraldehyde, monoxone and thiocarbamide is modified obtains, chitosan it is de-
Acetyl degree is 80%~95%；Viscosity is 50~800mPas.
Present invention also offers a kind of preparation method of the thiocarbamide modification of chitosan, including：
(1) the microwave synthesis of cross-linking modified chitosan：Dissolve the chitosan in acetic acid solution, add glutaraldehyde water-soluble
Liquid, reacts 0.5~1.5h under microwave radiation in 15~35 DEG C and obtains cross-linking modified chitosan；
(2) the microwave synthesis of thiocarbamide modification of chitosan：The cross-linking modified chitosan that step (1) is obtained is soaked in NaOH water
In solution, monoxone is added, reacting 0.5~1.5h under microwave radiation in 25~45 DEG C obtains monoxone modification of chitosan；Then
Thiocarbamide is added, 0.5~1.5h is reacted under microwave radiation in 25~45 DEG C, the thiocarbamide modification shell is obtained after suction filtration, washing and is gathered
Sugar.
Preferably, the intrinsic viscosity of the chitosan is 50~800mPas.
Preferably, in step (1), the mass fraction of acetic acid solution is 1~5%, and 30~70mL second is added in every g chitosans
Acid solution.
Preferably, in step (1), the mass fraction of glutaraldehyde water solution is 20~30%, per g chitosans in add 1~
2mL glutaraldehyde water solutions.
Preferably, in step (1), the microwave irradiation power is 300~500W.
Preferably, in step (2), the mass fraction of the NaOH aqueous solution can for the consumption of 3~7%, the NaOH aqueous solution
It is adjusted, is defined by being completely soaked sample according to actual conditions.
Preferably, in step (2), chloroacetic dosage is 0.1~0.5 times of chitosan mass in step (1), with
Monoxone adds the increase of ratio, and the function base conversion of thiocarbamide modification of chitosan takes the lead in reducing after increase.Further preferably, chloroethene
The dosage of acid is 0.2~0.5 times of chitosan mass in step (1).
Preferably, in step (2), reaction temperature is 15~35 DEG C, and in the temperature range, function base conversion ratio is with anti-
Answer the rising of temperature and raise, the rise of temperature contributes to the positive progress of synthetic reaction, i.e. temperature is higher, and conversion ratio is higher.
Further preferably, reaction temperature is 25~35 DEG C.
Preferably, in step (2), the mol ratio 1~5 of thiocarbamide and chitosan in step (1)：1.The molar ratio of thiocarbamide
When relatively low, function base conversion ratio becomes big with the increase of mol ratio, and this is due to the rise with ligand concentration so that part with
The reactivity site contact increase of parent, contributes to the positive progress of synthetic reaction, and therefore function base conversion ratio also increases；But
After reactivity site has reached saturation state, with the continuation increase of mol ratio, the positive progress of synthetic reaction is hindered,
Significant changes no longer occur substantially for function base conversion ratio.Further preferably, the mol ratio 2~3 of thiocarbamide and step (1) chitosan：
1。
Preferably, in step (2), the microwave irradiation power is 300~500W.
Present invention also offers a kind of application of above-mentioned thiocarbamide modification of chitosan in absorption amaranth.
Present invention also offers the application that a kind of above-mentioned thiocarbamide modification of chitosan analyzes detection amaranth in the beverage.This hair
The separation and concentration and context of detection of bright edible synthesized coloring matter in the beverage are widely used, and can have by thiocarbamide modification of chitosan
Edible synthesized coloring matter in the separation and concentration beverage of effect, by being detected with UV-VIS spectrophotometry combination, the method
Easy to operate, cost is low, precision is high, good separating effect, the rate of recovery high.
The present invention has the advantages that relative to prior art：
1st, raw material chitosan of the invention has good biocompatibility and adsorptivity, and because with nontoxic, chemistry
Property is stable, biodegradable.Cost it is low can and the characteristic such as efficiently concentrating, be widely used in biotechnology chemical industry, light textile
The fields such as industry, food industry.And there is stronger change to this containing a large amount of active hydroxyls and amino in chitosan macromolecular
Respond is learned, it is easily modified, and by surface graft modification, make the amaranth pigment that chitosan can be in enriched food.Meanwhile, close
Into simple to operate, it is more suitable for the detection to food synthetic pigment.
