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CN120859006A - All-carbon-based bamboo mildew preventive and preparation method and application thereof - Google Patents

All-carbon-based bamboo mildew preventive and preparation method and application thereof

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Publication number
CN120859006A
CN120859006A CN202511034527.0A CN202511034527A CN120859006A CN 120859006 A CN120859006 A CN 120859006A CN 202511034527 A CN202511034527 A CN 202511034527A CN 120859006 A CN120859006 A CN 120859006A
Authority
CN
China
Prior art keywords
nitrogen
quantum dots
carbon quantum
doped carbon
bamboo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202511034527.0A
Other languages
Chinese (zh)
Inventor
陶祖起
朱愿
唐明宇
庞祥超
陶玉婷
吴东城
李晓静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Mingyang Zhuyong Technology Co ltd
Central South University of Forestry and Technology
Original Assignee
Hunan Mingyang Zhuyong Technology Co ltd
Central South University of Forestry and Technology
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Filing date
Publication date
Application filed by Hunan Mingyang Zhuyong Technology Co ltd, Central South University of Forestry and Technology filed Critical Hunan Mingyang Zhuyong Technology Co ltd
Priority to CN202511034527.0A priority Critical patent/CN120859006A/en
Publication of CN120859006A publication Critical patent/CN120859006A/en
Pending legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • 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
    • 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/20—Removing fungi, molds or insects

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Forests & Forestry (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本发明公开了一种全碳基竹材防霉剂及其制备方法和应用，全碳基竹材防霉剂原料包括氮掺杂碳量子点和有机杀菌剂，有机杀菌剂通过共价键和非共价键与氮掺杂碳量子点表面的极性基团相作用而负载于氮掺杂碳量子点的表面，氮掺杂碳量子点和有机杀菌剂的质量比为1:10～20。一方面，氮掺杂碳量子点和有机杀菌剂具有高效协同，提升防治效率的功效，因为氮掺杂碳量子点本身具有一定的抑菌活性，与有机防霉剂形成协同增效作用，能使得单位体积内的有效防霉成分浓度更高、作用更全面。另一方面，氮掺杂碳量子点具有超强渗透性，有利于实现深度防护，能够以更低的药剂载入量达到更优的防霉效果，防治效率显著提升。This invention discloses a fully carbon-based bamboo antifungal agent, its preparation method, and its application. The raw materials for the fully carbon-based bamboo antifungal agent include nitrogen-doped carbon quantum dots and an organic bactericide. The organic bactericide is loaded onto the surface of the nitrogen-doped carbon quantum dots by covalent and non-covalent bonds interacting with the polar groups on the surface of the nitrogen-doped carbon quantum dots. The mass ratio of nitrogen-doped carbon quantum dots to organic bactericide is 1:10-20. On one hand, nitrogen-doped carbon quantum dots and organic bactericide have a highly synergistic effect, improving the control efficiency. This is because nitrogen-doped carbon quantum dots themselves have certain antibacterial activity, forming a synergistic effect with the organic antifungal agent, resulting in a higher concentration of effective antifungal components per unit volume and a more comprehensive effect. On the other hand, nitrogen-doped carbon quantum dots have strong permeability, which is beneficial for achieving deep protection, enabling better antifungal effects with lower agent loading, and significantly improving control efficiency.

Description

All-carbon-based bamboo mildew preventive and preparation method and application thereof
Technical Field
The invention relates to the technical field of bamboo protection, in particular to an all-carbon-based bamboo mildew preventive, and a preparation method and application thereof.
Background
Bamboo is widely used as a renewable resource which grows rapidly by virtue of high strength, high toughness and good processability. However, bamboo is rich in nutrients and porous in structure, and is extremely susceptible to bioerosion such as mold. Under the condition of proper temperature and humidity, mould grows rapidly to cause mould spots on the surface, so that the appearance quality and commercial value are seriously damaged, and even the structural performance is influenced. Therefore, the implementation of effective mildew-proof treatment is a key for guaranteeing long-term application of bamboo.
