CN102977271B - Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma - Google Patents
Method for preparing chitosan/crylic acid composite through initiating polymerization by using glow discharge electrolysis plasma Download PDFInfo
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Abstract
The invention provides a method for preparing a chitosan/crylic acid composite which is prepared by using chitosan and crylic acid as raw materials and N,N'-methylene bisacrylamide as a crosslinking agent through initiating polymerization by using glow discharge electrolysis plasma in an acetic acid water solution in a one-step manner. The chitosan/crylic acid composite has the advantages of high water absorption rate, high salt tolerance, good recycling property and large dye absorption quantity so as to be a composite water absorbing material with excellent property, and can be used in fields such as agriculture and forestry, gardening, purification of sewage and medicine slow release. In addition, the preparation method has the advantages of easily available raw materials, simple preparation process and low synthesis cost; and an initiating agent is not needed, thus the preparation method avoids the secondary pollution caused by the initiating agent, is a green synthesis technology according with the sustainable development, and has a potential application prospect.
Description
Technical field
The invention belongs to field of compound material, relate to the preparation method of a kind of chitosan/acrylic hydrogel matrix material, particularly relate to a kind of method utilizing glow discharge electrolysis plasma body to cause synthesis chitosan/acrylic hydrogel.
Background technology
Chitosan (Chitosan; CS) be a kind of natural cationic high molecular polymer that chitin obtains through deacetylation; be made up of glucosamine unit and 2-Acetamido-2-deoxy-D-glucose unit; it is the alkaline polysaccharide that nature uniquely exists in a large number; not only abundance, and there is good histocompatibility, biodegradability and adhesion.But the free amine group in chitosan molecule can accept proton salify, can dissolve in an acidic solution, cause loss, seriously limit its application.Therefore, improving acid resistance is one of focus of current chitin modified research.
Hydroxyl abundant on chitosan molecule chain and amino make it be easy to carry out chemically modified; as through the modified introducing stimuli responsive polymers of acidylate, carboxylation and hydroxylation or small molecules; give the stuctures and properties that chitosan is new; become by natural polysaccharide and the molecular intelligent macromolecule hydrogel with three-dimensional net structure of synthesis high score; substantially improve the water-soluble of chitosan and moisture retention, and change the liberation characteristic of chitosan molecule side-chain radical in different pH value.Accordingly, chitosan-based hydrogel material is expected to have certain using value in health care, agriculture and garden, sewage purification, biomaterial etc.Up to now, the main preparation methods of chitosan-based hydrogel has chemistry initiation method, radiation causes method and light-initiated method, has recently also occurred some reports caused about microwave.
Glow discharge electrolysis plasma body (GDEP) belongs to nonequilibrium plasma, is a kind of electrochemical method of novel generation plasma body.The phenomenon occurred in glow discharge electrolysis process and general electrolytic are obviously different, and Hickling etc. propose the chemical reaction that in the aqueous solution, glow discharge electrolysis causes and are:
H
2O
+ gas+
nH
2O →
nOH? +
nH
H?+H?→ H
2
OH + ?OH → H
2O
2
OH + H
2O
2→ HO
2? + H
2O
OH + HO
2? → H
2O+O
2
H? + ?OH → H
2O
Research shows, the most significant feature of glow discharge electrolysis is non-faraday's property (voltage is greater than 320 V, and product yield and Faraday's law depart from), and the amount of substance be namely converted greatly exceed the value calculating gained by Faradic electricity gauge.As Sengupta etc. uses Ce
3+draw the OH often being generated about 12 mol by 1 mol electronics in liquid phase reaction district when making OH trapping agent research glow discharge electrolysis, far exceed the output calculated by Faraday's law.Because OH has very high activity, can react with the amino on acrylic acid double bond, chitosan molecule chain in the aqueous solution etc. and form free radical, finally under linking agent effect, obtain CS/AA hydrogel.
Summary of the invention
The object of this invention is to provide a kind of method utilizing glow discharge electrolysis plasma-initiated polymerization to prepare chitosan/vinylformic acid matrix material.
The present invention utilizes glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, for raw material with chitosan and vinylformic acid, with N, N'-methylene-bisacrylamide is linking agent, utilize glow discharge electrolysis plasma body initiated polymerization in acetic acid aqueous solution, a step obtains chitosan/vinylformic acid matrix material.