2nd, the present invention is modified with microwave irradiation to chitosan.Compare with traditional heating, when being substantially shorter reaction
Between, accelerate reaction rate, homogeneous heating, and reduction production cost, absorption property more excellent modification of chitosan can be obtained.
3rd, the thiocarbamide modification of chitosan that the present invention is provided is recyclable, reusable, it is possible to increase the utilization rate of resource.
Brief description of the drawings
Fig. 1 is that chitosan (CTS), cross-linking modified chitosan (GCTS), monoxone modification of chitosan (CCTS) and thiocarbamide change
The infrared spectrogram of property chitosan microball (TCCTS)；
Fig. 2 is the thermogravimetric curve of chitosan (CTS), thiocarbamide (THU) and thiocarbamide modification of chitosan (TCCTS)；
Fig. 3 is absorption property result figures of the TCCTS under condition of different pH to amaranth solution；
Fig. 4 is the absorption property result figures of TCCTS at different temperatures to amaranth solution.
Embodiment
In the present invention, the method for computing function base conversion ratio (%) is as follows：
1.000~2.000mg thiocarbamide modification of chitosan microballoons are accurately weighed by millionth balance, masking foil is used
It is sequentially placed into after parcel in pallet and waits sample analysis.Thiocarbamide, which is determined, using Vario EL type III elemental analysers is modified shell
The content of N element in glycan microballoon, and function base conversion ratio in thiocarbamide modification of chitosan microballoon is calculated by below equation
(functionalgroup conversion, %).
In above formula, x is function base conversion ratio,
F0For amino content in chitosan (mmol/g),
N0For the nitrogen content (%) of chitosan,
NcFor the nitrogen content (%) of thiocarbamide modification of chitosan microballoon,
MLFor the molal weight (g/mol) of part,
nNFor the number of nitrogen-atoms in ligand molecular.
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Embodiment 1
The preparation method of the thiocarbamide modification of chitosan of the present invention, comprises the following steps：
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 20ml 2%, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；Add the glutaraldehyde solutions of 0.5ml 25% and stir, be positioned in microwave reactor, 300W microwave radiation work(
Under rate, using 300rmp rotating speed heating-up temperature as 35 DEG C, 1h is stirred.Natural cooling, is carried out suction filtration and is washed for several times, in 50
24h is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS).
(2) product of step (1) is soaked in 50ml 5%NaOH solution and carried out after vibration 4h, add 0.1g chloroethene
Acid, is positioned in microwave reactor, under 300W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is carried out under the conditions of 35 DEG C
Reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and shell in step (1)
The mol ratio of glycan is 2:1, continue to react after 1h, obtained product natural cooling at 35 DEG C, carry out filtering and washing to neutrality.
24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 33.66%.
Gained chitosan (CTS), cross-linking modified chitosan (GCTS), monoxone modification of chitosan (CCTS) and thiocarbamide are modified
The infrared spectrum of chitosan microball (TCCTS) is as shown in figure 1, from figure 1 it appears that chitosan (CTS) and cross-linking modified shell
3400cm in glycan (GCTS)-1The absworption peak at place is overlapping by O-H and N-H stretching vibration, and GCTS is in 1649cm-1Locate C=N
Characteristic absorption peak enhancing, after this is due to glutaraldehyde cross-linking, form schiff bases.CCTS is in 1071cm-1The absworption peak at place increases
By force, C is illustrated6Changed on-O, in 1601cm-1Place occurs in that carboxylate radical COO- antisymmetric stretching vibrations peak, illustrates chloroethene
Acid and C6On hydroxyl reacted.TCCTS is in 1400cm-1The carboxylate radical COO- at place symmetrical stretching vibration peak weakens, and says
It is bright to be reacted on carboxyl, and in 1662cm-1Place occurs in that the stretching vibration absworption peak of C=O in acid amides, C=S characteristic peaks
In 1020~1250cm-1, the peak intensity is weaker, and in summary, thiocarbamide is successfully introduced into chitosan.
