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CN108739807B - Vegetable oleic acid-chitosan-based nano-microcapsule pesticide, preparation method and application thereof - Google Patents

Vegetable oleic acid-chitosan-based nano-microcapsule pesticide, preparation method and application thereof Download PDF

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CN108739807B
CN108739807B CN201810643828.7A CN201810643828A CN108739807B CN 108739807 B CN108739807 B CN 108739807B CN 201810643828 A CN201810643828 A CN 201810643828A CN 108739807 B CN108739807 B CN 108739807B
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chitosan
pesticide
oleic acid
acid
microcapsule
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CN108739807A (en
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李普旺
周闯
杨子明
陶金龙
李思东
陈煜�
孔令学
吕明哲
王超
何祖宇
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Agricultural Products Processing Research Institute of CATAS
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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
    • 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
    • A01N25/26—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 in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A—HUMAN NECESSITIES
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    • 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
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
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    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
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    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
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    • C08G18/40—High-molecular-weight compounds
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Abstract

本发明公开一种植物油酸‑壳聚糖基纳米微胶囊农药，以多元异氰酸酯‑植物油酸‑壳聚糖基多元醇复合材料为壁材，以农药为芯材，芯材包埋于壁材内，壁材与芯材质量比为1:1～5:1。本发明还提供了植物油酸‑壳聚糖基纳米微胶囊农药的制备方法以其在热带经济作物病虫害防治方面的应用。本发明所公开的植物油酸‑壳聚糖基纳米微胶囊农药不仅利用壳聚糖的可塑性、抗菌性，而且可以利用不饱和植物油酸长链的柔韧性，使其多功能化；此外，本发明还充分利用纳米载药粒子的小尺寸效应和大比表面效应，增大纳米农药与作物黏附性与覆盖率，以此提高农药的利用率。

Figure 201810643828

The invention discloses a vegetable oleic acid-chitosan-based nano-microcapsule pesticide, which uses a polyisocyanate-vegetable oleic acid-chitosan-based polyol composite material as a wall material, uses a pesticide as a core material, and the core material is embedded in the wall material , the mass ratio of wall material to core material is 1:1 to 5:1. The invention also provides a preparation method of vegetable oleic acid-chitosan-based nano-microcapsule pesticide and its application in the prevention and control of tropical economic crop diseases and insect pests. The vegetable oleic acid-chitosan-based nano-microcapsule pesticide disclosed in the present invention not only utilizes the plasticity and antibacterial properties of chitosan, but also utilizes the flexibility of the long chain of unsaturated vegetable oleic acid to make it multifunctional; It also makes full use of the small size effect and large specific surface effect of nano-drug-loaded particles to increase the adhesion and coverage of nano-pesticide and crops, thereby improving the utilization rate of pesticides.

Figure 201810643828

Description

Vegetable oleic acid-chitosan-based nano microcapsule pesticide, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a plant oleic acid-chitosan-based nano microcapsule pesticide, and a preparation method and application thereof.
Background
China is a big agricultural country, and pesticides are important material bases for preventing plant diseases and insect pests and guaranteeing grain production and have irreplaceable effects on maintaining the livelihood of the people. However, the traditional pesticide formulation has the serious disadvantages of short pesticide effect, low utilization rate and the like, which not only causes huge economic loss, but also causes serious environmental problems due to pesticide loss. In recent years, the development of efficient and safe novel pesticide formulations by utilizing nano science and technology to realize the quality improvement and efficiency enhancement, the energy saving and emission reduction and the reduction of residual pollution of chemical pesticides has become a current research hotspot.
Through the nanometer formulation of the traditional pesticide, the biological activity and the target utilization rate of the pesticide effect components can be improved, the lasting period is prolonged, the contents of organic solvents and auxiliaries are reduced, and the pesticide effect losses such as medicament falling, rain wash, leaching decomposition and the like are reduced, so that the effective utilization rate of the pesticide is greatly improved, the pesticide application dosage and frequency are reduced, and the pesticide residue of agricultural products is reduced. The nano microcapsule has the size of below 1000nm (1 micron), and has the features of nanometer size, hollow structure and slow release, and may enter cell directly to regulate the release rate of the coated matter and the permeation rate of outer matter via altering the permeating function of the capsule wall, so as to reach the similar controlled release effect. The method can reduce the application amount of the pesticide, reduce the burden of farmers, reduce environmental pollution and realize sustainable development of economy and society.
