CN102977271A - 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, relate in particular to a kind of method of utilizing the glow discharge electrolysis plasma body to cause synthetic chitosan/acrylic hydrogel.
Background technology
Chitosan (Chitosan; CS) be a kind of natural cationic high molecular polymer that chitin obtains through deacetylation; by glucosamine unit and 2-Acetamido-2-deoxy-D-glucose unit, formed; it is the alkaline polysaccharide of the unique a large amount of existence of nature; not only source is abundant, and has good histocompatibility, biodegradability and adhesion.Yet the free amine group in chitosan molecule can be accepted the proton salify, in acidic solution, can dissolve, cause loss, seriously limited its application.Therefore, improving acid resistance is one of focus of current chitin modified research.
Hydroxyl and amino abundant on the chitosan molecule chain make it be easy to carry out chemically modified; as introduced stimuli responsive type polymkeric substance or small molecules after acidylate, carboxylation and hydroxylation modification; give structure and performance that chitosan is new; it is become by natural polysaccharide and the molecular intelligent macromolecule hydrogel with three-dimensional net structure of synthetic high score; greatly improve the water-soluble and moisture retention of chitosan, and changed 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 at aspects such as health care, agriculture and garden, sewage purification, biomaterials.Up to now, the main preparation methods of chitosan-based hydrogel has chemical initiation method, radiation to cause method and light-initiated method, has also occurred some reports that cause about microwave recently.
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 the glow discharge electrolysis process is obviously different from common electrolysis, and the chemical reaction that in the proposition aqueous solution such as Hickling, glow discharge electrolysis causes is:
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 converted has substantially exceeded the value of calculating gained by faraday's electric weight.As the Ce such as Sengupta
3+draw and often by 1 mol electronics, in the liquid phase reaction district, generate the approximately OH of 12 mol while making OH trapping agent research glow discharge electrolysis, far surpassed the output of calculating by Faraday's law.Because OH has very high activity, can with the acrylic acid pair of key, chitosan molecule chain in the aqueous solution on the reactions such as amino form free radical, finally under the linking agent effect, obtain the CS/AA hydrogel.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the glow discharge electrolysis plasma-initiated polymerization to prepare chitosan/vinylformic acid matrix material.
The present invention utilizes the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, that to take chitosan and vinylformic acid be raw material, with N, the N'-methylene-bisacrylamide is linking agent, utilize glow discharge electrolysis plasma body initiated polymerization in acetic acid aqueous solution, a step makes chitosan/vinylformic acid matrix material.
Its concrete technology is: chitosan and linking agent fully are dissolved in acetic acid aqueous solution, add vinylformic acid, in 60 ~ 90 ℃, stir 10 ~ 30 min; Falling electric current after glow discharge 2 ~ 6 min again under voltage 550 ~ 650 V, electric current 65 ~ 40 mA is below 10 mA, stops electric discharge; Continue to stir 3 ~ 5 h, be cooled to room temperature, obtain jelly shape gel; By the jelly shape gel fragment that to shred to diameter be 2 ~ 5 mm, then be neutralized to degree of neutralization with NaOH solution and reach 60% ~ 90%, then water, washing with alcohol are removed unreacted monomer, and drying 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 40 ~ 70 ℃ of lower vacuum-dryings.
Below by infrared spectra, thermogravimetric analysis, scanning electron microscope, water-absorbent test, salt tolerance test, the structure of multifunctional composite prepared the present invention by pH sensitivity tests, absorbing dye methylene blue, pattern, performance are carried out analytic explanation.