The thermogravimetric curve of chitosan (CTS), thiocarbamide (THU) and thiocarbamide modification of chitosan (TCCTS) is as shown in Figure 2.Sulphur
Urea (THU) is basic without weightlessness between 25 DEG C to 200 DEG C, decomposes rapid between 200 DEG C to 300 DEG C, weight-loss ratio is about
89.51%.THU decomposes slow until decomposing complete, weight-loss ratio reaches 100% between 300 DEG C to 800 DEG C.Compared with chitosan,
TCCTS is decomposed slowly between 25 DEG C to 245 DEG C, it may be possible to which the evaporation of moisture, weight-loss ratio is about 8.99%.From 245 DEG C to 800 DEG C
Between, TCCTS is first decomposed rapidly, rear to decompose slow until decomposing complete, the about ashes and residue of residue 37.29%, and more than CTS
Remaining weight, illustrates that TCCTS is modified successfully.TCCTS is resistant to less than 245 DEG C of temperature, and thermally-stabilised preferable, more than 600 DEG C can
Decompose completely, environmental pollution is small.
Embodiment 2
The preparation method of the thiocarbamide modification of chitosan of the present invention, comprises the following steps：
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 15ml 5%, stirring to dissolving；Add 0.5ml
25% glutaraldehyde solution is simultaneously stirred, and is positioned in microwave reactor, under 300W microwave irradiation powers, is heated with 300rmp rotating speed
Temperature is 35 DEG C, stirs 1h.Natural cooling, is carried out suction filtration and is washed for several times, centre is obtained in being dried in vacuo 24h at 50 DEG C
The cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in 60ml 5%NaOH solution and carried out after vibration 4h, add 0.1g chloroethene
Acid, is positioned in microwave reactor, under 400W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is carried out under the conditions of 35 DEG C
Reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and shell in step (1)
The mol ratio of glycan is 2:1, continue to react after 1h, obtained product natural cooling at 30 DEG C, carry out filtering and washing to neutrality.
24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 27.8%.
Embodiment 3
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 35ml 1%, stirring to dissolving；Add 1.0ml
25% glutaraldehyde solution is simultaneously stirred, and is positioned in microwave reactor, under 300W microwave irradiation powers, is heated with 300rmp rotating speed
Temperature is 30 DEG C, stirs 1.5h.Natural cooling, is carried out suction filtration and is washed for several times, in vacuum drying 24h is obtained at 50 DEG C
Between the cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in 70ml 3%NaOH solution and carried out after vibration 4h, add 0.25g chlorine
Acetic acid, is positioned in microwave reactor, under 300W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is entered under the conditions of 35 DEG C
Row reaction 1.5h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of middle chitosan is 3:1, continue to react after 1h, obtained product natural cooling at 35 DEG C, carry out filtering and washing extremely
It is neutral.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 31.74%.
Embodiment 4
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 20ml 3%, stirring to dissolving；Add 1.0ml
20% glutaraldehyde solution is simultaneously stirred, and is positioned in microwave reactor, under 500W microwave irradiation powers, is heated with 300rmp rotating speed
Temperature is 15 DEG C, stirs 1.5h.Natural cooling, is carried out suction filtration and is washed for several times, in vacuum drying 24h is obtained at 50 DEG C
Between the cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in 75ml 3%NaOH solution and carried out after vibration 5h, add 0.2g chloroethene
Acid, is positioned in microwave reactor, under 300W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is carried out under the conditions of 45 DEG C
Reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).Add in thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of chitosan is 3:1, continue to react after 1h, obtained product natural cooling at 45 DEG C, carry out filtering and washing into
Property.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 32.06%.