The vegetable oil is widely distributed, generally has 1-3 unsaturated double bonds in the structure, and many of the vegetable oil also contain active reaction groups such as hydroxyl, carboxyl and the like, and biomass high polymer materials are synthesized by chemically modifying natural vegetable oil, such as alkylation, ester exchange, hydrolysis, epoxidation and the like, so that the scientific research value and the economic value of vegetable oil resources are increased, the application range of the vegetable oil is expanded, and the method has important significance.
As a novel high molecular functional material, chitosan has excellent biological performance, but the solubility of the chitosan is poor, and the chitosan can only be dissolved in some dilute acid, and cannot be dissolved in water, alkaline solution and most organic solvents, so that the application range of the chitosan is greatly limited. In order to overcome the defects of poor solubility and the like and expand the application range of the chitosan, physical and chemical means are usually adopted to modify the chitosan so as to improve the physical and chemical properties of the chitosan. Based on the existence of characteristic groups such as hydroxyl, amino and the like in chitosan molecules, quaternary phosphonium salinization, sulfhydrylation and the like can be carried out on the amino and the hydroxyl, and due to the introduction of special functional group groups, the steric hindrance is large, the hydration capability is strong, the hydrogen bond effect among the chitosan molecules can be weakened to a great extent, so that the water solubility of the chitosan derivative is increased, or a hydrophobic group is introduced, and the amphiphilic multifunctional modified chitosan is prepared.
The novel nano microcapsule pesticide is constructed by using the modified chitosan as a base material and adopting a layer-by-layer self-assembly method, an in-situ polymerization method, a complex coacervation method and the like and utilizing the electrostatic attraction, hydrogen bonds, flocculation and the like of a carrier material, so that the application amount of the pesticide can be reduced, the economic burden of farmers can be reduced, the environmental pollution can be reduced, and the sustainable development of economy and society can be realized.
In the prior art, patent CN103493803A discloses a novel botanical pesticide preparation, which takes chitosan-Arabic gum as a wall material and leaf alcohol as a core material to prepare leaf alcohol microcapsules by a complex coacervation method, wherein the grain diameter of the prepared microcapsules is in a micron level.
Patent CN101519475A discloses a preparation method of a rotenone/carboxymethyl chitosan grafted ricinoleic acid nano-particle water dispersion preparation, the invention firstly grafts chitosan grafted ricinoleic acid, then reacts with chloroacetic acid to prepare carboxymethyl chitosan grafted ricinoleic acid copolymer, and finally mixes and stirs with rotenone acetone solution to prepare the rotenone/carboxymethyl chitosan grafted ricinoleic acid nano-particle water dispersion preparation.
Although the two inventions use chitosan or chitosan derivatives as wall materials to prepare the microcapsule pesticide, the modification process does not mention the synthesis of the vegetable oleic acid-chitosan-based polyol by the click reaction of the product of the reaction of vegetable oil and chitosan and mercaptan under the condition of ultraviolet light, and the preparation of the nano microcapsule pesticide by using the plant oleic acid-chitosan-based polyol as the wall material is essentially different from the invention.
Disclosure of Invention
The invention aims to provide a vegetable oleic acid-chitosan-based nano microcapsule pesticide, a preparation method and application thereof, so as to solve one or more of the problems.
According to one aspect of the invention, the plant oleic acid-chitosan-based nano microcapsule pesticide is provided, a polymer formed by plant oleic acid-chitosan-based polyol and polyisocyanate is used as a wall material, the pesticide is used as a core material, the core material is embedded in the wall material, and the mass ratio of the wall material to the core material is 1: 1-5: 1.
In some embodiments, the pesticide is preferably at least one of abamectin, thymol, fluopyram, lambda-cyhalothrin, fenpropathrin, bifenthrin, clothianidin, fosthiazate, imidacloprid, chlorfenapyr, or chlorantraniliprole.
