CN117549392A - Modification method for improving mildew-proof antibacterial property of bamboo wood - Google Patents
Modification method for improving mildew-proof antibacterial property of bamboo wood Download PDFInfo
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- CN117549392A CN117549392A CN202311731941.8A CN202311731941A CN117549392A CN 117549392 A CN117549392 A CN 117549392A CN 202311731941 A CN202311731941 A CN 202311731941A CN 117549392 A CN117549392 A CN 117549392A
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 310
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 310
- 241001330002 Bambuseae Species 0.000 title claims abstract description 310
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 310
- 239000011425 bamboo Substances 0.000 title claims abstract description 310
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 28
- 238000002715 modification method Methods 0.000 title claims abstract description 16
- 239000002023 wood Substances 0.000 title claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 188
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 122
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229920001661 Chitosan Polymers 0.000 claims abstract description 86
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 82
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 44
- 239000000284 extract Substances 0.000 claims abstract description 38
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 453
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 282
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 150
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 118
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000002904 solvent Substances 0.000 claims description 78
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 65
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 48
- 244000298697 Actinidia deliciosa Species 0.000 claims description 46
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims description 46
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 36
- 238000002791 soaking Methods 0.000 claims description 33
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 5
- 238000003672 processing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229940055350 kiwi fruit extract Drugs 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 241000132012 Atractylodes Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229940068517 fruit extracts Drugs 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K9/00—Chemical or physical treatment of reed, straw, or similar material
- B27K9/002—Cane, bamboo
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/0207—Pretreatment of wood before impregnation
- B27K3/0214—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/04—Impregnating in open tanks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a modification method for improving mildew-proof antibacterial property of bamboo, which comprises the following steps: (1) drying fresh bamboo chips to obtain dried bamboo chips; (2) Coating a chitosan layer on the surface of the bamboo chip, and treating the bamboo chip with a rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to obtain a once treated bamboo chip; (3) Treating with acetone solution of succinic anhydride and ethanol solution of aniline to obtain mildew-proof antibacterial bamboo chip. The bamboo processed by the method has good mildew resistance and corrosion resistance, so that the durability of the bamboo is obviously improved, mildew spots are not easy to generate, and the attractiveness of the bamboo is improved.
Description
Technical Field
The invention relates to the technical field of bamboo processing, in particular to a modification method for improving mildew-proof antibacterial property of bamboo.
Background
Mould microorganisms widely exist in the nature, and the mould microorganisms are tiny in individuals, large in quantity, high in metabolism, fast in propagation and strong in adaptability, and can propagate on the surface of the wood easily when meeting a humid environment and a proper temperature, and various organic acids, hydrolytic enzymes and toxins are produced, so that the wood products are mildewed and spoiled, the usable value of the wood is influenced, the performance of the wood is reduced, and the commodity value of the wood is further seriously reduced. The advantages of mildew-proof wood are numerous. Firstly, the natural property of the wood is well maintained, and the wood is natural, environment-friendly, attractive and safe; secondly, the wood has the advantages of decay resistance, mildew resistance and worm damage resistance, so that the service life of the wood can be prolonged by 3 times generally, and the maximum time can be up to 10 times; thirdly, can satisfy the multiple requirement of design, can all use in house internal and external structure, platform, pier, bridge, railing, outdoor pavement, interior outer wall decoration, landing stage etc. and it is very convenient to make horticulture view work.
For a long time, wood mildew preventive agents mainly comprise sodium pentachlorophenate, are effective in preventing the harm of microorganisms, and belong to broad-spectrum antibacterial agents. But is relatively toxic and has many adverse effects on both humans and the environment. So many processes currently choose to use green plant extracts for mildew proofing of wood.