At present, mildew prevention mainly depends on two physical and chemical methods. The physical method (such as heat treatment) has high energy consumption, and the mildew-proof effect is reduced when the treated bamboo absorbs moisture again. Chemical mildewcides are most widely used and are often applied by dipping or the like, such as organic phosphorus, organic iodine, quaternary ammonium salts, and the like. However, the traditional chemical mildew preventive has the obvious defects that firstly, the environment and health risks are caused, part of highly toxic medicaments possibly pollute the environment and harm the health, and the environment-friendly requirement is difficult to meet, secondly, the anti-loss property is poor, a plurality of water-soluble medicaments are easy to lose in a damp and hot environment, so that the effectiveness is weakened, secondary pollution is caused, thirdly, the penetration depth is limited, particularly for high-density bamboo, the medicaments are difficult to penetrate, the protection is limited on the surface layer, and fourthly, the color, smell or mechanical property of the bamboo can be changed.
Researchers are exploring green mildewcides, but often have poor efficacy, poor stability, high volatility or fast loss, and difficulty in providing long-term protection. Therefore, development of novel treatment technology is needed in the bamboo mildew prevention field, so that the defects of traditional medicaments can be overcome, high permeability, excellent anti-loss performance and high-efficiency mildew prevention are realized, and the environment protection of materials and processes can be ensured.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing an all-carbon-based bamboo mildew preventive with good mildew prevention effect and anti-loss, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The raw materials of the all-carbon-based bamboo mildew preventive comprise nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:10-20.
As a further improvement to the above technical solution:
The organic bactericide comprises, by weight, 10-15 parts of isothiazolinone derivatives, 10-15 parts of epoxiconazole, 3-5 parts of penflufen, 1-3 parts of silane coupling agents, 15-25 parts of phenoxyethanol, 15-20 parts of dipropylene glycol methyl ether and 30-40 parts of surfactants.
The surfactant comprises at least one of alkylphenol ethoxylates and alkyl sulfonates.
Preferably, the particle size of the nitrogen-doped carbon quantum dots is 2-10 nm, so that the nitrogen-doped carbon quantum dots can smoothly penetrate through the microstructure of bamboo.
Preferably, the isothiazolinone derivative comprises at least one of N-octyl-4-isothiazolin-3-one or N-butyl-1, 2-benzisothiazolin-3-one.
The invention further provides a preparation method of the all-carbon-based bamboo mildew preventive, which comprises the following steps of mixing nitrogen-doped carbon quantum dots with an organic bactericide according to a mass ratio of 1:10-20, and carrying out stirring reaction at a temperature of 40-60 ℃ to enable organic bactericide molecules to be loaded on the surfaces of the nitrogen-doped carbon quantum dots, so that the all-carbon-based bamboo mildew preventive is obtained.
As a further improvement to the above technical solution:
The stirring speed of the stirring reaction is 1200-3000 rpm, and the reaction time is 30-60 min.
The preparation of the nitrogen-doped carbon quantum dots comprises the following steps:
taking chitosan quaternary ammonium salt as a carbon source to carry out hydrothermal reaction at the temperature of 150-200 ℃ to obtain a crude product;
Centrifuging the crude product, and dialyzing and purifying the supernatant to obtain a purified solution;
and freeze-drying the purified solution to obtain the nitrogen-doped carbon quantum dots.
The invention selects the organic green mildew preventive as a main carrier, prepares the nitrogen-doped carbon quantum dot by taking biomass (chitosan quaternary ammonium salt) as a raw material, and the whole treatment system is nontoxic and biodegradable. The treatment process does not use toxic and harmful chemicals, the treated bamboo products are safe and environment-friendly, the severe requirements of high-end markets on health and environment protection are met, and the added value and market competitiveness of the products are improved. The nitrogen-doped carbon quantum dot structurally contains quaternary ammonium salt groups, and has a certain bactericidal property compared with other nitrogen-doped carbon quantum dots structurally containing nitrogen.
The hydrothermal reaction time is 10-15 h.
Preferably, the chitosan quaternary ammonium salt is 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan), and the quaternary ammonium salt structure can impart excellent antibacterial activity to the final product.
Preferably, the centrifugal force is 13,000~18,000 rpm when the centrifugal force is applied, and the molecular weight cut-off is less than 1 kDa when the dialysis is purified.