In some embodiments, the polyisocyanate is preferably at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, or lysine diisocyanate.
In some embodiments, the vegetable oil acid is at least one of ricinoleic acid, eleostearic acid, linoleic acid, or oleic acid.
In some embodiments, the chitosan has a viscosity average molecular weight of 1.2 × 103～2.5×105The deacetylation degree is more than or equal to 90 percent.
According to another aspect of the invention, a preparation method of the plant oleic acid-chitosan-based nano microcapsule pesticide is provided, which comprises the following specific steps:
1) preparing vegetable oleic acid-chitosan-based polyol into an aqueous solution, adding polyisocyanate into the aqueous solution of the vegetable oleic acid-chitosan-based polyol, stirring, adding a catalyst, and reacting to obtain a prepolymer;
2) adding an oil-soluble pesticide into acetone to prepare a pesticide solution, uniformly mixing the pesticide solution with the prepolymer obtained in the step 1), then adding the mixture into an aqueous solution containing an emulsifier to form an oil-in-water emulsion system, adding a chain extender, reacting at a constant temperature of 60-80 ℃ for 2-4 h, and continuously stirring to obtain the vegetable oleic acid-chitosan-based nano microcapsule pesticide.
In some embodiments, the vegetable oleic acid-chitosan based polyol has a mass concentration of 1.0% to 5.0%.
In some embodiments, the polyisocyanate is preferably at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), or Lysine Diisocyanate (LDI).
In some embodiments, the amount of catalyst is 1% to 2% of the total mass of the system, preferably at least one of dibutyltin dilaurate, stannous octoate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, or triethylenediamine, or tetraisobutyl titanate.
In some embodiments, the reaction temperature in the step 1) is preferably 50-80 ℃, the reaction time is preferably 5-15 h, and the stirring speed is preferably 100-2000 r/min;
in some embodiments, the pesticide in step 2) has a mass concentration of preferably 1% to 5%, and is preferably at least one of abamectin, thymol, fluopyram, lambda-cyhalothrin, fenpropathrin, bifenthrin, clothianidin, fosthiazate, imidacloprid, chlorfenapyr, or chlorantraniliprole.
In some embodiments, the mass ratio of the prepolymer to the pesticide is preferably 1:1 to 5: 1.
In some embodiments, the amount of the chain extender is preferably 1 to 3% of the total mass of the system, and preferably at least one of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, Diethylaminoethanol (DEAE), ethylenediamine (DA), or N, N-dihydroxy (diisopropyl) aniline (HPA)
In some embodiments, the emulsifier is preferably at least one of tween-80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, fatty acid polyoxyethylene ether, or cetyl trimethylammonium bromide.
In some embodiments, the mass concentration of the pesticide in the pesticide solution in the step 2) is preferably 1-5%; the stirring speed is preferably 100 to 2000 r/min.
The preparation method of the vegetable oleic acid-chitosan-based polyol comprises the following steps: mixing the chitosan grafted plant oleic acid copolymer with mercaptan and a free radical photoinitiator, magnetically stirring for 0-5 h at 100-1000 r/min under the irradiation of 100-1000W UV light, then diluting with a first organic solvent, washing with a saturated inorganic salt solution, drying with a drying agent, filtering, finally removing the first organic solvent through a rotary evaporator, and placing the product in a vacuum drying oven for drying to obtain the plant oleic acid-chitosan based polyol.
The reaction formula of the preparation method of the vegetable oleic acid-chitosan-based polyol is shown as the formula (I):
Figure GDA0002834938590000041
wherein n, k is 0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16.
In some embodiments, the thiol is at least one of 2-mercaptoethanol, 3-mercapto-1-propanol, 2, 3-dimercaptopropanol, 1-mercapto-2-propanol, 2-mercapto-3-propanol, 6-mercaptohex-1-ol, 3-mercapto-2-butanol, 11-mercapto-1-undecanol.
In some embodiments, the free radical photoinitiator is preferably 2-hydroxy-2-methyl-1-phenylpropanone (1173), 1-hydroxycyclohexylphenylketone (trade name 184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (trade name 907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (trade name TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name IHT-PI) 910, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (trade name 659), methyl benzoylformate (trade name MBF).