Disclosure of Invention
Therefore, the invention provides a modification method for improving mildew-proof antibacterial property of bamboo, which comprises the following steps:
(1) Drying the fresh bamboo chips at 90 ℃ until the water content is 5% -8%, and obtaining dried bamboo chips;
(2) Preparing acetic acid solution of chitosan; soaking the dried bamboo chips in citric acid solution for more than 3 hours, taking out the bamboo chips, washing the bamboo chips with deionized water for more than 3 hours, and drying the bamboo chips at 60 ℃ for more than 30 minutes; keeping the temperature of the acetic acid solution of the chitosan in a water bath at 60+/-2 ℃, keeping the temperature, soaking dried bamboo chips in the acetic acid solution of the chitosan at 60+/-2 ℃ for more than 20 minutes, adding glutaraldehyde solution into the solution, continuously stirring the solution at 60+/-2 ℃ for more than 10 minutes after the addition, then adding sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, stirring the solution at 60+/-2 ℃ for more than 30 minutes, adjusting the pH value of the solution to 4.5 by dilute hydrochloric acid, adding rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution in a nitrogen protection atmosphere at 60+/-2 ℃ under the constant temperature condition, continuously stirring the solution at 60+/-2 ℃ for more than 6 hours after the addition, taking out the bamboo chips, washing the bamboo chips with ethanol for more than 2 times, washing deionized water for more than 2 times, and drying the solution at 60 ℃ for more than 30 minutes to obtain once treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride and an ethanol solution of aniline; soaking the once treated bamboo chips in an acetone solution of succinic anhydride, then keeping the temperature of the water bath at a constant temperature of 50 ℃ for more than 3 hours, taking out the bamboo chips, drying the bamboo chips at a temperature of 60 ℃ for more than 30 minutes, soaking the bamboo chips in an ethanol solution of aniline again after drying, stirring the solution for more than 10 minutes, then adding an ammonium persulfate solution into the solution in a stirring state, continuously stirring the solution for more than 3 hours after the addition is finished, taking out the bamboo chips, washing the bamboo chips with ethanol for more than 2 times, washing the bamboo chips with deionized water for more than 2 times, and drying the bamboo chips at a temperature of 60 ℃ for more than 10 hours to obtain the mildew-proof antibacterial bamboo chips.
Further, the preparation method of the Guanzhong atractylodes rhizome-kiwi fruit compound extract comprises the following steps: cutting rhizoma atractylodis leaves and kiwi fruit pulp into rhizoma atractylodis She Suiding and kiwi fruit pieces respectively, mixing the rhizoma atractylodis She Suiding and the kiwi fruit pieces to form a mixture, soaking the mixture in an ethanol water solution, extracting at a constant temperature of 60+/-2 ℃ for 70-80 min in a water bath, then air-cooling to normal temperature, carrying out solid-liquid separation, and concentrating the liquid phase under reduced pressure to obtain the rhizoma atractylodis-kiwi fruit compound extract.
Further, the mixing mass ratio of the rhizoma atractylodis She Suiding to the kiwi fruit dices is the rhizoma atractylodis She Suiding: kiwi fruit dices=1:1-5; the mixture is soaked in ethanol water solution, and the solid-liquid mass ratio of the mixture to the ethanol water solution is 1:20; the volume percentage of the ethanol in the ethanol water solution is 45-50%; the liquid phase was concentrated under reduced pressure to 1/2 of the pre-unconcentrated volume.
Further, in the step (2), the acetic acid solution of chitosan is prepared by mixing chitosan with an aqueous solution of chitosan/acetic acid=1 g:300mL of the solution is dissolved in an acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water.
Further, in the step (2), the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is that the acetic acid solution of the dried bamboo chips/chitosan is=1:30; in the glutaraldehyde solution, the mass percentage of glutaraldehyde is 2%, and the solvent is ethanol; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; in the sodium hydroxide solution, the mass percentage of sodium hydroxide is 5%, and the solvent is water; the mass percentage of the solute in the dilute hydrochloric acid is 5%, and the solvent is water.