Preferably, the preparation of the organic bactericide comprises the following steps of stirring and emulsifying all raw materials of the organic bactericide until the raw materials are clear and transparent, and obtaining the water-soluble organic mildew inhibitor.
As a general inventive concept, the invention also provides application of the all-carbon-based bamboo mildew preventive in bamboo mildew preventive treatment.
The application comprises the following steps of placing bamboo to be treated in the full-carbon-based bamboo mildew preventive, and fully penetrating the full-carbon-based bamboo mildew preventive into the bamboo by adopting normal pressure soaking, vacuum soaking or vacuum-pressure soaking technology, drying and curing to obtain the bamboo after mildew prevention treatment.
Comprising at least one of scheme A and scheme B:
scheme a when a vacuum-pressure impregnation process is used, comprising the steps of:
Firstly, vacuumizing an impregnating tank filled with bamboo to-0.05 to-0.08 MPa, maintaining the pressure for 30-60 minutes, injecting a full-carbon-based bamboo mildew preventive, and maintaining the pressure for 1-2 hours under the pressure of 1.5-2.0 MPa. According to the invention, the nitrogen-doped carbon quantum dots (the nitrogen-doped carbon quantum dots are of nano-scale size and have excellent surface activity) are used as carriers, the extremely small size of the nitrogen-doped carbon quantum dots can easily penetrate through the high-density structure and microscopic pores of the bamboo, and the organic mildew preventive is conveyed to the deep inside the bamboo through the synergistic effect of the vacuum-pressurizing process and the small-size penetration of the nitrogen-doped carbon quantum dots, so that the limitation that the traditional medicament can only act on the surface layer is overcome, and the three-dimensional and deep protection from the surface to the inside is realized.
And the scheme B comprises the following steps of drying the bamboo at the temperature of 60-80 ℃ to enable the nitrogen-doped carbon quantum dots and the organic bactericide in the all-carbon-based bamboo mildew inhibitor to be deposited and cured on the inner walls (such as cell cavities and ducts) of microscopic holes of the bamboo (the nitrogen-doped carbon quantum dots and the organic bactericide in the all-carbon-based bamboo mildew inhibitor form firm physical adsorption or chemical bonding with a bamboo matrix, so that in-situ fixation of the mildew inhibitor is realized) until the moisture content of the bamboo reaches a target value.
Preferably, in the scheme B, the target value is 8% -14%.
Compared with the prior art, the invention has the beneficial effects that:
The all-carbon-based bamboo mildew preventive comprises nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the action of covalent bonds and non-covalent bonds and polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:10-20. On one hand, the nitrogen-doped carbon quantum dots and the organic bactericide have the effects of high efficiency and improving the control efficiency, and because the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups on the molecular structure, the nitrogen-doped carbon quantum dots have certain antibacterial activity, and form a synergistic effect with the organic mildew inhibitor, the concentration of effective mildew-proof components in unit volume is higher, and the effect is more comprehensive. On the other hand, the nitrogen-doped carbon quantum dot has super-strong permeability, is favorable for realizing deep protection, can achieve better mildew-proof effect with lower medicament loading amount, and remarkably improves the prevention and treatment efficiency.
The application of the all-carbon-based bamboo mildew preventive in the bamboo mildew prevention treatment is based on the fact that the organic mildew preventive is coupled to the surface of the nitrogen-doped carbon quantum dot, the organic mildew preventive is promoted to be firmly combined with a bamboo matrix through a drying and curing stage, the dissolution rate and the loss rate of the mildew preventive in a damp and hot environment are remarkably reduced, the durability of the mildew preventive effect is guaranteed, and secondary environmental pollution caused by medicament loss is avoided.
Detailed Description
The present invention will be described in further detail below. The instruments or materials used in the present invention are commercially available unless otherwise specified.
Example 1
The raw materials of the all-carbon-based bamboo mildew preventive comprise nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the action of covalent bonds and non-covalent bonds on polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in the molecular structure, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:10.
