CN115537030A - Preparation of hydrophilic chitosan compound solution and application of hydrophilic chitosan compound solution in liquid mulching film - Google Patents
Preparation of hydrophilic chitosan compound solution and application of hydrophilic chitosan compound solution in liquid mulching film Download PDFInfo
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- CN115537030A CN115537030A CN202211181468.6A CN202211181468A CN115537030A CN 115537030 A CN115537030 A CN 115537030A CN 202211181468 A CN202211181468 A CN 202211181468A CN 115537030 A CN115537030 A CN 115537030A
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- chitosan
- urea
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- polyvinyl alcohol
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 112
- 150000001875 compounds Chemical class 0.000 title abstract description 20
- 239000007788 liquid Substances 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004471 Glycine Substances 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- 108010010803 Gelatin Proteins 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 9
- 229920000159 gelatin Polymers 0.000 claims abstract description 9
- 239000008273 gelatin Substances 0.000 claims abstract description 9
- 235000019322 gelatine Nutrition 0.000 claims abstract description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 9
- 235000011187 glycerol Nutrition 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- KKUGLUXXIGKECX-ODZAUARKSA-N (z)-but-2-enedioic acid;urea Chemical compound NC(N)=O.OC(=O)\C=C/C(O)=O KKUGLUXXIGKECX-ODZAUARKSA-N 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002689 soil Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 238000001556 precipitation Methods 0.000 description 17
- 229960000583 acetic acid Drugs 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0262—Mulches, i.e. covering material not-pre-formed in mats or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/52—Mulches
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
Abstract
The invention relates to the technical field of agriculture and forestry, and discloses a preparation method of a hydrophilic chitosan compound solution and application of the hydrophilic chitosan compound solution in a liquid mulching film, wherein maleic anhydride and hydroxymethyl of urea-based chitosan are subjected to esterification reaction, and further subjected to addition reaction with glycine in a sodium hydroxide system to obtain carboxyl-urea-based chitosan, glutaraldehyde is taken as a cross-linking agent and is subjected to chemical cross-linking with polyvinyl alcohol to obtain hydrophilic polyvinyl alcohol grafted chitosan, and the hydrophilic grafted chitosan is compounded with film forming additives of glycerol, carboxymethyl cellulose and gelatin to obtain the hydrophilic chitosan compound solution; the chitosan composite membrane contains hydrophilic amino and urea groups, so that the hydrophilicity, the water absorption rate and the water retention property are enhanced, and the soil is beneficial to moisture retention; the chitosan and polyvinyl alcohol containing structure is easy to biodegrade, is green and pollution-free, and has wide application prospect in the aspects of mulching film materials, soil water retention agents, soil conditioners and the like.
Description
Technical Field
The invention relates to the technical field of agriculture and forestry, in particular to a hydrophilic chitosan compound solution.
Background
The mulching film is widely applied in agriculture and forestry, and has wide application in aspects of agriculture and forestry water conservation, soil water retention and moisture preservation, economic crop growth promotion, ecological management and the like, the most used mulching film is the polyethylene plastic mulching film at present, but the polyethylene plastic mulching film is difficult to degrade and causes serious white pollution, and the residual polyethylene mulching film loses the soil structure and the fertility, so that the development of novel degradable liquid mulching films becomes a research trend, such as mulching film materials of cellulose, chitosan, polylactic acid and the like.
As a biodegradable biomass resource with good biocompatibility, the chitosan has important application in the fields of mulching film materials, seed coating agents, soil improvement, environmental protection and the like, improves the hydrophilicity and the film forming property of the chitosan and the mechanical strength of film materials thereof, and can effectively expand the development and application of the chitosan materials in the aspects of mulching film materials, soil water-retaining agents, soil conditioners and the like.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hydrophilic chitosan compound solution which is applied to the field of liquid mulching films and improves the hydrophilicity, water retention and mechanical strength of chitosan film materials.
(II) technical scheme
In order to realize the purpose, the invention provides the following technical scheme: a hydrophilic chitosan complex solution prepared by the following steps:
s1, adding chitosan and urea into an acetic acid solution, uniformly stirring, then dropwise adding a potassium persulfate solution and a sodium bisulfite solution into a nitrogen atmosphere, and stirring for reaction to obtain urea-based chitosan; and then dissolving urea-based chitosan into N, N-dimethylformamide, uniformly stirring, adding maleic anhydride and 4-dimethylaminopyridine, reacting for 3-8h at 80-110 ℃ in a nitrogen atmosphere, adding acetone for precipitation after reaction, filtering, and washing with acetone and ethanol in sequence to obtain the maleate-urea-based chitosan.