In some embodiments, the first organic solvent is at least one of acetone, ethyl acetate, tetrahydrofuran, N-dimethylformamide, dichloromethane, isopropanol, methyl butanone.
In some embodiments, the inorganic salt is at least one of sodium sulfate, magnesium sulfate, sodium chloride, or potassium chloride.
In some embodiments, the desiccant is preferably at least one of calcium chloride, phosphorus pentoxide, calcium sulfate, or magnesium sulfate.
The preparation method of the chitosan grafted plant oleic acid (CS-g-VO) copolymer comprises the following steps: preparing vegetable oleic anhydride by carrying out a sealing reaction on vegetable oleic acid and acetic anhydride, then mixing chitosan and a sodium iodide solution, dropwise adding vegetable oleic anhydride and pyridine, stirring and mixing uniformly, reacting for 6-16 h at 50-80 ℃, then soaking, washing and dehydrating by using a second organic solvent, finally placing in a vacuum drying oven for drying treatment for 4-48 h at 40-80 ℃ to obtain a chitosan grafted vegetable oleic acid copolymer, wherein the synthetic reaction formula is shown as formula (II):
Figure GDA0002834938590000051
wherein n, k is 0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16.
Wherein the viscosity average molecular weight of chitosan is 1.2 × 103～2.5×105The deacetylation degree is more than or equal to 90 percent; the mass ratio of the chitosan to the sodium iodide is 1: 1-1: 6, the molar ratio of the vegetable oleic anhydride to the chitosan is 1: 1-5: 1, and the molar ratio of the pyridine to the vegetable oleic anhydride is 2: 1-6: 1.
According to the invention, firstly, chitosan is grafted on vegetable oleic acid to obtain a copolymer, then, a double bond and mercaptan click reaction are initiated by UV light to synthesize vegetable oleic acid-chitosan-based polyol, and finally, an interfacial polymerization method is adopted, and a polybasic isocyanate-polyol system is used as a wall material of a microcapsule to prepare the vegetable oleic acid-chitosan-based nano microcapsule pesticide, the adopted raw materials are renewable, pollution-free and degradable, and the preparation method has the advantages of mild reaction conditions, short reaction time, high utilization rate and the like, and not only can utilize the plasticity and antibacterial property of chitosan, but also can utilize the flexibility of unsaturated vegetable oleic acid long chains to prepare the multifunctional-based nano microcapsule pesticide; in addition, the invention also fully utilizes the small-size effect and the large-specific surface effect of the nano drug-loaded particles, and increases the adhesiveness and the coverage rate of the nano pesticide and crops, thereby improving the utilization rate of the pesticide.
The invention takes chitosan as a base material, and performs ester exchange reaction through amino in the chitosan and unsaturated vegetable oleic acid; then, through the click reaction of sulfydryl and double bonds under ultraviolet light, introducing long chains and C-S bonds to prepare the vegetable oleic acid-chitosan polyol; and finally, the multifunctional nano microcapsule pesticide is constructed by taking the modified carrier material as a wall material and utilizing physical and chemical methods such as intermolecular electrostatic attraction, an emulsion template, flocculation, curing and crosslinking of the modified carrier material, and the multifunctional nano microcapsule pesticide can be prepared by utilizing the plasticity and antibacterial property of chitosan and the flexibility of the long chain of unsaturated vegetable oleic acid. Therefore, the unsaturated vegetable oleic acid and the chitosan are subjected to chemical reaction to generate a target product, and the target product is used as a base material to prepare the nano microcapsule pesticide, so that the research idea is innovative, and the method has important scientific research significance and economic significance on the application research of the natural oleic acid and the chitosan.
According to another aspect of the invention, the application of the plant oleic acid-chitosan-based nano microcapsule pesticide in the aspect of pest control of tropical commercial crops (such as bananas, longans, mangos, pineapples and the like) is provided.