Further, the mass ratio of the rhizoma atractylodis-kiwi fruit composite extract to the hydrogen peroxide added to the bamboo chips in the solution is that the rhizoma atractylodis-kiwi fruit composite extract is as follows: hydrogen peroxide: bamboo splints = 6-10:2-5:1; the mass percentage of the solute in the hydrogen peroxide is 20%.
Further, in the step (3), in the acetone solution of the succinic anhydride, the mass percentage of the succinic anhydride is 5%, and the solvent is acetone; in the ethanol solution of the aniline, the mass percentage of the aniline is 30 percent, and the solvent is ethanol; the mass ratio of the primary treated bamboo chips immersed in the acetone solution of the succinic anhydride is that the primary treated bamboo chips: acetone solution of succinic anhydride = 1:50; the dried bamboo chips are soaked in the ethanol solution of the aniline again, and the mass ratio of the dried bamboo chips is as follows: ethanol solution of aniline = 1:50; the concentration of ammonium persulfate in the ammonium persulfate solution is 0.5-0.6 g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo chips=4 to 5:1.
The invention has the beneficial effects that: the bamboo processed by the method has good mildew resistance and corrosion resistance, so that the durability of the bamboo is obviously improved, mildew spots are not easy to generate, and the attractiveness of the bamboo is improved.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
A modification method for improving mildew-proof antibacterial property of bamboo comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the added mass of the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to the bamboo chips in the solution is the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 6:2:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.5g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 4:1; and continuously stirring the solution for 3 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the mildew-proof antibacterial bamboo chips.
The preparation method of the rhizoma atractylodis-kiwi fruit compound extract comprises the following steps: cutting the leaf of rhizoma atractylodis and the pulp of kiwi fruit into pieces of rhizoma atractylodis She Suiding and kiwi fruit respectively, mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into a mixture, and mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into pieces of kiwi fruit according to the mass ratio of rhizoma atractylodis She Suiding: kiwi fruit pieces = 1:1; soaking the mixture in an ethanol water solution, wherein the solid-liquid mass ratio of the mixture to the ethanol water solution is (1:20); the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the final product.
Example 2
A modification method for improving mildew-proof antibacterial property of bamboo comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the added mass of the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to the bamboo chips in the solution is the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 8:3:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.5g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 4:1; and continuously stirring the solution for 3 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the mildew-proof antibacterial bamboo chips.
The preparation method of the rhizoma atractylodis-kiwi fruit compound extract comprises the following steps: cutting the leaf of rhizoma atractylodis and the pulp of kiwi fruit into pieces of rhizoma atractylodis She Suiding and kiwi fruit respectively, mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into a mixture, and mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into pieces of kiwi fruit according to the mass ratio of rhizoma atractylodis She Suiding: kiwi fruit pieces = 1:3; soaking the mixture in an ethanol water solution, wherein the solid-liquid mass ratio of the mixture to the ethanol water solution is (1:20); the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the final product.
Example 3
A modification method for improving mildew-proof antibacterial property of bamboo comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the added mass of the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to the bamboo chips in the solution is the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 8:4:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.6g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 5:1; and continuously stirring the solution for 3 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the mildew-proof antibacterial bamboo chips.
The preparation method of the rhizoma atractylodis-kiwi fruit compound extract comprises the following steps: cutting the leaf of rhizoma atractylodis and the pulp of kiwi fruit into pieces of rhizoma atractylodis She Suiding and kiwi fruit respectively, mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into a mixture, and mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into pieces of kiwi fruit according to the mass ratio of rhizoma atractylodis She Suiding: kiwi fruit pieces = 1:3; soaking the mixture in an ethanol water solution, wherein the solid-liquid mass ratio of the mixture to the ethanol water solution is (1:20); the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the final product.