Its concrete technology is: chitosan and linking agent are fully dissolved in acetic acid aqueous solution, add vinylformic acid, stirs 10 ~ 30 min in 60 ~ 90 DEG C; Under voltage 550 ~ 650 V, electric current 65 ~ 40 mA, falling electric current after glow discharge 2 ~ 6 min is again 10 below mA, stops electric discharge; Continue stirring 3 ~ 5 h, be cooled to room temperature, obtain g., jelly-like gel; Being shredded by g., jelly-like gel to diameter is the fragment of 2 ~ 5 mm, then is neutralized to degree of neutralization by NaOH solution and reaches 60% ~ 90%, then removes unreacted monomer by water, washing with alcohol, dry, obtains chitosan/acrylic hydrogel; Pulverize, cross 100 mesh sieves, obtain chitosan/vinylformic acid xerogel matrix material.
Described chitosan and acrylic acid mass ratio are 1:20 ~ 1:3.
The mass ratio of described linking agent and chitosan is 1:1 ~ 1:6.
The mass percent of described acetic acid aqueous solution is 1% ~ 5%.
Described drying is vacuum-drying at 40 ~ 70 DEG C.
Below by infrared spectra, thermogravimetric analysis, scanning electron microscope, water-absorbent test, salt tolerance test, pH sensitivity tests, absorbing dye methylene blue carry out analytic explanation to the structure of multifunctional composite prepared by the present invention, pattern, performance.
1, infrared spectra
Fig. 1 is the infrared spectra of vinylformic acid (AA), chitosan (CS) and chitosan/acrylic hydrogel (CS/AA) matrix material.As can be seen from Figure 1, after forming hydrogel, vinylformic acid 1632 cm
-1the stretching vibration peak of place C=C disappears, 1706 cm
-1the absorption peak of place C=O shifts to lower wave number (1642 cm
-1) and peak shape weaken to some extent.Stretching vibration absorption peak (2876 cm of chitosan methylene radical
-1) shift to lower wave number (2936 cm
-1) and intensity greatly strengthen, 1598 cm of chitosan
-1the acid amides II peak (N-H in-plane bending vibration) at place disappears, and to show on acrylic acid double bond and chitosan-NH
2group there occurs addition reaction.Moreover, formed and to have occurred two new characteristic peaks after hydrogel, 1571 cm
-1with 1410 cm
-1, they are-COO respectively
-asymmetrical stretching vibration peak and symmetrical stretching vibration peak.Chitosan C
3-OH(1090) and C6-OH(1030) C-O stretching vibration absorption peak on position not only do not weaken but also obtain after forming hydrogel and strengthen and superposition (1070), describe graft reaction and do not occur on these 2 positions.Because if carboxyethyl group addition, on these 2 C atoms, due to its space steric effect, can weaken C
3-O or C
6the stretching vibration of-O, makes its absorption intensity reduce.Raw materials of chitosan is at 1383 cm
-1acid amides III peak (C-N stretching vibration) be offset to 1323 cm
-1and strength reduction, illustrate and introduce-CH in the molecule of chitosan
2.As can be seen here, there is addition reaction and define CS/AA hydrogel in vinylformic acid and chitosan under glow discharge electrolysis plasma body causes in amino of chitosan.
2, thermogravimetric analysis
Thermostability can show whether material is applicable to many-sided application, now compare the thermogravimetric curve (see figure 2) of CS, cross linked polyacrylate and CS/AA hydrogel composite material, can find out that three kinds of materials have weightless peak near 200 DEG C, this is caused by the removal of physical absorption water and middle water; After this, CS/AA obviously accelerates, this is because CS/AA polymer chain mesochite polysaccharide chains starts fracture between cross-linked acrylic acid and chitosan the weightlessness value of 250 ~ 300 DEG C.The weightless temperature of chitosan, cross-linked acrylic acid and CS/AA 50% is respectively 285,384 and 520 DEG C; Also as can be seen from Fig. 2, CS/AA residual volume 800 DEG C time is maximum simultaneously.These results illustrate, CS adds the thermostability contributing to improving hydrogel, be difficult to decompose, and the envrionment temperature of such materials'use is generally 0 ~ 40 DEG C, can meet general service requirements before 200 DEG C.