Drawings
FIG. 1(A) is a scanning electron microscope image of linoleic acid-chitosan-based clothianidin nano-microcapsule pesticide of example 1 of the present invention under 500 times magnification;
FIG. 1(B) is a scanning electron microscope image of linoleic acid-chitosan-based clothianidin nano-microcapsule pesticide of example 1 of the present invention under 1000 times magnification;
FIG. 1(C) is a scanning electron microscope image of linoleic acid-chitosan-based clothianidin nano-microcapsule pesticide of example 1 of the present invention under 2000 times amplification;
FIG. 2 is a comparison graph of IR spectra of linoleic acid and linoleic acid-chitosan based polyols in example 1 of the present invention, wherein a and b are linoleic acid and linoleic acid-chitosan based polyols, respectively;
FIG. 3 is a graph showing the comparison of nuclear magnetic hydrogen spectra of linoleic acid and linoleic acid-chitosan-based polyol in example 1 of the present invention, wherein a and b are linoleic acid-chitosan-based polyol and linoleic acid, respectively.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1 linoleic acid-Chitosan-based clothianidin Nanofulp Pest
The preparation method of the linoleic acid-chitosan-based clothianidin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of glacial acetic acid 1% (v/v) aqueous solution, adding 70mL of methanol, vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 2-mercaptoethanol and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) serving as a photoinitiator, placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 2-mercaptoethanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 2-mercaptoethanol, drying and filtering phosphorus pentoxide, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
3) The preparation method of the linoleic acid-chitosan-based clothianidin nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 3.0% by using the linoleic acid-chitosan-based polyol prepared in the step 2), adding diphenylmethane diisocyanate (MDI) into the water solution, wherein the molar ratio of the hydroxyl group of the linoleic acid-chitosan-based polyol to the diphenylmethane diisocyanate (MDI) is 2:1, adding stannous octoate accounting for 1.5% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at the temperature of 65 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding a pesticide clothianidin into an organic solvent acetone to prepare a pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 3 hours, then adding 2.0% of a chain extender, namely Diethylaminoethanol (DEAE), and continuously stirring and reacting for 4 hours at 65 ℃ to obtain the linoleic acid-chitosan-based clothianidin nano microcapsule pesticide.
Example 2 eleostearic acid-chitosan based avermectin nano microcapsule pesticide
The preparation method of the eleostearic acid-chitosan-based avermectin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted eleostearic acid copolymer:
29.85g of eleostearic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 139 ℃ to react for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red brown tung oil anhydride liquid, drying, sealing and storing;
weighing the mixture with viscosity-average molecular weight of 1.2 × 1051g of chitosan having a degree of deacetylation of 90% was dissolved in 30mL of a 1% (v/v) aqueous solution of glacial acetic acidAdding 70mL of methanol and vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding tung oil anhydride and pyridine, wherein the molar ratio of the tung oil anhydride to the chitosan amino group is 3:1, and the molar ratio of the pyridine to the tung oil anhydride is 3:1, vigorously stirring to enable the tung oil anhydride and the pyridine to be uniformly mixed, reacting for 10 hours at 70 ℃, soaking and washing for 3 times with acetone, dehydrating with diethyl ether, washing for 3 times with ethanol, and vacuum drying for 48 hours at 50 ℃ to obtain the chitosan grafted tung oil acid.
2) Preparing eleostearic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted eleostearic acid copolymer obtained in the step 1) with 2-mercaptoethanol and a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), placing the mixture in a 500W photochemical reaction instrument, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 2-mercaptoethanol to the chitosan grafted eleostearic acid copolymer is 3:1, the amount of the photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173) is 2% of the total mass of the system, and the stirring speed is 600 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated sodium chloride solution to remove unreacted 2-mercaptoethanol, drying by using anhydrous calcium chloride, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the eleostearic acid-chitosan-based polyol.