S2, adding maleate-urea chitosan into a sodium hydroxide solution, then adding glycine and an ethanol solvent, reacting at 40-55 ℃ for 12-36h, dropwise adding dilute hydrochloric acid after the reaction until the pH value of the solution is 4-5, uniformly stirring, adding ethanol for precipitation, filtering the solvent, and washing with ethanol to obtain the carboxyl-urea chitosan.
And S3, heating, stirring and dissolving the polyvinyl alcohol and the carboxyl-urea-based chitosan, then dropwise adding a glutaraldehyde aqueous solution, stirring and reacting at 30-45 ℃ for 6-18h, adding ethanol for precipitation after reaction, filtering a solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
And S4, mixing the polyvinyl alcohol grafted chitosan, glycerol, carboxymethyl cellulose and gelatin with 0.2-0.5% of acetic acid solution according to the mass ratio of 1.24-0.6.
Preferably, the mass ratio of the urea-based chitosan, the maleic anhydride and the 4-dimethylaminopyridine in the step (1) is 1.5-4.
Preferably, the mass fraction of the sodium hydroxide solution in the step (2) is 1-3%.
Preferably, in the step (2), the mass ratio of the maleate to the urea-based chitosan to the glycine is 1.
Preferably, the mass fraction of the aqueous solution of glutaraldehyde in (3) is 3-8%.
Preferably, the mass ratio of the polyvinyl alcohol to the carboxyl-urea-based chitosan in the step (3) is 0.1-0.3.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
reacting urea with amino of chitosan to obtain urea-based chitosan with high substitution degree; then 4-dimethylamino pyridine is used as a catalyst, and maleic anhydride and hydroxymethyl of urea chitosan are subjected to esterification reaction to obtain maleate-urea chitosan; in a sodium hydroxide system, alkenyl and glycine are subjected to addition reaction to obtain carboxyl-urea chitosan, so that rich hydrophilic carboxyl and urea groups are introduced into a side chain of chitosan, glutaraldehyde is taken as a cross-linking agent to be chemically cross-linked with polyvinyl alcohol to obtain hydrophilic polyvinyl alcohol grafted chitosan, and the hydrophilic chitosan grafted chitosan is compounded with film-forming additives such as glycerol, carboxymethyl cellulose and gelatin to obtain a hydrophilic chitosan compound solution.
Detailed Description
The urea-based chitosan is prepared by referring to Master thesis, preparation of novel chitosan urea derivatives and research on antioxidant activity thereof: dissolving 2g of chitosan into 1% glacial acetic acid solution, stirring the solvent, adding 2.2g of urea, dropwise adding a solution of 0.8% of potassium persulfate and 0.026% of sodium bisulfite in a nitrogen atmosphere, reacting for 5 hours at 70 ℃, dropwise adding a sodium hydroxide solution after reaction for neutralizing and precipitating, filtering, and washing with ethanol and distilled water to obtain urea-based chitosan;
example 1
S1, dissolving 2g of urea-based chitosan into 50mL of N, N-dimethylformamide, uniformly stirring, adding 3g of maleic anhydride and 0.08g of 4-dimethylaminopyridine, reacting for 8 hours at 100 ℃ in a nitrogen atmosphere, adding acetone for precipitation after reaction, filtering, and washing with acetone and ethanol in sequence to obtain maleate-urea-based chitosan;
s2, adding 1g of maleic acid into 20mL of 2% sodium hydroxide solutionEster-urea chitosan, then 2g of glycine and 20mL of ethanol solvent are added, the mixture reacts for 24 hours at the temperature of 45 ℃, dilute hydrochloric acid is added dropwise after the reaction until the pH value of the solution is 4, the mixture is stirred uniformly, ethanol is added for precipitation, the solvent is filtered, and the ethanol is washed, so that carboxyl-urea chitosan is obtained;
and S3, heating, stirring and dissolving 0.4g of polyvinyl alcohol and 4g of carboxyl-urea chitosan, then dropwise adding 5mL of 3% glutaraldehyde aqueous solution, stirring and reacting at 45 ℃ for 12 hours, adding ethanol for precipitation after reaction, filtering the solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
S4, mixing 20g of polyvinyl alcohol grafted chitosan, 6.5g of glycerol, 2g of carboxymethyl cellulose and 1.2g of gelatin with 300mL of 0.2% acetic acid solution, and stirring and dissolving to obtain a hydrophilic chitosan compound solution.
Example 2
S1, dissolving 2g of urea-based chitosan into 100mL of N, N-dimethylformamide, uniformly stirring, adding 6.2g of maleic anhydride and 0.1g of 4-dimethylaminopyridine, reacting at 80 ℃ for 8 hours in a nitrogen atmosphere, adding acetone after reacting, precipitating, filtering, and washing with acetone and ethanol in sequence to obtain the maleate-urea-based chitosan.