1, infrared spectra
The infrared spectra that Fig. 1 is 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 the C=C of place disappears, 1706 cm
-1the absorption peak of the C=O of place is shifted 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 shows on acrylic acid pair of key and chitosan-NH
2addition reaction has occurred in group.Moreover, after the formation hydrogel 1571 cm two new characteristic peaks appearred,
-1with 1410 cm
-1, they are respectively-COO
-asymmetrical stretching vibration peak and symmetrical stretching vibration peak.Chitosan C
3-OH(1090) and C6-OH(1030) C on position-O stretching vibration absorption peak forms after hydrogel and not only do not weaken but also obtained strengthening and stack (1070), illustrated that graft reaction does not occur on these 2 positions.Because if the addition of propyloic group, on these 2 C atoms, due to its space steric effect, can weaken C
3-O or C
6the stretching vibration of-O, reduce its absorption intensity.Raw materials of chitosan is at 1383 cm
-1acid amides III peak (C-N stretching vibration) be offset to 1323 cm
-1and strength reduction, introduced-CH is described in the molecule of chitosan
2.As can be seen here, addition reaction occurs and has formed the CS/AA hydrogel in vinylformic acid and chitosan under the glow discharge electrolysis plasma body causes on 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 ℃, this is by due to the removal of physical absorption water and middle water; After this, CS/AA accelerates between cross-linked acrylic acid and chitosan and obviously the weightlessness value of 250 ~ 300 ℃, and this is because CS/AA polymer chain mesochite polysaccharide chains starts fracture.The weightless temperature of chitosan, cross-linked acrylic acid and CS/AA 50% is respectively 285,384 and 520 ℃; From Fig. 2, also can find out, CS/AA is the residual volume maximum in the time of 800 ℃ simultaneously.These presentation of results, CS adds the thermostability that contributes to improve hydrogel, before 200 ℃, be difficult to decompose, and the envrionment temperature of such materials'use is generally 0 ~ 40 ℃, can meet general service requirements.
3, morphology analysis
The scanning electron microscope that Fig. 3 is the CS/AA hydrogel (a amplifies 2000 times, and b amplifies 10000 times).As can be seen from Figure 3, the surface of CS/AA hydrogel is very coarse, and the inhomogeneous cavity of unordered size is arranged, these holes that are similar to sponge have increased the specific surface area of gel, be conducive to water molecules or dye molecule and be diffused into gel inside, thereby improve the water suction of CS/AA hydrogel, the amount of inhaling salt, absorbing dye.
4, water suction kinetic test
Survey the water absorbent rate of multifunctional composite by weighting method.Testing method is: accurately take the material of certain mass in beaker, add distilled water, after making its water suction certain hour (5,10,15,20,30,40,50 min), cross the unnecessary water of 200 eye mesh screen elimination, by formula (1), calculate water absorbent rate:
Wherein,
m 0quality (g) for the front dry substance that absorbs water;
m tfor the quality (g) after water suction certain hour in distilled water.
The swelling curve that Fig. 4 is the CS/AA hydrogel composite material.As can be seen from Figure 4, in 10 min, rate of water absorption is very fast, and 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 afterwards, and water absorbent rate reaches 320 g/g left and right, illustrates that this material has rate of water absorption faster.
5, pH susceptibility
Configure respectively diluted alkaline and the dilute acid soln of 0.1 mol/L with NaOH and HCl, adding distil water dilution makes pH reach respectively 2,3,4,5,6,7,8,9,10,11,12, and by the pH value of pH meter solution that Accurate Measurement is joined.Accurately take certain mass (
w 1) the CS/AA xerogel be placed in different pH solution and make it abundant swelling 24 h, cross the unnecessary water of 200 eye mesh screen elimination, claim hydrogel after swelling quality (
w 2), calculate swelling ratio by formula (2):
The swelling ratio difference of hydrogel in different pH solution, because the swelling ratio of " negative ion " hydrogel is subject to the impact of ionic strength consumingly, thereby do not use buffered soln 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, it is maximum that the swelling that is 6 o'clock hydrogels in the pH value reaches, and is 340g/g.In acid ph value (pH<4), most of carboxyls are by protonated, and hydrophobic interaction is occupied an leading position.This is that the interaction of hydrogen bond between hydroxyl, carboxyl and amino is strengthened, and has produced extra physical crosslinking effect because on the one hand.Therefore, three-dimensional network is tending towards shrinking and subsiding, and swelling ratio descends.In pH neutral (6 ~ 9), carboxyl starts ionization, and interaction of hydrogen bond is broken, and electrostatic repulsion increases, the expansion of hydrogel network structure, and swelling ratio increases.In strong base solution, (pH value>10) swelling ratio descends mainly due to due to unnecessary sodium ion " electron screening effect ", protected-COO of this shielding effect
-, effectively stoped the electrostatic repulsion between negatively charged ion.