3, morphology analysis
Fig. 3 is the scanning electron microscope (a amplifies 2000 times, and b amplifies 10000 times) of CS/AA hydrogel.As can be seen from Figure 3, the surface of CS/AA hydrogel is very coarse, and the cavity having unordered size uneven, these holes being similar to sponge increase the specific surface area of gel, be conducive to water molecules or dye molecule is diffused into gel inside, thus improve the water suction of CS/AA hydrogel, inhale the amount of salt, absorbing dye.
4, water-absorption kinetics test
The water absorbent rate of multifunctional composite is surveyed by weighting method.Testing method is: the material accurately taking certain mass, in beaker, adds distilled water, after making its certain hour that absorbs water (5,10,15,20,30,40,50 min), crosses the water that 200 eye mesh screen eliminations are unnecessary, calculates water absorbent rate by formula (1):
（1）
Wherein,
m 0for the quality (g) of the front dry substance that absorbs water;
m tfor the quality (g) after the certain hour that absorbs water in distilled water.
Fig. 4 is the swelling curve of CS/AA hydrogel composite material.As can be seen from Figure 4, in 10 min, rate of water absorption is very fast, and afterwards along with the increase rate of water absorption of time is slack-off, after 50 min, rate of water absorption tends to be steady substantially, and water absorbent rate reaches about 320 g/g, illustrates that this material has rate of water absorption faster.
5, pH susceptibility
Configure diluted alkaline and the dilute acid soln of 0.1 mol/L respectively with NaOH and HCl, adding distil water dilution makes pH reach 2,3,4,5,6,7,8,9,10,11,12 respectively, and with pH meter Accurate Measurement join the pH value of solution.Accurately take certain mass (
w 1) CS/AA xerogel be placed in different pH solution and make it fully swelling 24 h, cross the water that 200 eye mesh screen eliminations are unnecessary, claim swelling rear hydrogel quality (
w 2), calculate swelling ratio by formula (2):
（2）
In different pH solution, the swelling ratio of hydrogel is different, swelling ratio due to " negative ion " hydrogel is subject to the impact of ionic strength consumingly, thus buffered soln is not used in this experiment, but with distilled water respectively dilute hydrochloric acid (pH=1.0) and NaOH(pH=13.0) solution, reach the pH value of required solution.
Fig. 5 is that hydrogel is in different pH(1 ~ 13) swelling ratio in solution.As seen from Figure 5, when pH value is 6, the swelling of hydrogel reaches maximum, is 340g/g.At acid ph value (pH<4), most of carboxyl is protonated, and hydrophobic interaction is occupied an leading position.This is because on the one hand, hydroxyl, interaction of hydrogen bond between carboxyl and amino are strengthened, and create extra physical crosslinking effect.Therefore, three-dimensional network is tending towards shrinking and subsiding, and swelling ratio declines.In pH neutral (6 ~ 9), carboxyl starts ionization, and interaction of hydrogen bond is broken, and electrostatic repulsion increases, and hydrogel network structure is expanded, and swelling ratio increases.In strong base solution (pH value > 10) swelling ratio decline mainly due to unnecessary sodium ion " electron screening effect " caused by, this shielding effect protects-COO
-, effectively prevent the electrostatic repulsion between negatively charged ion.
6, reversible swelling behavior
Because CS/AA hydrogel shows different swelling behaviors in different pH solution, therefore, have studied swelling and deswelling (switching over) behavior that this material is reversible in the solution of pH=6 and pH=2, the results are shown in Figure 6.Can find out, hydrogel sample reaches balance through certain water absorption and swelling time in the solution of pH=6, and after filtering, this hydrogel joins in the solution of pH=2, starts to shrink and reach balance in the short period of time.This is due to when pH=6, the electrostatic repulsion between negatively charged ion, and three-dimensional net structure is expanded, and hydrogel starts swelling; And when pH=2 ,-COO
-protonation and hydrogen bond action gel volume was shunk in several minutes.This swelling and deswelling behavior is expected to the Co ntrolled release making gel for medicine.
Experiment also proves, CS/AA hydrogel has pH susceptibility and reversible swelling behavior, and after swelling deswelling repeats 3 times, water regain still remains unchanged substantially, illustrates that this material has swelling function repeatedly, namely absorb water-releases water-absorb water again, therefore reusable edible.