S2, adding 1g of maleate-urea-based chitosan into 30mL of 2% sodium hydroxide solution, then adding 3.5g of glycine and 30mL of ethanol solvent, reacting at 55 ℃ for 12h, dropwise adding dilute hydrochloric acid until the pH value of the solution is 5, stirring uniformly, adding ethanol for precipitation, filtering the solvent, and washing with ethanol to obtain the carboxyl-urea-based chitosan.
And S3, heating, stirring and dissolving 0.8g of polyvinyl alcohol and 4g of carboxyl-urea chitosan, then dropwise adding 5mL of 4% glutaraldehyde aqueous solution, stirring and reacting at 40 ℃ for 12 hours, adding ethanol for precipitation after reaction, filtering the solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
S4, mixing 20g of polyvinyl alcohol grafted chitosan, 4.8g of glycerol, 3.5g of carboxymethyl cellulose and 1.3g of gelatin with 500mL of 0.5% acetic acid solution, and stirring and dissolving to obtain a hydrophilic chitosan compound solution.
Example 3
S1, dissolving 2g of urea-based chitosan into 100mL of N, N-dimethylformamide, uniformly stirring, adding 4.8g of maleic anhydride and 0.16g of 4-dimethylaminopyridine, reacting at 110 ℃ for 5 hours in a nitrogen atmosphere, adding acetone for precipitation after reaction, filtering, and washing with acetone and ethanol in sequence to obtain the maleate-urea-based chitosan.
S2, adding 1g of maleate-urea chitosan into 25mL of 1% sodium hydroxide solution, then adding 3g of glycine and 25mL of ethanol solvent, reacting at 55 ℃ for 24h, dropwise adding dilute hydrochloric acid after reaction until the pH value of the solution is 4, uniformly stirring, adding ethanol for precipitation, filtering the solvent, and washing with ethanol to obtain the carboxyl-urea chitosan.
And S3, heating, stirring and dissolving 1g of polyvinyl alcohol and 4g of carboxyl-urea chitosan, then dropwise adding 4mL of 5% glutaraldehyde aqueous solution, stirring and reacting at 30 ℃ for 18h, adding ethanol for precipitation after reaction, filtering a solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
S4, mixing 20g of polyvinyl alcohol grafted chitosan, 4.8g of glycerol, 6g of carboxymethyl cellulose, 1.6g of gelatin and 1000mL of 0.2% acetic acid solution, and stirring for dissolving to obtain a hydrophilic chitosan compound solution.
Example 4
S1, dissolving 2g of urea-based chitosan into 80mL of N, N-dimethylformamide, uniformly stirring, adding 5.6g of maleic anhydride and 0.08g of 4-dimethylaminopyridine, reacting at 90 ℃ for 8h in a nitrogen atmosphere, adding acetone for precipitation after reaction, filtering, and washing with acetone and ethanol in sequence to obtain the maleate-urea-based chitosan.
S2, adding 1g of maleate-urea chitosan into 30mL of 1% sodium hydroxide solution, then adding 6g of glycine and 30mL of ethanol solvent, reacting at 55 ℃ for 12h, dropwise adding dilute hydrochloric acid after reaction until the pH value of the solution is 5, uniformly stirring, adding ethanol for precipitation, filtering the solvent, and washing with ethanol to obtain the carboxyl-urea chitosan.
S3, heating, stirring and dissolving 1.2g of polyvinyl alcohol and 4g of carboxyl-urea chitosan, then dropwise adding 2mL of 5% glutaraldehyde aqueous solution, stirring and reacting at 40 ℃ for 12 hours, adding ethanol for precipitation after reaction, filtering a solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
S4, mixing 20g of polyvinyl alcohol grafted chitosan, 12g of glycerol, 2.8g of carboxymethyl cellulose and 1.6g of gelatin with 800mL of 0.3% acetic acid solution, and stirring for dissolving to obtain a hydrophilic chitosan compound solution.
Example 5
S1, dissolving 2g of urea-based chitosan into 100mL of N, N-dimethylformamide, uniformly stirring, adding 8g of maleic anhydride and 0.16g of 4-dimethylaminopyridine, reacting for 8 hours at 80 ℃ in a nitrogen atmosphere, adding acetone after reaction for precipitation, filtering, and washing with acetone and ethanol in sequence to obtain the maleate-urea-based chitosan.