Example 4
A modification method for improving mildew-proof antibacterial property of bamboo comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the added mass of the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to the bamboo chips in the solution is the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 10:5:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.6g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 5:1; and continuously stirring the solution for 3 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the mildew-proof antibacterial bamboo chips.
The preparation method of the rhizoma atractylodis-kiwi fruit compound extract comprises the following steps: cutting the leaf of rhizoma atractylodis and the pulp of kiwi fruit into pieces of rhizoma atractylodis She Suiding and kiwi fruit respectively, mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into a mixture, and mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into pieces of kiwi fruit according to the mass ratio of rhizoma atractylodis She Suiding: kiwi fruit pieces = 1:5; soaking the mixture in an ethanol water solution, wherein the solid-liquid mass ratio of the mixture to the ethanol water solution is (1:20); the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the final product.
Comparative example 1
A bamboo processing method for comparison comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding rhizoma atractylodis extract and hydrogen peroxide into the solution at a constant temperature of 60+/-2 ℃, wherein the mass ratio of the rhizoma atractylodis extract to the hydrogen peroxide added to the bamboo chips in the solution is as follows: hydrogen peroxide: bamboo splints = 8:4:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.6g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 5:1; and after the addition is finished, continuously stirring the solution for 3 hours, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the bamboo chips finally treated in the comparative example.
The preparation method of the rhizoma atractylodis extract comprises the following steps: cutting rhizoma atractylodis leaves to form rhizoma atractylodis She Suiding, soaking rhizoma atractylodis She Suiding in an ethanol water solution, wherein the solid-liquid mass ratio of rhizoma atractylodis She Suiding in the ethanol water solution is rhizoma atractylodis She Suiding/ethanol water solution=1:20; the volume percentage of ethanol in the ethanol water solution is 45%; extracting in water bath at constant temperature of 60+ -2deg.C for 70min, air cooling to room temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain rhizoma Atractylodis extract.
Comparative example 2
A bamboo processing method for comparison comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the kiwi fruit extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the kiwi fruit extract to the hydrogen peroxide added to the bamboo chips in the solution is that: hydrogen peroxide: bamboo splints = 8:4:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.6g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 5:1; and after the addition is finished, continuously stirring the solution for 3 hours, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the bamboo chips finally treated in the comparative example.
The preparation method of the kiwi fruit extract comprises the following steps: cutting kiwi fruit pulp into kiwi fruit pieces, and soaking the kiwi fruit pieces in an ethanol water solution, wherein the solid-liquid mass ratio of the kiwi fruit pieces to the ethanol water solution is kiwi fruit pieces/ethanol water solution=1:20; the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid and liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the fructus Actinidiae chinensis extract.
Comparative example 3
A bamboo processing method for comparison comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding hydrogen peroxide into the solution at a constant temperature of 60+/-2 ℃, wherein the mass ratio of the hydrogen peroxide to the bamboo chips in the solution is hydrogen peroxide: bamboo splints = 4:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; preparing an ethanol solution of aniline, wherein in the ethanol solution of aniline, the mass percentage of aniline is 30%, and the solvent is ethanol; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, dried for 30 minutes at 60 ℃, then soaked in the ethanol solution of the aniline again, and the dried bamboo chips are soaked in the ethanol solution of the aniline again according to the mass ratio of the bamboo chips: ethanol solution of aniline = 1:50; stirring the solution for 10min, and then adding an ammonium persulfate solution into the solution in a stirring state, wherein the concentration of ammonium persulfate in the ammonium persulfate solution is 0.6g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo splints = 5:1; and after the addition is finished, continuously stirring the solution for 3 hours, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at 60 ℃ for 10 hours to obtain the bamboo chips finally treated in the comparative example.