3) The preparation method of the eleostearic acid-chitosan-based avermectin nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 2% by using the eleostearic acid-chitosan based polyol prepared in the step 2), adding toluene diisocyanate, wherein the molar ratio of hydroxyl of the eleostearic acid-chitosan based polyol to the toluene diisocyanate is 2:1, then adding dibutyltin dilaurate accounting for 1.5% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 8 hours in a constant-temperature water bath kettle at the temperature of 60 ℃ at the stirring speed of 600r/min to obtain a prepolymer;
adding pesticide avermectin into organic solvent acetone to prepare pesticide with the mass concentration of 2%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 3:1, adding the prepolymer to an emulsifier containing 3% of hexadecyl trimethyl ammonium bromide under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 2 hours, then adding 2% of chain extender 1, 4-butanediol, and continuously stirring and reacting for 3 hours at the temperature of 60 ℃ to obtain the eleostearic acid-chitosan-based avermectin nano microcapsule pesticide.
Example 3 ricinoleic acid-Chitosan-based beta-cyfluthrin nano microcapsule pesticide
The preparation method of the ricinoleic acid-chitosan-based efficient cyfluthrin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted ricinoleic acid copolymer:
29.85g of ricinoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, the oil bath is heated to 130 ℃, and the reaction is carried out for 3 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red brown ricinoleic anhydride liquid, drying, sealing and storing;
weighing the mixture with viscosity-average molecular weight of 1.5 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol and vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding ricinoleic anhydride and pyridine, wherein the molar ratio of ricinoleic anhydride to chitosan amino reaction is 4:1, the molar ratio of pyridine to ricinoleic anhydride reaction is 4:1, vigorously stirring to enable the mixture to be uniformly mixed, reacting for 8 hours at 80 ℃, soaking with acetone, washing for 3 times, dehydrating with diethyl ether, washing for 3 times with ethanol, and vacuum drying for 24 hours at 60 ℃ to obtain the chitosan grafted ricinoleic acid.
2) Preparation of ricinoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted ricinoleic acid copolymer obtained in the step 1), 3-mercapto-1-propanol and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-1-propanol to the chitosan grafted ricinoleic acid copolymer is 3:1, the amount of the photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 3-mercapto-1-propanol, drying by using anhydrous calcium chloride, filtering, removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the ricinoleic acid-chitosan-based polyol.
3) The preparation of ricinoleic acid-chitosan group high-efficiency cyfluthrin nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 2.5% by using the ricinoleic acid-chitosan based polyol prepared in the step 2), adding isophorone diisocyanate (IPDI), wherein the molar ratio of hydroxyl of the ricinoleic acid-chitosan based polyol to the isophorone diisocyanate (IPDI) is 3:1, then adding zinc naphthenate accounting for 1.0% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at 70 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding the pesticide beta-cyfluthrin into an organic solvent acetone to prepare a pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl benzene sulfonate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 2.5 hours, then adding 1.5% of a chain extender 1, 4-butanediol, and continuously stirring and reacting for 3 hours at 70 ℃ to obtain the ricinoleic acid-chitosan-based beta-cyfluthrin nano microcapsule pesticide.
Example 4 Linseed oil acid-Chitosan-based Chlorantraniliprole Nanofulfop-Ensul-cide
The preparation method of the linoleic acid-chitosan group chlorantraniliprole nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 120 ℃ for reaction for 5 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red brown linolenic acid anhydride liquid, drying, sealing and storing;
weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linolenic acid and pyridine, wherein the reaction molar ratio of linolenic acid to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linolenic acid is 4:1, and vigorously stirring to enable the linolenic acid and the pyridine to be uniformly mixed; reacting at 80 deg.C for 8h, soaking in acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 deg.C for 24h to obtain chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1), 3-mercapto-1-propanol and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-1-propanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) is 1.5 percent of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with a solvent isopropanol, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 3-mercapto-1-propanol, drying by using anhydrous calcium sulfate, filtering, removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
3) The preparation of the linoleic acid-chitosan group chlorantraniliprole nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 2.5% by using the linoleic acid-chitosan based polyol prepared in the step 2), adding diphenylmethane diisocyanate (MDI), adding stannous octoate with the total mass of 1.0% of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at 70 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding pesticide chlorantraniliprole into organic solvent acetone to prepare pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 2.5 hours, then adding 1.5% of chain extender trimethylolpropane, and continuously stirring and reacting for 3 hours at 70 ℃ to obtain the linoleic acid-chitosan group chlorantraniliprole nano microcapsule pesticide.