S2, adding 1g of maleate-urea chitosan into 30mL of 2% sodium hydroxide solution, then adding 5g of glycine and 30mL of ethanol solvent, reacting at 55 ℃ for 36h, dropwise adding dilute hydrochloric acid after reaction until the pH value of the solution is 4, uniformly stirring, adding ethanol for precipitation, filtering the solvent, and washing with ethanol to obtain the carboxyl-urea chitosan.
And S3, heating, stirring and dissolving 1g of polyvinyl alcohol and 4g of carboxyl-urea chitosan, then dropwise adding 2mL of 8% glutaraldehyde aqueous solution, stirring and reacting at 45 ℃ for 6 hours, adding ethanol for precipitation after reaction, filtering a solvent, and washing with ethanol to obtain the hydrophilic polyvinyl alcohol grafted chitosan.
S4, mixing 20g of polyvinyl alcohol grafted chitosan, 10g of glycerol, 4.5g of carboxymethyl cellulose and 1.5g of gelatin with 500mL of 0.3% acetic acid solution, and stirring for dissolving to obtain a hydrophilic chitosan compound solution.
Casting the hydrophilic chitosan composite solution on the surface of a glass plate and drying to form a film, preparing a film sample with the thickness of 120mm multiplied by 30mm multiplied by 0.4mm, and testing the tensile strength by adopting a tensile testing machine, wherein the tensile rate is 50mm/min.
And (2) drying the hydrophilic chitosan compound solution to remove water, then weighing 0.20g of the hydrophilic chitosan compound solution, adding the hydrophilic chitosan compound solution into 500mL of distilled water to swell for 12 hours, taking out the hydrophilic chitosan compound solution after swelling, draining residual water, weighing, and measuring the water absorption rate, wherein the water absorption rate is = (mass after water absorption-mass before water absorption) ÷ mass before water absorption).
Casting hydrophilic chitosan compound solution on the surface of a glass plate, drying to form a film, preparing a square film sample, randomly taking 1000g of agricultural soil, crushing, sieving, adding 200mL of distilled water, adding 1.0g of film sample, uniformly mixing, spraying 10mL of distilled water every 10 days, standing for 90 days to simulate degradation, taking out the undegraded film sample, cleaning the residual soil, drying, weighing, and determining the degradation rate.
Degradation rate = (mass before degradation-mass after degradation) ÷ mass before degradation.
Claims (6)
1. A hydrophilic chitosan complex solution, comprising: the hydrophilic chitosan complex solution is prepared by the following steps:
s1, adding chitosan and urea into an acetic acid solution, uniformly stirring, then dropwise adding a potassium persulfate solution and a sodium bisulfite solution in a nitrogen atmosphere, and stirring for reaction to obtain urea-based chitosan; dissolving urea-based chitosan into N, N-dimethylformamide, uniformly stirring, adding maleic anhydride and 4-dimethylaminopyridine, reacting for 3-8 hours at 80-110 ℃ in a nitrogen atmosphere, precipitating after reaction, filtering, and washing to obtain maleate-urea-based chitosan;
s2, adding maleate-urea-based chitosan into a sodium hydroxide solution, then adding glycine and an ethanol solvent, reacting at 40-55 ℃ for 12-36h, dropwise adding dilute hydrochloric acid after the reaction until the pH value of the solution is 4-5, uniformly stirring, precipitating, filtering and washing to obtain carboxyl-urea-based chitosan;
s3, heating, stirring and dissolving polyvinyl alcohol and carboxyl-urea chitosan, then dropwise adding a glutaraldehyde aqueous solution, stirring and reacting at 30-45 ℃ for 6-18h, precipitating after reaction, filtering and washing to obtain hydrophilic polyvinyl alcohol grafted chitosan;
and S4, mixing the polyvinyl alcohol grafted chitosan, glycerol, carboxymethyl cellulose and gelatin with 0.2-0.5% of acetic acid solution according to the mass ratio of 1.24-0.6.
2. The hydrophilic chitosan complex solution of claim 1, wherein: in the step (1), the mass ratio of urea-based chitosan, maleic anhydride and 4-dimethylaminopyridine is 1.5-4.
3. The hydrophilic chitosan complex solution of claim 1, wherein: the mass fraction of the sodium hydroxide solution in the step (2) is 1-3%.
4. The hydrophilic chitosan complex solution of claim 1, wherein: and (3) adding maleic acid ester-urea chitosan in the step (2), and then adding glycine in a mass ratio of 1.
5. The hydrophilic chitosan complex solution of claim 1, wherein: the mass fraction of the aqueous solution of glutaraldehyde in (3) is 3-8%.
6. The hydrophilic chitosan complex solution of claim 1, wherein: the mass ratio of the polyvinyl alcohol to the carboxyl-urea chitosan in the step (3) is 0.1-0.3.
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