6, reversible swelling behavior
Because the CS/AA hydrogel shows different swelling behaviors in different pH solution, therefore, studied reversible swelling and deswelling (switching over) behavior in the solution of pH=6 and pH=2 of this material, the results are shown in Figure 6.Can find out, the hydrogel sample water absorption and swelling time that process is certain in the solution of pH=6 also reaches balance, 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 the pH=6, and the electrostatic repulsion between negatively charged ion makes the three-dimensional net structure expansion, 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 are expected to make gel to discharge for the control of medicine.
Experiment is proof also, and the CS/AA hydrogel has pH susceptibility and reversible swelling behavior, and after the swelling deswelling repeats 3 times, water regain still remains unchanged substantially, illustrates that this material has swelling function repeatedly, absorb water-releases water-absorb water again so reusable edible.
7, the impact of different salt concn on the gel swelling behavior
Ionic strength also can affect the swelling ability of hydrogel.Accurately take certain mass (
w 1) the CS/AA xerogel be placed in various salts and make it abundant swelling, cross the unnecessary water of 200 eye mesh screen elimination, claim hydrogel after swelling 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), and this is because along with the increase of external solution concentration, due to the permeable pressure head between hydrogel and external solution descends.In addition, the cationic charge shielding effect is another factor that affects hydrogel swelling ability in salts solution, once the appearance of positively charged ion shielding effect will stop the electrostatic repulsion between negatively charged ion-negatively charged ion.From Fig. 7, can also find, the swelling ratio difference of hydrogel in the various salts of same concentrations, in 0.15 mol/L solution salt solution, 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+can with the hydrogel chain on carboxyl, hydroxyl ,-NH-forms intermolecular and molecule inner complex, causes the hydrogel deswelling and volumetric shrinkage; Moreover, the anionic sites in the hydrogel chain and polyvalent cation (Mg
2+, Ca
2+, Fe
3+) between the electrostatic attraction that increases can cause the ionomer degree of hydrogel to increase, and then make the gel rigidity reinforced, swelling behavior is lost.
8, the absorption behavior in methylene blue (MB) solution
Accurately take 0.065 g CS/AA in 250 mL Erlenmeyer flasks, the methylene blue solution that adds 1000 mg/L of 200 mL pH=5.7, in the constant temperature oscillation case of 25 ℃, in 120 r/min, vibrate, (5,10,15,20,25,30,40,50,60,90,120,150,180,240,300 min) accurately takes out 5 mL supernatant liquors and (then adds 5 mL distilled water in Erlenmeyer flask at regular intervals, the constancy of volume that keeps solution), filter, after the filtrate dilution, on ultraviolet spectrophotometer, measure, each sample repeats 3 times, average, adsorptive capacity (
q)by formula (3), calculate:
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 is the impact of CS/AA on the MG adsorptive capacity in different time.Can find out, CS/AA increases rapidly the adsorptive capacity of MB dyestuff in 60 min, and afterwards, adsorptive capacity changes less.Thereby CS/AA can be divided into 2 stages to the adsorption process of MB, it is the quick adsorption stage that 60 min be take interior, 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 the aqueous solution, GDEP produces HO, H, HO
2, H
2o
2contour active particle, these particles can cause unusual solution chemistry reaction.When CS and AA exist in solution, they can be used 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) neutralization part COOH
Originally, water molecules obtains sufficiently high energy and forms the free radicals (reacting 1) such as HO from plasma body; Then the further attack CS of high energy HO and AA form new CS(a) free radical and AA(b) free radical, cause the initiation (reacting 2) of polymeric chain.From the infrared spectra of hydrogel, graft copolymerization occur in chitosan-NH
2above form free radical (a).Polymerizing acrylamide triggered and cause when double bond containing lipid acid, in the aqueous solution, hydroxylation, hydration and hydrogenation occur simultaneously and all find at GDEP, initiated polymerization is Radical Addition, HO adds on hydrogeneous more carbon atom, thereby is conducive to the formation of free radical (b).Then these new free radicals (a, b) become the free radical contributor and offer adjacent monomer molecule, cause the growth of chain to form free radical (c, d) (reacting 3), because the life-span of HO is extremely short, are only 10
-9s, and surrounded by monomer, corresponding monomer free radical can only be formed in the short period of time.In addition, acrylate homopolymer also may form, but finally under the linking agent effect, all polyradical, copolymerization free radical jointly form the CS/AA hydrogel and cause polymerization end stopping of chain (reacting 4).Finally with in 0.1mol/L NaOH and the COOH in polymer chain make degree of neutralization reach 90%, just can obtain the COO that has that part neutralizes
, COOH, NH and OH group hydrogel (reacting 5).