The preparation method of the all-carbon-based bamboo mildew preventive comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts, 12 parts of isothiazolinone derivative (N-octyl-4-isothiazolin-3-ketone in the embodiment, N-butyl-1, 2-benzisothiazolin-3-ketone in other embodiments), 14 parts of epoxiconazole, 5 parts of penflufen, 1 part of KH-550 type silane coupling agent, 18 parts of phenoxyethanol, 18 parts of dipropylene glycol methyl ether and 32 parts of alkylphenol polyoxyethylene. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive from step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 of 80 g is slowly added into a kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated in impregnation equipment, starting a vacuum pump to vacuum to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo wood mildew preventive under vacuum until the plates are completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the finished product of the all-carbon-based bamboo wood mildew preventive, closing a vacuum system, applying pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Example 2
The raw materials of the all-carbon-based bamboo mildew preventive comprise nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:15.
The preparation method of the all-carbon-based bamboo mildew preventive is approximately the same as that of the embodiment 1, and is different in that the mass ratio of the nitrogen-doped carbon quantum dots to the mildew preventive mother solution is 1:15, and comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (N-octyl-4-isothiazolin-3-ketone in the embodiment), 12 parts of epoxiconazole, 3 parts of penflufen, 3 parts of KH-550 type silane coupling agent, 17 parts of phenoxyethanol, 15 parts of dipropylene glycol methyl ether and 40 parts of alkylphenol polyoxyethylene ether. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive from step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 of 53.3 g is slowly added into the kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Example 3
The raw materials of the all-carbon-based bamboo mildew preventive comprise nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:20.
The preparation method of the all-carbon-based bamboo mildew preventive is approximately the same as that of the embodiment 1, and is different in that the mass ratio of the nitrogen-doped carbon quantum dots to the mildew preventive mother solution is 1:20, and comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (n-butyl-1, 2-benzisothiazolin-3-one in the embodiment), 10 parts of epoxiconazole, 3 parts of penflufen, 2 parts of KH-550 type silane coupling agent, 20 parts of phenoxyethanol, 19 parts of dipropylene glycol methyl ether and 36 parts of alkylphenol ethoxylate. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive from step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 of 40 g is slowly added into a kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 1
The all-carbon-based bamboo mildew preventive comprises raw materials including nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:8.
The preparation method of the all-carbon-based bamboo mildew preventive of the comparative example is approximately the same as that of the embodiment 3, and is different in that the mass ratio of the nitrogen-doped carbon quantum dots to the organic mildew preventive is 1:8, and the preparation method comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (n-butyl-1, 2-benzisothiazolin-3-one in the embodiment), 10 parts of epoxiconazole, 3 parts of penflufen, 2 parts of KH-550 type silane coupling agent, 20 parts of phenoxyethanol, 19 parts of dipropylene glycol methyl ether and 36 parts of alkylphenol ethoxylate. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8kg of the mother liquor of the mildew preventive from step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 of 100 g is slowly added into a kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 2
The all-carbon-based bamboo mildew preventive comprises raw materials including nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:25.
The preparation method of the all-carbon-based bamboo mildew preventive of the comparative example is approximately the same as that of the embodiment 3, and is different in that the mass ratio of the nitrogen-doped carbon quantum dots to the organic mildew preventive is 1:25, and the preparation method comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (n-butyl-1, 2-benzisothiazolin-3-one in the embodiment), 10 parts of epoxiconazole, 3 parts of penflufen, 2 parts of KH-550 type silane coupling agent, 20 parts of phenoxyethanol, 19 parts of dipropylene glycol methyl ether and 36 parts of alkylphenol ethoxylate. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive from step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, 32 g of the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 is slowly added into the kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 3
The raw materials of the all-carbon-based bamboo mildew preventive comprise nitrogen-doped carbon quantum dots, wherein the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups on molecular structures, and the all-carbon-based bamboo mildew preventive does not comprise an organic mildew preventive.