Embodiment 5
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 15ml 5%, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；Add the glutaraldehyde solutions of 2ml 20% and stir, be positioned in microwave reactor, 500W microwave irradiation powers
Under, using 300rmp rotating speed heating-up temperature as 15 DEG C, stir 1.5h.Natural cooling, is carried out suction filtration and is washed for several times, in 50
24h is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS).
(2) product of step (1) is soaked in 60ml 3%NaOH solution and carried out after vibration 4h, add 0.05g chlorine
Acetic acid, is positioned in microwave reactor, under 500W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is entered under the conditions of 40 DEG C
Row reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of middle chitosan is 4:1, continue to react after 0.5h, obtained product natural cooling at 40 DEG C, carry out filtering and washing
To neutrality.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 27.58%.
Embodiment 6
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 20ml 2%, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；Add the glutaraldehyde solutions of 0.5ml 25% and stir, be positioned in microwave reactor, 300W microwave radiation work(
Under rate, using 300rmp rotating speed heating-up temperature as 35 DEG C, 1h is stirred.Natural cooling, is carried out suction filtration and is washed for several times, in 50
24h is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS).
(2) product of step (1) is soaked in 50ml 5%NaOH solution and carried out after vibration 4h, add 0.05g chlorine
Acetic acid, is positioned in microwave reactor, under 500W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is entered under the conditions of 35 DEG C
Row reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of middle chitosan is 1:1, continue to react after 0.5h, obtained product natural cooling at 35 DEG C, carry out filtering and washing
To neutrality.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 23.75%.
Embodiment 7
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 20ml 2%, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；Add the glutaraldehyde solutions of 0.5ml 25% and stir, be positioned in microwave reactor, 300W microwave radiation work(
Under rate, using 300rmp rotating speed heating-up temperature as 35 DEG C, 1h is stirred.Natural cooling, is carried out suction filtration and is washed for several times, in 50
24h is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS).
(2) product of step (1) is soaked in 50ml 5%NaOH solution and carried out after vibration 4h, add 0.25g chlorine
Acetic acid, is positioned in microwave reactor, under 400W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is entered under the conditions of 25 DEG C
Row reaction 1.5h obtains intermediate product monoxone modification of chitosan (CCTS).Add thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of middle chitosan is 5:1, continue to react after 1h, obtained product natural cooling at 30 DEG C, carry out filtering and washing extremely
It is neutral.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 25.13%.
Embodiment 8
(1) take 0.5g chitosans to be placed in beaker, add the acetic acid solvents of 20ml 2%, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；Add the glutaraldehyde solutions of 0.3ml 30% and stir, be positioned in microwave reactor, 300W microwave radiation work(
Under rate, using 300rmp rotating speed heating-up temperature as 35 DEG C, 1h is stirred.Natural cooling, is carried out suction filtration and is washed for several times, in 50
24h is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS).
(2) product of step (1) is soaked in 50ml 5%NaOH solution and carried out after vibration 4h, add 0.15g chlorine
Acetic acid, is positioned in microwave reactor, under 300W microwave irradiation powers, with 300rmp rotating speeds, and heating stirring is entered under the conditions of 35 DEG C
Row reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).Add in thiocarbamide (THU), added thiocarbamide and step (1)
The mol ratio of chitosan is 3:1, continue to react after 1.5h, obtained product natural cooling at 30 DEG C, carry out filtering and washing extremely
It is neutral.24h is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS).
After testing, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 31.54%.
Embodiment 9~14
Accurately weigh 6 parts of 10mg thiocarbamide modification of chitosan in iodine flask, be separately added into 20mL pH for 1.0,2.0,
3.0th, 4.0,5.0 and 6.0 acetic acid-sodium acetate (HAc-NaAc) cushioning liquid is swelled it, and it is dense to add 5mL after immersion 24h
The amaranth solution for 0.1mg/mL is spent, is tested using the solution for being not added with thiocarbamide modification of chitosan as blank control, in 298K, vibration
Frequency is that constant temperature oscillation is until adsorption equilibrium under the conditions of 100rmp, and it is dense using UV-VIS spectrophotometry to determine amaranth
Degree, the calculation formula of adsorption capacity is as follows:
In formula：
QeThe static saturated adsorption capacity (mg/g) of-thiocarbamide modification of chitosan adsorbent,
C0Amaranth concentration (mg/mL) in solution before-absorption,
CeAmaranth concentration (mg/mL) in solution after-adsorption equilibrium,
The volume (mL) of V-adsorbent solution,
The quality (g) of m-thiocarbamide modification of chitosan adsorbent.