In sum, the relative prior art of the present invention has the following advantages:
1, to take chitosan and vinylformic acid be raw material in the present invention, N, and the N'-methylene-bisacrylamide is linking agent, utilize the glow discharge electrolysis plasma-initiated polymerization, a step has made chitosan/acrylic hydrogel matrix material, and its raw material is easy to get, preparation technology is simple, and reaction conditions is gentle (without 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 that meets " Sustainable development " causes new synthesis technology.
3, the whole preparation process of the present invention is carried out fully in acetic acid solution, simplified the technique that the enrichment of CS/AA material is purified, reduced the pollution of emulsifying agent to material, improved the purity of CS/AA material, strengthen CS/AA material biological safety, thereby expanded the application of CS/AA material: can be used for agricultural, gardening, environment, medicine and other fields.
4, the chitosan that prepared by the present invention/acrylic hydrogel matrix material has rate of water absorption, higher dye adsorption amount, good salt resistant character and reusing faster, thereby is a kind of composite absorbent material of excellent performance.
5, the chitosan that prepared by this law/acrylic hydrogel matrix material thermostability is higher, before 200 ℃, be difficult to decompose, and the envrionment temperature of such materials'use is generally 0 ~ 40 ℃, thereby the scope of application is wider.
The accompanying drawing explanation
Fig. 1 is vinylformic acid (a), chitosan (b), the FT-IR spectrum of chitosan/acrylic hydrogel (c);
The TG curve that Fig. 2 is chitosan (a), cross linked polyacrylate (b) and chitosan/acrylic hydrogel (c);
The SEM pattern that Fig. 3 is chitosan/polyacrylic acid hydrogel;
The swelling curve that Fig. 4 is the 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 the CS/AA absorbing dye.
Embodiment
Preparation method and performance thereof below in conjunction with specific embodiment to CS/AA hydrogel of the present invention 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 consists of the stainless steel cathode of the platinum filament anode that diameter 0.3 ~ 0.7 mm is housed, 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 is put into the controlled oil bath of temperature, puts into magnetic stir bar in there-necked flask to keep solution to mix.
The acetic acid solution that adds the mass percent 2% of 0.2 g CS, 0.07g MBA and 35 mL in the there-necked flask of 250 mL, 70 ℃ of stirrings are dissolved thoroughly mixture, add 12 mL AA, continue to stir 10 min, switch on power, carry out glow discharge 5 min in 600 V, 43 mA, electric current is reduced to 14 Am; Stop electric discharge, after continuing to stir 3 ~ 4 h in 75 ℃ of oil baths, be cooled to room temperature, obtain jelly shape gel; Take out product, shred to about 2 ~ 5 mm, with the NaOH neutralization, make degree of neutralization reach 90%; Water, ethanol repetitive scrubbing are removed unreacted raw material, finally, 50 ℃ of vacuum-dryings, obtain the CS/PAA hydrogel, pulverize, and cross 100 mesh sieves, obtain the 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 maximum amount of inhaling distilled water is 250 g/g, and the water suction in the sodium chloride solution of 0.1 mol/L is 115 g/g.Adsorptive capacity to methylene blue is 1843 mg/g.