The preparation method of the all-carbon-based bamboo mildew preventive of the comparative example is substantially the same as that of the example 1, except that the organic mildew preventive is not added, and comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed into 100 mL deionized water, transferred to a 200 mL autoclave, and subjected to hydrothermal reaction at 180℃for 12 hours. After cooling, the reaction product was centrifuged at 15,000 rpm for 20 minutes at high speed, and the supernatant was taken. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Dissolving nitrogen-doped carbon quantum dots in water
To a 10L reactor was added 0.8 kg tap water, mechanical stirring (2500 rpm) was turned on and the temperature was raised to 50 ℃. Subsequently, the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 of 80 g is slowly added into a kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. After the reaction is finished, the volume of the reaction solution is fixed to 10L total volume by tap water, and then the finished product of the all-carbon-based bamboo mildew preventive is obtained.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 4
According to the all-carbon-based bamboo mildew preventive of the comparative example, the raw materials comprise an organic bactericide, and nitrogen-doped carbon quantum dots are not added.
The preparation method of the all-carbon-based bamboo mildew preventive of the comparative example is approximately the same as that of the embodiment 3, except that no nitrogen-doped carbon quantum dots are added, and comprises the following steps:
1.1 Preparation of mother liquor of organic mildew preventive
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (n-butyl-1, 2-benzisothiazolin-3-one in the embodiment), 10 parts of epoxiconazole, 3 parts of penflufen, 2 parts of KH-550 type silane coupling agent, 20 parts of phenoxyethanol, 19 parts of dipropylene glycol methyl ether and 36 parts of alkylphenol ethoxylate. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.2 Dilution of mildew inhibitor
To a 10L reaction kettle, 0.8 kg of the mildewproof agent mother liquor was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃ and the mixture was allowed to react for 50 minutes to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the all-carbon-based bamboo mildew preventive in bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 5
The bamboo mildew preventive comprises nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the action of covalent bonds and non-covalent bonds on polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:20, and the organic bactericide is a commercially available organic mildew preventive (the main component is propiconazole and tebuconazole compound).
The preparation method of the bamboo mildew preventive of the comparative example is substantially the same as that of example 3, except that the kind of the organic mildew preventive is different, and includes the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
2.0 G of 2-hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan) was weighed and dissolved in 100 mL deionized water, transferred to a 200 mL high-pressure reaction kettle, subjected to hydrothermal reaction at 180 ℃ for 12 hours, cooled, and the reaction product was centrifuged at a high speed of 15,000 rpm for 20 minutes to obtain a supernatant. Dialyzing the supernatant for 72 hours by using a dialysis bag with the molecular weight cut-off of 1000 Da, and finally freeze-drying to obtain the powdery nitrogen-doped carbon quantum dots for later use.
The nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots with quaternary ammonium salt groups on the molecular structure, and the average particle size of the nitrogen-doped carbon quantum dots is about 5 nm after detection.
1.2 Preparation of mildew preventive mother liquor
The bamboo wood organic mildew preventive mother liquor sold in the market at present is selected.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive in step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, 32 g of the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 is slowly added into the kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the bamboo mildew preventive in the bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a bamboo mildew preventive finished product under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
Comparative example 6
According to the bamboo mildew preventive of the comparative example, raw materials comprise nitrogen-doped carbon quantum dots and organic bactericides, the organic bactericides are loaded on the surfaces of the nitrogen-doped carbon quantum dots through covalent bonds and non-covalent bonds and the action of polar groups (-OH, -COOH, -NH 2 and the like) on the surfaces of the nitrogen-doped carbon quantum dots, the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericides is 1:20, the organic bactericides are commercially available nitrogen-doped carbon quantum dots (produced by SiAN certain company, nitrogen-doped carbon dots|nitrogen-doped carbon quantum dots (N-CQDs), and the nitrogen-doped carbon quantum dots only contain nitrogen elements on molecular structures.
The preparation method of the bamboo mildew preventive of the comparative example is substantially the same as that of the example 3, except that the mildew preventive mother liquor is different in kind, and comprises the following steps:
1.1 Preparation of nitrogen-doped carbon quantum dots (N-CQDs)
The currently marketed nitrogen-doped carbon quantum dots are selected for use.