The present embodiment have studied absorption property of the thiocarbamide modification of chitosan to amaranth solution under condition of different pH, as a result
As shown in figure 3, as seen from the figure, the influence that the different pH value of solution adsorb amaranth to thiocarbamide modification of chitosan is larger, and it is adsorbed
Amount changes with pH change.At low ph conditions, with pH rise, absorption of the thiocarbamide modification of chitosan to amaranth is held
Amount increases therewith, and optimal adsorption pH is that 3, TCCTS is higher to the adsorption capacity of amaranth, and its maximal absorptive capacity is 533.3mg/
g.In acid condition, absorption of the thiocarbamide modification of chitosan to amaranth is conducive to.This is due to that in an acidic solution, thiocarbamide changes
- the NH of property chitosan2Protonation, formation-NH3 +, and the sulfonic acid group on amaranth naphthalene nucleus is in an acidic solution then with anion
Form exist, thiocarbamide modification of chitosan adsorbs amaranth by electrostatic interaction.When pH value of solution continues to increase, two kinds of modified shells
The adsorption capacity of glycan is decreased.This is due to that the effect of thiocarbamide modification of chitosan protonated amino is gradually reduced, and electrostatic is made
With decrease so that its adsorption capacity is reduced.
Embodiment 15~17
Three parts of 10mg thiocarbamide modification of chitosan adsorbent is weighed in iodine flask, it is 3 to be separately added into 20mL in pH
Soaked in HAc-NaAc cushioning liquid after 24h, it is 0.1mg/mL amaranth standard liquids to add 5mL concentration, respectively 288K,
298K and 308K, frequency of oscillation is adsorbed for constant temperature oscillation under the conditions of 100rmp.A small amount of solution is pipetted at regular time and quantity to be surveyed
Fixed, until remaining amaranth concentration no longer changes in solution, i.e., adsorption experiment reaches balance.
The present embodiment have studied absorption heating power of the thiocarbamide modification of chitosan to amaranth under temperature 288K, 298K and 308K
Property is learned, as a result as shown in figure 4, from map analysis, in the absorption starting stage, because amaranth concentration is larger, and thiocarbamide changes
The adsorption site of property chitosan is more, larger mass transfer force cause thiocarbamide modification of chitosan to the rate of adsorption of amaranth compared with
It hurry up, therefore increase over time, TCCTS increases rapid to the adsorbance of amaranth.But with the further progress of absorption,
TCCTS adsorption site is being gradually decreased, and the amaranth concentration in solution is also being gradually reduced, and adsorption space steric hindrance becomes
Greatly so that the TCCTS rate of adsorption reduces, finally absorption reaches poised state.TCCTS is to the time of equilibrium adsorption of amaranth
10h.From figure it is also seen that, temperature has a certain impact to the rate of adsorption and adsorbance.With the rise of temperature, accordingly
Ground, TCCTS maximal absorptive capacity is also increased, and it is an endothermic process, the liter of temperature to illustrate absorption of the TCCTS to amaranth
Height is conducive to the positive progress of absorption.
Embodiment 18~20
After thiocarbamide modification of chitosan after adsorption saturation in embodiment 16 is filtered out, with the HAc-NaAc buffer solutions that pH is 3
Wash for several times and dry respectively with deionized water, then add NaOH, NH respectively4Cl and NaCl is used as strippant, constant temperature oscillation
Amaranth concentration in solution is determined after to desorption balance.Wherein desorption efficiency (E) calculation formula is as follows：
In formula：
CdThe concentration (mg/mL) of amaranth after-desorption balance,
VdThe volume (mL) of-stripping workshop,
The volume (mL) of V-adsorbent solution,
C0The initial concentration (mg/mL) of-absorption phase amaranth,
CeThe equilibrium concentration (mg/mL) of-absorption phase amaranth.