Comparative example 4
A bamboo processing method for comparison comprises the following steps:
(1) Drying fresh bamboo chips at 90 ℃ until the water content is 5%, and obtaining dried bamboo chips;
(2) Preparing an acetic acid solution of chitosan, wherein the acetic acid solution of chitosan is prepared by mixing chitosan with chitosan/acetic acid water solution=1 g:300mL of the aqueous solution is dissolved in acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water; soaking the dried bamboo chips in a citric acid solution for 3 hours, wherein the concentration of the citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; then taking out the bamboo chips, washing the bamboo chips with deionized water for 3, and drying the bamboo chips at 60 ℃ for 30min; the acetic acid solution of the chitosan is subjected to water bath constant temperature to 60+/-2 ℃ and is subjected to heat preservation, the dried bamboo chips are soaked in the acetic acid solution of the chitosan, and the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is 1:30; soaking for 20min at the constant temperature of 60+/-2 ℃, and then adding glutaraldehyde solution into the solution, wherein the glutaraldehyde solution contains 2% of glutaraldehyde by mass and ethanol as a solvent; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 10min after the addition is finished, then adding a sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, wherein the sodium hydroxide solution comprises 5 mass percent of sodium hydroxide and water as a solvent; stirring the solution at the constant temperature of 60+/-2 ℃ for 30min, and after the stirring is completed, regulating the pH value of the solution to 4.5 by using dilute hydrochloric acid, wherein the mass percentage of solute in the dilute hydrochloric acid is 5%, and the solvent is water; in a nitrogen protection atmosphere, adding the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution at the constant temperature of 60+/-2 ℃, wherein the mass ratio of the added mass of the rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide to the bamboo chips in the solution is the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 8:4:1; the mass percentage of the solute in the hydrogen peroxide is 20%; continuously stirring the solution at the constant temperature of 60+/-2 ℃ for 6 hours after the addition is finished, then taking out the bamboo chips, washing with ethanol for 2 times, washing with deionized water for 2 times, and drying at the temperature of 60 ℃ for 30 minutes to obtain once-treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride, wherein the mass percentage of the succinic anhydride in the acetone solution of the succinic anhydride is 5%, and the solvent is acetone; the primary treated bamboo chips are soaked in the acetone solution of the succinic anhydride, and the mass ratio of the primary treated bamboo chips soaked in the acetone solution of the succinic anhydride is that the primary treated bamboo chips are: acetone solution of succinic anhydride = 1:50; then the water bath is kept at a constant temperature to 50 ℃ for 3 hours, the bamboo chips are taken out, washed with ethanol for 2 times, washed with deionized water for 2 times, and dried at 60 ℃ for 10 hours, and the bamboo chips finally treated in this comparative example are obtained.
The preparation method of the rhizoma atractylodis-kiwi fruit compound extract comprises the following steps: cutting the leaf of rhizoma atractylodis and the pulp of kiwi fruit into pieces of rhizoma atractylodis She Suiding and kiwi fruit respectively, mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into a mixture, and mixing the pieces of rhizoma atractylodis She Suiding and kiwi fruit into pieces of kiwi fruit according to the mass ratio of rhizoma atractylodis She Suiding: kiwi fruit pieces = 1:3; soaking the mixture in an ethanol water solution, wherein the solid-liquid mass ratio of the mixture to the ethanol water solution is (1:20); the volume percentage of ethanol in the ethanol water solution is 45%; extracting at constant temperature of 60+ -2deg.C in water bath for 70min, air cooling to normal temperature, separating solid from liquid, concentrating the liquid phase under reduced pressure to 1/2 of the volume before concentrating to obtain the final product.