7, different salt concn is on the impact of gel swelling behavior
Ionic strength also can affect the Swelling Capacity of hydrogel.Accurately take certain mass (
w 1) CS/AA xerogel be placed in various salts and make it fully swelling, cross the water that 200 eye mesh screen eliminations are unnecessary, claim swelling rear hydrogel quality (
w 2), calculate the swelling ratio in salts solution by formula (2).Fig. 7 is the swelling behavior curve of CS/AA hydrogel in different salt.Fig. 7 shows, in various salts, the swelling ratio of hydrogel reduces with the increase of concentration of salt solution (0.001 ~ 0.15 mol/L), this is because along with the increase of external solution concentration, caused by the permeable pressure head between hydrogel and external solution declines.In addition, cationic charge shielding effect is another factor affecting hydrogel Swelling Capacity in salts solution, and positively charged ion shielding effect, once occur, will stop the electrostatic repulsion between negatively charged ion-negatively charged ion.Can also find from Fig. 7, in the various salts of same concentrations, the swelling ratio of hydrogel is different, and in 0.15 mol/L solution saline solutions, swelling ratio from being up to minimum order is:
K
+> Na
+ > Mg
2+> Ca
2+>Fe
3+
This is because Mg
2+, Ca
2+, Fe
3+intermolecular and molecule inner complex can be formed with the carboxyl on hydrogel chain, hydroxyl ,-NH-, cause hydrogel deswelling and volumetric shrinkage; Moreover, the anionic sites in hydrogel chain and polyvalent cation (Mg
2+, Ca
2+, Fe
3+) between the electrostatic attraction that increases the ionomer degree of hydrogel can be caused to increase, and then make gel rigidity reinforced, swelling behavior forfeiture.
8, the absorption behavior in methylene blue (MB) solution
Accurately take 0.065 g CS/AA in 250 mL Erlenmeyer flasks, add the methylene blue solution of 1000 mg/L of 200 mL pH=5.7, in 120 r/min vibrations in the constant temperature oscillation case of 25 DEG C, (5,10,15,20,25,30,40,50,60,90,120,150,180,240,300 min) accurate 5 mL supernatant liquors that take out (then add 5 mL distilled water in Erlenmeyer flask at regular intervals, keep the constancy of volume of solution), filter, measure on ultraviolet spectrophotometer after filtrate dilution, each sample repeats 3 times, average, adsorptive capacity (
q)calculate by formula (3):
（3）
Wherein,
qthe adsorptive capacity (mg/g0 of MB;
c 0with
cthe concentration (mg/L) of dye solution before and after absorption;
vliquor capacity (L),
mit is the quality (g) of xerogel used.
Fig. 8 be in different time CS/AA on the impact of MG adsorptive capacity.Can find out, CS/AA increases rapidly to the adsorptive capacity of MB dyestuff in 60 min, and afterwards, adsorptive capacity change is less.Thus CS/AA can be divided into 2 stages to the adsorption process of MB, is the quick adsorption stage within 60 min, and 60 min are absorption phase at a slow speed later, substantially reach adsorption equilibrium after 3 h.Maximal absorptive capacity after its 3 h is 1602 mg/g.
9, GDEP Initiating polymerization mechanism
In aqueous, GDEP produces HO, H, HO
2, H
2o
2contour active particle, these particles can cause unusual solution chemistry reaction.When CS and AA exists in solution, they can as the trapping agent of HO and H, and triggering mechanism is as follows:
(1) formation of free radical; (2) chain causes; (3) chainpropagation; (4) chain termination; (5) part COOH is neutralized
Originally, water molecules obtains sufficiently high energy and forms the free radicals such as HO (reaction 1) from plasma body; Then the further attack of high energy HO CS and AA forms new CS(a) free radical and AA(b) free radical, cause the initiation (reaction 2) of polymeric chain.From the infrared spectra of hydrogel, graft copolymerization occurs in the-NH of chitosan
2above form free radical (a).GDEP polymerizing acrylamide triggered and cause double bond containing lipid acid occur in aqueous simultaneously hydroxylation, hydration and hydrogenation time all find, initiated polymerization is Radical Addition, HO adds on hydrogeneous more carbon atom, thus is conducive to the formation of free radical (b).Then these new free radicals (a, b) become free radical contributor and are supplied to adjacent monomer molecule, cause the growth of chain to form free radical (c, d) (reaction 3), because the life-span of HO is extremely short, are only 10
-9s, and surrounded by monomer, corresponding monomer radical can only be formed in the short period of time.In addition, acrylate homopolymer also may be formed, but final under linking agent effect equal polyradical, copolymerization free radical jointly form CS/AA hydrogel and cause polymerization end stopping of chain (reacting 4).Finally make degree of neutralization reach 90% with the COOH in 0.1mol/L NaOH and in polymer chain, what just can obtain part neutralization has COO
?, COOH, NH and OH group hydrogel (reaction 5).