1.2 Preparation of mildew preventive mother liquor
The components are weighed according to the following weight parts of 10 parts of isothiazolinone derivative (n-butyl-1, 2-benzisothiazolin-3-one in the embodiment), 10 parts of epoxiconazole, 3 parts of penflufen, 2 parts of KH-550 type silane coupling agent, 20 parts of phenoxyethanol, 19 parts of dipropylene glycol methyl ether and 36 parts of alkylphenol ethoxylate. Stirring and mixing at room temperature until clear and transparent mother liquor of the organic mildew preventive is formed for standby.
1.3 Nitrogen-doped carbon quantum dot and mildew preventive mother liquor compounding
To a 10L reactor, 0.8 kg of the mother liquor of the mildew preventive in step 1.2 was added, mechanical stirring (2500 rpm) was started and the temperature was raised to 50 ℃. Subsequently, 32 g of the nitrogen-doped carbon quantum dot powder prepared in the step 1.1 is slowly added into the kettle. The mixture was allowed to react for 50 minutes at 50 ℃ and 2500 rpm ℃ to complete the coupling. And after the reaction is finished, diluting the reaction liquid by tap water, and fixing the volume to the total volume of 10L to obtain the finished product of the all-carbon-based bamboo mildew preventive.
The application of the bamboo mildew preventive in the bamboo mildew prevention treatment comprises the following steps:
And (3) carrying out vacuum-pressure impregnation treatment on the bamboo wood, namely placing a batch of bamboo wood plates to be treated into impregnation equipment. Starting a vacuum pump to vacuumize to-0.06 MPa, keeping for 45 minutes, injecting a finished product of the all-carbon-based bamboo mildew preventive under vacuum until the board is completely submerged, ensuring the smoothness of the injection process due to the high uniformity and stability of the composite liquid, closing the vacuum system, applying the pressure of 1.8 MPa, and maintaining the pressure for 1.5 hours.
And (3) drying and curing the impregnated bamboo wood, namely taking out the impregnated board, cleaning the surface, naturally airing for 24 hours, then transferring the board into a drying kiln, and performing constant-temperature drying at the temperature of 70 ℃ by programming until the water content is reduced to 12%.
The products of each example and comparative example of the present invention were used for bamboo, and mildew-proof test experiments were designed with reference to the standards GB/T18261-2013 and LY/T2230-2013, and after 28 days of test, the affected value of the veneer was evaluated and recorded with reference to Table 3, and then the mildew-proof efficacy of the modified veneer of the adhesive was calculated according to the formula (I).
TABLE 1 rating criteria for Single Board affected value
(I)
Wherein E is the control efficiency,%, D 1 is the average damage value of the bamboo processed by each example or comparative example of the invention, and D 0 is the average damage value of the untreated bamboo.
TABLE 2 mildew control efficacy for examples and comparative examples
The result shows that after 28 days of testing, the nitrogen-doped carbon quantum dots and the organic mildew preventive mother liquor have obvious synergistic effect, the proportion of the nitrogen-doped carbon quantum dots and the organic mildew preventive mother liquor is in the range of 1:10 to 1:20 (wt%) to form an efficient 'synergistic window', and the nitrogen-doped carbon quantum dots and the organic mildew preventive mother liquor can fully act in the window, so that the prevention and control efficiency of the bamboo wood can reach more than 97%. When the dosage of the nitrogen-doped carbon quantum dots is lower than the range, the effective concentration is insufficient, and the comprehensive protection cannot be formed.
In addition, when the nitrogen-doped carbon quantum dot prepared by the method is compounded with a commercial mildew preventive, or when an organic mildew preventive mother solution is compounded with the commercial nitrogen-doped carbon quantum dot, the prevention and treatment effects are not ideal. The precursor adopted by the nitrogen-doped carbon quantum dots of the embodiments is hydroxypropyl trimethyl ammonium chloride chitosan (HAC-chitosan), and the carbon quantum dots have certain antibacterial property due to the quaternary ammonium salt group, nitrogen of the nitrogen-doped carbon quantum dots mainly emphasizes nitrogen of the quaternary ammonium salt group, and other nitrogen-doped carbon quantum dots have low sterilization efficiency due to no sterilization property, so that the excellent mildew resistance of the invention is not simply due to random superposition of the components, but highly depends on precise matching and synergistic effect among specific components.