Example 5
The bamboo chips treated in each of the above examples and comparative examples and untreated raw bamboo chips were tested for corrosion resistance according to the requirements of standard GB/T13942.1-2009. In addition, the bamboo chips treated by the methods of the examples and the comparative examples and the untreated raw bamboo chips are placed in an open air environment for 30 days, and the surface mildew condition is observed, wherein a grade 0 represents that the surface is free from mildew; grade 1 represents mildew area < 1/4 of the whole area; the level 2 represents that the mildew area is 1/4 to 1/2 of the whole area; the level 3 represents that the mildew area is 1/2-3/4 of the whole area; grade 4 represents mildew area > 3/4 of the overall area; the results are shown in Table 1. As shown in Table 1, the bamboo treated by the method has good mildew resistance and corrosion resistance, so that the durability of the bamboo is obviously improved, mildew spots are not easy to generate, and the attractiveness of the bamboo is improved. The method is mainly characterized in that a mildew-resistant antibacterial chitosan layer is formed on the surface of the treated bamboo chips, active antibacterial groups are formed on the surface of the chitosan, the antibacterial effect of the chitosan is improved, the rhizoma atractylodis and kiwi fruit extracts have a synergistic effect on improving the antibacterial effect, and the modification effect of the composite extract is far better than that of a single extract. In addition, through grafting aniline groups and surface part succinic anhydride acylation treatment, the surface amino groups are easier to form protonated amine, the amino groups are promoted to combine with bacteria or mold lipoprotein, the lipoprotein efficacy is destroyed, and the antibacterial and mildew-proof effects are achieved.
TABLE 1
The foregoing detailed description of the embodiments of the present invention will be provided to those skilled in the art, and the detailed description and the examples should not be construed as limiting the invention.
Claims (7)
1. The modification method for improving the mildew-proof antibacterial property of the bamboo is characterized by comprising the following steps of:
(1) Drying the fresh bamboo chips at 90 ℃ until the water content is 5% -8%, and obtaining dried bamboo chips;
(2) Preparing acetic acid solution of chitosan; soaking the dried bamboo chips in citric acid solution for more than 3 hours, taking out the bamboo chips, washing the bamboo chips with deionized water for more than 3 hours, and drying the bamboo chips at 60 ℃ for more than 30 minutes; keeping the temperature of the acetic acid solution of the chitosan in a water bath at 60+/-2 ℃, keeping the temperature, soaking dried bamboo chips in the acetic acid solution of the chitosan at 60+/-2 ℃ for more than 20 minutes, adding glutaraldehyde solution into the solution, continuously stirring the solution at 60+/-2 ℃ for more than 10 minutes after the addition, then adding sodium hydroxide solution dropwise into the solution to adjust the pH value of the solution to 12, stirring the solution at 60+/-2 ℃ for more than 30 minutes, adjusting the pH value of the solution to 4.5 by dilute hydrochloric acid, adding rhizoma atractylodis-kiwi fruit composite extract and hydrogen peroxide into the solution in a nitrogen protection atmosphere at 60+/-2 ℃ under the constant temperature condition, continuously stirring the solution at 60+/-2 ℃ for more than 6 hours after the addition, taking out the bamboo chips, washing the bamboo chips with ethanol for more than 2 times, washing deionized water for more than 2 times, and drying the solution at 60 ℃ for more than 30 minutes to obtain once treated bamboo chips;
(3) Preparing an acetone solution of succinic anhydride and an ethanol solution of aniline; soaking the once treated bamboo chips in an acetone solution of succinic anhydride, then keeping the temperature of the water bath at a constant temperature of 50 ℃ for more than 3 hours, taking out the bamboo chips, drying the bamboo chips at a temperature of 60 ℃ for more than 30 minutes, soaking the bamboo chips in an ethanol solution of aniline again after drying, stirring the solution for more than 10 minutes, then adding an ammonium persulfate solution into the solution in a stirring state, continuously stirring the solution for more than 3 hours after the addition is finished, taking out the bamboo chips, washing the bamboo chips with ethanol for more than 2 times, washing the bamboo chips with deionized water for more than 2 times, and drying the bamboo chips at a temperature of 60 ℃ for more than 10 hours to obtain the mildew-proof antibacterial bamboo chips.