In sum, hinge structure of the present invention has the following advantages:
1, the present invention is with chitosan and vinylformic acid for raw material, and N, N'-methylene-bisacrylamide is linking agent, utilize glow discharge electrolysis plasma-initiated polymerization, a step has obtained chitosan/acrylic hydrogel matrix material, and its raw material is easy to get, preparation technology is simple, and reaction conditions gentleness is (without the need to N
2), energy consumption is low, cost is low;
2, the present invention does not need to add initiator, reacts the advantages such as controlled, non-secondary pollution, is that a green meeting " Sustainable development " causes new synthesis technology.
3, the whole preparation process of the present invention is carried out completely in acetic acid solution, simplify the technique of CS/AA material Enrichment purification, decrease the pollution of emulsifying agent to material, improve the purity of CS/AA material, enhance CS/AA material biological safety, thus expanded the application of CS/AA material: can be used for agricultural, gardening, environment, medicine and other fields.
4, chitosan/acrylic hydrogel matrix material that prepared by the present invention has rate of water absorption, higher dye adsorption amount, good salt resistant character and reusing faster, because of but a kind of composite absorbent material of excellent performance.
5, chitosan/acrylic hydrogel matrix material thermostability of preparing of this law is higher, and be difficult to decompose before 200 DEG C, and the envrionment temperature of such materials'use is generally 0 ~ 40 DEG C, thus the scope of application is wider.
Accompanying drawing explanation
Fig. 1 is vinylformic acid (a), chitosan (b), the FT-IR spectrum of chitosan/acrylic hydrogel (c);
Fig. 2 is the TG curve of chitosan (a), cross linked polyacrylate (b) and chitosan/acrylic hydrogel (c);
Fig. 3 is the SEM pattern of chitosan/polyacrylic acid hydrogel;
Fig. 4 is the swelling curve of CS/AA hydrogel composite material;
Fig. 5 is the influence curve of pH to the behavior of CS/AA swelling behavior;
Fig. 6 is the switch swelling behavior curve of CS/AA hydrogel in the solution of pH=6 and pH=2;
Fig. 7 is the swelling behavior curve of CS/AA hydrogel in different salt;
Fig. 8 is the impact of time on CS/AA absorbing dye.
Embodiment
Below in conjunction with specific embodiment, the preparation method of CS/AA hydrogel of the present invention and performance thereof are described further.
Experimental installation comprises high-voltage power supply and reactor.The voltage range of LW100J1 DC current regulator power supply (power friend, Shanghai) is 0 ~ 1000 V, and range of current is 0 ~ 1 A.Reactor is formed by being equipped with the platinum filament anode of diameter 0.3 ~ 0.7 mm, the stainless steel cathode of diameter 4 ~ 8 mm and the there-necked flask of reflux condensing tube.The degree of depth of anode and cathode immersed in liquid level is 6 ~ 12 mm, and the distance between two electrodes is 10 ~ 20 mm, and reactor puts into the oil bath of temperature-controllable, puts into magnetic stir bar and mix to keep solution in there-necked flask.
Embodiment 1
The acetic acid solution of the mass percent 2% of 0.2 g CS, 0.07g MBA and 35 mL is added in the there-necked flask of 250 mL, 70 DEG C of stirrings make mixture dissolve thoroughly, add 12 mL AA, continue stirring 10 min, switch on power, carry out glow discharge 5 min in 600 V, 43 mA, electric current reduces to 14 Am; Stop electric discharge, after continuing to stir 3 ~ 4 h in 75 DEG C of oil baths, be cooled to room temperature, obtain g., jelly-like gel; Take out product, shred to about 2 ~ 5 mm, make degree of neutralization reach 90% with NaOH neutralization; Remove unreacted raw material with water, ethanol repetitive scrubbing, finally 50 DEG C of vacuum-dryings, obtain CS/PAA hydrogel, pulverize, cross 100 mesh sieves, namely obtain CS/AA matrix material, productive rate 53%.
Performance index are as follows:
The amount of inhaling distilled water during 10 min is about 233 g/g, and the amount of maximum suction distilled water is 250 g/g, and the water suction in the sodium chloride solution of 0.1 mol/L is 115 g/g.Be 1843 mg/g to the adsorptive capacity of methylene blue.