While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art, or equivalent embodiments with equivalent variations can be made, without departing from the scope of the invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.

Claims (10)

1. The all-carbon-based bamboo mildew preventive is characterized in that raw materials comprise nitrogen-doped carbon quantum dots and an organic bactericide, wherein the organic bactericide is loaded on the surfaces of the nitrogen-doped carbon quantum dots through the interaction of covalent bonds and non-covalent bonds with polar groups on the surfaces of the nitrogen-doped carbon quantum dots, the nitrogen-doped carbon quantum dots are nitrogen-doped carbon quantum dots containing quaternary ammonium salt groups in molecular structures, and the mass ratio of the nitrogen-doped carbon quantum dots to the organic bactericide is 1:10-20.
2. The all-carbon-based bamboo mildew preventive is characterized by comprising, by weight, 10-15 parts of isothiazolinone derivatives, 10-15 parts of epoxiconazole, 3-5 parts of penflufen, 1-3 parts of silane coupling agents, 15-25 parts of phenoxyethanol, 15-20 parts of dipropylene glycol methyl ether and 30-40 parts of surfactants.
3. The all-carbon-based bamboo mildew preventive according to claim 2, wherein the surfactant comprises at least one of alkylphenol ethoxylates and alkylsulfonates.
4. A preparation method of the all-carbon-based bamboo mildew preventive according to any one of claims 1 to 3 is characterized by comprising the steps of mixing nitrogen-doped carbon quantum dots with an organic bactericide according to a mass ratio of 1:10-20, and carrying out stirring reaction at a temperature of 40-60 ℃ to enable organic bactericide molecules to be loaded on the surfaces of the nitrogen-doped carbon quantum dots, so that the all-carbon-based bamboo mildew preventive is obtained.
5. The method for preparing the all-carbon-based bamboo mildew preventive according to claim 4, wherein the stirring speed of the stirring reaction is 1200-3000 rpm, and the reaction time is 30-60 min.
6. The method for preparing the all-carbon-based bamboo mildew preventive according to claim 4, wherein the preparation of the nitrogen-doped carbon quantum dots comprises the following steps:
taking chitosan quaternary ammonium salt as a carbon source to carry out hydrothermal reaction at the temperature of 150-200 ℃ to obtain a crude product;
Centrifuging the crude product, and dialyzing and purifying the supernatant to obtain a purified solution;
and freeze-drying the purified solution to obtain the nitrogen-doped carbon quantum dots.
7. The method for preparing the all-carbon-based bamboo mildew preventive according to claim 6, wherein the hydrothermal reaction time is 10-15 h.
8. Use of the all-carbon-based bamboo mildew preventive according to any one of claims 1 to 3 or the all-carbon-based bamboo mildew preventive prepared by the preparation method of the all-carbon-based bamboo mildew preventive according to any one of claims 4 to 7 in bamboo mildew preventive treatment.
9. The method of claim 8, wherein the method comprises the steps of placing the bamboo material to be treated in an all-carbon-based bamboo material mildew preventive, and fully penetrating the all-carbon-based bamboo material mildew preventive into the bamboo material by adopting a normal pressure soaking, vacuum soaking or vacuum-pressure soaking process, drying and curing to obtain the mildew-proof treated bamboo material.
10. The method of claim 9, comprising at least one of scheme A and scheme B:
scheme a when a vacuum-pressure impregnation process is used, comprising the steps of:
Firstly, vacuumizing an impregnating tank filled with bamboo to-0.05 to-0.08 MPa, maintaining pressure for 30-60 minutes, injecting a full-carbon-based bamboo mildew preventive, and maintaining pressure for 1-2 hours under the pressure of 1.5-2.0 MPa;
And the scheme B comprises the following steps of drying the bamboo at the temperature of 60-80 ℃ to enable the nitrogen-doped carbon quantum dots and the organic bactericide in the all-carbon-based bamboo mildew inhibitor to be deposited and cured on the inner walls of microscopic holes of the bamboo until the moisture content of the bamboo reaches a target value.
CN202511034527.0A 2025-07-25 2025-07-25 All-carbon-based bamboo mildew preventive and preparation method and application thereof Pending CN120859006A (en)

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