The desorption ability size of thiocarbamide modification of chitosan is to evaluate a key factor of its absorption property quality.Energy of desorption
The magnitude relationship of power to the regenerability of thiocarbamide modification of chitosan, the organic efficiency of amaranth, and actual application value, because
This, the present embodiment is inquired into the desorption ability of thiocarbamide modification of chitosan, and experimental result is as shown in table 1.
Desorption efficiency of the different strippants of 1 three kinds of table to TCCTS
As seen from the above table, the difference of the species of strippant and concentration can have large effect to desorption effect.Right
In the desorption process of amaranth, TCCTS desorption efficiencies in the presence of 2mol/L NaOH are maximum, and TCCTS maximum desorption efficiency is
95.4%.
Embodiment 21
In desorption process, strippant may influence the absorption property of thiocarbamide modification of chitosan.Therefore this experiment with
2mol/L NaOH has inquired into the absorption-desorption recycling experiment of thiocarbamide modification of chitosan, weight as TCCTS strippant
Attached-desorption process 5 times is relapsed, its repeat usage is calculated, experimental result is shown in Table 2.
Table 2TCCTS adsorption rate
The result of regeneration tests is shown, after 5 repetitions are tested, and TCCTS is saturation first to the adsorbance of amaranth
The 78.9% of adsorbance.It can to sum up obtain, TCCTS has preferable power of regeneration and repeat performance.
Claims (7)
1. a kind of thiocarbamide modification of chitosan, with the structure as shown in formula (I)：
In formula, n=1,2,3 ...；
The thiocarbamide modification of chitosan by chitosan is through glutaraldehyde, monoxone and thiocarbamide is modified obtains, chitosan it is deacetylated
Spend for 80%~95%；Viscosity is 50~800mPas.
2. a kind of preparation method of thiocarbamide modification of chitosan according to claim 1, it is characterised in that including：
(1) the microwave synthesis of cross-linking modified chitosan：Dissolve the chitosan in acetic acid solution, add glutaraldehyde water solution, in
15~35 DEG C are reacted 0.5~1.5h under microwave radiation and obtain cross-linking modified chitosan；
(2) the microwave synthesis of thiocarbamide modification of chitosan：The cross-linking modified chitosan that step (1) is obtained is soaked in the NaOH aqueous solution
In, monoxone is added, reacting 0.5~1.5h under microwave radiation in 25~45 DEG C obtains monoxone modification of chitosan；It is subsequently added
Thiocarbamide, 0.5~1.5h is reacted in 25~45 DEG C under microwave radiation, and the thiocarbamide modification of chitosan is obtained after suction filtration, washing.
3. the preparation method of thiocarbamide modification of chitosan according to claim 2, it is characterised in that in step (1), glutaraldehyde
The mass fraction of the aqueous solution is 20~30%, and 1~2mL glutaraldehyde water solutions are added in every g chitosans.
4. the preparation method of thiocarbamide modification of chitosan according to claim 2, it is characterised in that described micro- in step (2)
Wave radiation power is 300~500W.
5. the preparation method of thiocarbamide modification of chitosan according to claim 2, it is characterised in that in step (2), monoxone
Dosage be 0.1~0.5 times of chitosan mass in step (1).
6. a kind of application of thiocarbamide modification of chitosan according to claim 1 in absorption amaranth.
7. a kind of thiocarbamide modification of chitosan according to claim 1 analyzes the application of detection amaranth in the beverage.
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| CN114849658A (en) * | 2022-04-28 | 2022-08-05 | 浙江海拓环境技术有限公司 | Sulfenyl chitosan fiber adsorbent for adsorbing Ag (I), preparation and application thereof |
| CN114849658B (en) * | 2022-04-28 | 2024-03-19 | 浙江海拓环境技术有限公司 | Sulfur chitosan fiber adsorbent for adsorbing Ag (I), preparation and application thereof |
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