2. The modification method for improving mildew-proof antibacterial property of bamboo wood according to claim 1, wherein the preparation method of the rhizoma atractylodis-kiwi fruit compound extract is as follows: cutting rhizoma atractylodis leaves and kiwi fruit pulp into rhizoma atractylodis She Suiding and kiwi fruit pieces respectively, mixing the rhizoma atractylodis She Suiding and the kiwi fruit pieces to form a mixture, soaking the mixture in an ethanol water solution, extracting at a constant temperature of 60+/-2 ℃ for 70-80 min in a water bath, then air-cooling to normal temperature, carrying out solid-liquid separation, and concentrating the liquid phase under reduced pressure to obtain the rhizoma atractylodis-kiwi fruit compound extract.
3. The modification method for improving mildew-proof antibacterial property of bamboo wood according to claim 2, wherein the mixing mass ratio of rhizoma atractylodis She Suiding to kiwi fruit dices is rhizoma atractylodis She Suiding: kiwi fruit dices=1:1-5; the mixture is soaked in ethanol water solution, and the solid-liquid mass ratio of the mixture to the ethanol water solution is 1:20; the volume percentage of the ethanol in the ethanol water solution is 45-50%; the liquid phase was concentrated under reduced pressure to 1/2 of the pre-unconcentrated volume.
4. The modification method for improving mildew-proof antibacterial property of bamboo wood according to claim 2, wherein in the step (2), the acetic acid solution of chitosan is prepared by mixing chitosan with an aqueous solution of chitosan/acetic acid=1g: 300mL of the solution is dissolved in an acetic acid aqueous solution, wherein the mass percentage of acetic acid in the acetic acid aqueous solution is 2%, and the solvent is water.
5. The modification method for improving mildew-proof antibacterial property of bamboo wood according to claim 2, wherein in the step (2), the concentration of citric acid in the citric acid solution is 1mol/L, and the solvent is water; the mass ratio of the dried bamboo chips immersed in the citric acid solution is that the dried bamboo chips/the citric acid solution=1:50; the mass ratio of the dried bamboo chips to the acetic acid solution of the chitosan is that the acetic acid solution of the dried bamboo chips/chitosan is=1:30; in the glutaraldehyde solution, the mass percentage of glutaraldehyde is 2%, and the solvent is ethanol; the mass ratio of glutaraldehyde solution to bamboo chips immersed in acetic acid solution of chitosan is glutaraldehyde solution: bamboo splints = 5:1; in the sodium hydroxide solution, the mass percentage of sodium hydroxide is 5%, and the solvent is water; the mass percentage of the solute in the dilute hydrochloric acid is 5%, and the solvent is water.
6. The modification method for improving mildew-proof antibacterial property of bamboo wood according to claim 2, wherein the mass ratio of the rhizoma atractylodis-kiwi fruit composite extract to the hydrogen peroxide added to the bamboo chips in the solution is that the rhizoma atractylodis-kiwi fruit composite extract: hydrogen peroxide: bamboo splints = 6-10:2-5:1; the mass percentage of the solute in the hydrogen peroxide is 20%.
7. The modification method for improving mildew-proof antibacterial property of bamboo according to claim 2, wherein in the step (3), the mass percentage of succinic anhydride in the acetone solution of succinic anhydride is 5%, and the solvent is acetone; in the ethanol solution of the aniline, the mass percentage of the aniline is 30 percent, and the solvent is ethanol; the mass ratio of the primary treated bamboo chips immersed in the acetone solution of the succinic anhydride is that the primary treated bamboo chips: acetone solution of succinic anhydride = 1:50; the dried bamboo chips are soaked in the ethanol solution of the aniline again, and the mass ratio of the dried bamboo chips is as follows: ethanol solution of aniline = 1:50; the concentration of ammonium persulfate in the ammonium persulfate solution is 0.5-0.6 g/L, and the solvent is water; the mass ratio of the ammonium persulfate solution to the bamboo chips in the solution is that: bamboo chips=4 to 5:1.
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