Embodiment 2
0.3 g CS, 0.07 g MBA and 40mL mass percent 1% acetic acid is added in 250 mL there-necked flasks, about 75 DEG C stirrings make mixture dissolve thoroughly, then add 9mL AA and, continue to stir 15min, switch on power, the 3 min after-currents that discharge under voltage 600 V, electric current 49 mA reduce to 11 mA, stop electric discharge, continue to stir 3 ~ 4 h (post polymerization) at 75 DEG C, be cooled to room temperature, obtain g., jelly-like gel; Take out product, cut the fragment for diameter about 2 ~ 5 mm, then make degree of neutralization reach 90% with 0.1 mol/L NaOH neutralization; Products in water, ethanol repetitive scrubbing remove unreacted raw material, 50 DEG C of vacuum-dryings to constant weight, namely obtain CS/PAA hydrogel, after pulverizing 100 mesh sieves, obtain oyster white matrix material, productive rate 49%.
Performance index are as follows:
The amount of inhaling distilled water during 10 min is about 294.9 g/g, and inhale distilled water during 50 min and substantially reach saturated, the amount of maximum suction distilled water is 323 g/g; Water suction in the sodium chloride solution of 0.1 mol/L is 125 g/g; Be 1859 mg/g to the adsorptive capacity of methylene blue.
Embodiment 3
The acetic acid solution of 0.4 g CS, 0.14 g MBA and 35 mL mass percents 5% is added in the there-necked flask of 250 mL, 80 DEG C of stirrings make mixture dissolve thoroughly, add 10 mL AA and continue stirring 10 min, insert two electrodes and switch on power, carrying out glow discharge 4.5min electric current in 600 V, 49 mA and reduce to 4 Am; Stop electric discharge, after continuing to stir 3 ~ 4 h in 75 DEG C of oil baths, be cooled to room temperature, take out product, shred to about 2 ~ 5 mm, make degree of neutralization reach 90% with NaOH neutralization.Remove unreacted raw material with water, ethanol repetitive scrubbing, finally 50 DEG C of vacuum-dryings, namely obtain CS/PAA hydrogel; Pulverize, after crossing 100 mesh sieves, namely obtain CS/AA matrix material, productive rate 51%.
Performance index are as follows:
The amount of inhaling distilled water during 10 min is about 245 g/g, and inhale distilled water during 50 min and substantially reach saturated, the amount of maximum suction distilled water is 262 g/g; Water regain in the sodium chloride solution of 0.1 mol/L is 118 g/g; Be 1842 mg/g to the adsorptive capacity of methylene blue.
Claims (5)
1. utilize glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, for raw material with chitosan and vinylformic acid, with N, N'-methylene-bisacrylamide is linking agent, utilize glow discharge electrolysis plasma body initiated polymerization in acetic acid aqueous solution, a step obtains chitosan/vinylformic acid matrix material; Concrete technology is: chitosan and linking agent are fully dissolved in acetic acid aqueous solution, add vinylformic acid, stirs 10 ~ 30 min in 60 ~ 90 DEG C; Under voltage 550 ~ 650 V, electric current 65 ~ 40 mA, falling electric current after glow discharge 2 ~ 8 min is again 10 below mA, stops electric discharge; Continue stirring 3 ~ 5 h, be cooled to room temperature, obtain g., jelly-like gel; Being shredded by g., jelly-like gel to diameter is the fragment of 2 ~ 5 mm, then is neutralized to degree of neutralization by NaOH solution and reaches 60% ~ 90%, then removes unreacted monomer by water, washing with alcohol, dry, obtains chitosan/acrylic hydrogel; Pulverize, cross 100 mesh sieves, obtain chitosan/vinylformic acid xerogel matrix material.
2. utilize glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material as claimed in claim 1, it is characterized in that: described chitosan and acrylic acid mass ratio are 1:20 ~ 1:3.
3. utilize glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material as claimed in claim 1, it is characterized in that: the mass ratio of described linking agent and chitosan is 1:1 ~ 1:6.
4. utilize glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material as claimed in claim 1, it is characterized in that: the mass percent of described acetic acid aqueous solution is 1% ~ 5%.
5. utilize glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material as claimed in claim 1, it is characterized in that: described drying is vacuum-drying at 40 ~ 70 DEG C.
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