Add 0.3 g CS, 0.07 g MBA and 40mL mass percent 1% acetic acid in 250 mL there-necked flasks, 75 ℃ of left and right are stirred mixture are dissolved thoroughly, then add 9mL AA and, continue to stir 15min, switch on power, under voltage 600 V, electric current 49 mA, electric discharge 3 min after-currents are reduced to 11 mA, stop electric discharge, continuation is stirred 3 ~ 4 h (post polymerization) at 75 ℃, is cooled to room temperature, obtains jelly shape gel; Take out product, cut the fragment into diameter 2 ~ 5 mm, then make degree of neutralization reach 90% with 0.1 mol/L NaOH neutralization; Product water, ethanol repetitive scrubbing are removed unreacted raw material, 50 ℃ of vacuum-dryings, to constant weight, obtain the CS/PAA hydrogel, after pulverizing 100 mesh sieves, obtain the 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, inhales distilled water during 50 min and substantially reaches saturatedly, and maximum amount of inhaling distilled water is 323 g/g; Water suction in the sodium chloride solution of 0.1 mol/L is 125 g/g; Adsorptive capacity to methylene blue is 1859 mg/g.
Embodiment 3
The acetic acid solution that adds 0.4 g CS, 0.14 g MBA and 35 mL mass percents 5% in the there-necked flask of 250 mL, 80 ℃ of stirrings are dissolved thoroughly mixture, add 10 mL AA to continue to stir 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 ℃ of oil baths, be cooled to room temperature, take out product, shred to about 2 ~ 5 mm, with the NaOH neutralization, make degree of neutralization reach 90%.Water, ethanol repetitive scrubbing are removed unreacted raw material, finally, 50 ℃ of vacuum-dryings, obtain the CS/PAA hydrogel; Pulverize, after crossing 100 mesh sieves, obtain the 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, inhales distilled water during 50 min and substantially reaches saturatedly, and maximum amount of inhaling distilled water is 262 g/g; Water regain in the sodium chloride solution of 0.1 mol/L is 118 g/g; Adsorptive capacity to methylene blue is 1842 mg/g.
Claims (6)
1. utilize the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, that to take chitosan and vinylformic acid be raw material, with N, the N'-methylene-bisacrylamide is linking agent, utilize glow discharge electrolysis plasma body initiated polymerization in acetic acid aqueous solution, a step makes chitosan/vinylformic acid matrix material.
2. utilize as claimed in claim 1 the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, it is characterized in that: by chitosan and linking agent, fully be dissolved in acetic acid aqueous solution, add vinylformic acid, in 60 ~ 90 ℃, stir 10 ~ 30 min; Falling electric current after glow discharge 2 ~ 8 min again under voltage 550 ~ 650 V, electric current 65 ~ 40 mA is below 10 mA, stops electric discharge; Continue to stir 3 ~ 5 h, be cooled to room temperature, obtain jelly shape gel; By the jelly shape gel fragment that to shred to diameter be 2 ~ 5 mm, then be neutralized to degree of neutralization with NaOH solution and reach 60% ~ 90%, then water, washing with alcohol are removed unreacted monomer, and drying obtains chitosan/acrylic hydrogel; Pulverize, cross 100 mesh sieves, obtain chitosan/vinylformic acid xerogel matrix material.
3. utilize as claimed in claim 1 or 2 the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, it is characterized in that: described chitosan and acrylic acid mass ratio are 1:20 ~ 1:3.
4. utilize as claimed in claim 1 or 2 the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, it is characterized in that: the mass ratio of described linking agent and chitosan is 1:1 ~ 1:6.
5. utilize as claimed in claim 1 or 2 the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, it is characterized in that: the mass percent of described acetic acid aqueous solution is 1% ~ 5%.
6. utilize as claimed in claim 1 the glow discharge electrolysis plasma-initiated polymerization to prepare the method for chitosan/vinylformic acid matrix material, it is characterized in that: described drying is 40 ~ 70 ℃ of lower vacuum-dryings.
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| CN113842507A (en) * | 2021-07-19 | 2021-12-28 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
| CN113842507B (en) * | 2021-07-19 | 2022-04-29 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
| WO2023000713A1 (en) * | 2021-07-19 | 2023-01-26 | 浙江大学 | Strong-adhesive polyelectrolyte hydrogel coating and preparation method therefor |
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