Example 5 oleic acid-Chitosan-methyl-cyanide-pyrethrin nano microcapsule pesticide
The preparation method of the oleic acid-chitosan-based fenpropathrin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted oleic acid copolymer:
29.85g of oleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain reddish brown oleic anhydride liquid, drying, sealing and storing. Weighing 1g of chitosan with the viscosity-average molecular weight of 3.0 multiplied by 105 and the deacetylation degree of 91%, dissolving the chitosan in 40mL of glacial acetic acid 1% (v/v) aqueous solution, adding 80mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding oleic anhydride and pyridine, wherein the reaction molar ratio of oleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to oleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted oleic acid.
2) Preparation of oleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted oleic acid copolymer obtained in the step 1) with 2, 3-dimercaptopropanol and a photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), placing the mixture in a photochemical reaction instrument with the power of 800W, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 2, 3-dimercaptopropanol to the chitosan grafted oleic acid copolymer is 4:1, the amount of the 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659) is 1.0 percent of the total mass of the system, and the stirring speed is 700 r/min. After the reaction is finished, diluting with methyl butanone serving as a solvent, washing for 3-4 times by using a saturated potassium chloride solution to remove unreacted 2, 3-dimercaptopropanol, drying by using anhydrous calcium chloride, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the oleic acid-chitosan-based polyol.
3) The preparation of the oleic acid-chitosan fenpropathrin nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing an aqueous solution with the mass solubility of 3.0% by using the oleic acid-chitosan-based polyol prepared in the step 2), adding Hexamethylene Diisocyanate (HDI), wherein the molar ratio of hydroxyl of the oleic acid-chitosan-based polyol to toluene diisocyanate is 2:1, adding stannous octoate with the total mass of 1.5% of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at 65 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding fenpropathrin as a pesticide into acetone as an organic solvent to prepare a pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 3 hours, then adding 2.0% of Diethylaminoethanol (DEAE) as a chain extender, and continuously stirring and reacting for 4 hours at 65 ℃ to obtain the oleic acid-chitosan-based fenpropathrin nano microcapsule pesticide.
Example 6 linoleic acid-Chitosan-based thymol Nanofulp pesticide
The preparation method of the linoleic acid-chitosan group thymol nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 1-mercapto-2-propanol and a photoinitiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (the trade name is TPO-L), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 1-mercapto-2-propanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the 2,4, 6-trimethylbenzoylphenylphosphonate ethyl ester (the trade name is TPO-L) is 1.5 percent of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with tetrahydrofuran serving as a solvent, washing for 3-4 times by using saturated magnesium sulfate solution to remove unreacted 1-mercapto-2-propanol, drying by using phosphorus pentoxide, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
3) The preparation of the linoleic acid-chitosan group thymol nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 3.0% by using the linoleic acid-chitosan-based polyol prepared in the step 2), adding diphenylmethane diisocyanate (MDI) into the water solution, wherein the molar ratio of the hydroxyl group of the linoleic acid-chitosan-based polyol to the diphenylmethane diisocyanate (MDI) is 2:1, adding lead octoate accounting for 1.5% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at the temperature of 65 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding a pesticide thymol into an organic solvent acetone to prepare a pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 3 hours, then adding 2.0% of chain extender sorbitol, and continuously stirring and reacting for 4 hours at 65 ℃ to obtain the linoleic acid-chitosan-based thymol nano microcapsule pesticide.
Example 7 oleic acid-Chitosan-based Fluopyram Nanocoapsules pesticide
The preparation method of the oleic acid-chitosan fluopyram nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted oleic acid copolymer:
29.85g of oleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain reddish brown oleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 3.0 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 40mL of 1% (v/v) glacial acetic acid aqueous solution, adding 80mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding oleic anhydride and pyridine, wherein the molar ratio of oleic anhydride to chitosan amino reaction is 4:1, and the molar ratio of pyridine to oleic anhydride reaction is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted oleic acid.
2) Preparation of oleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted oleic acid copolymer obtained in the step 1) with 3-mercapto-2-butanol and a photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone (the trade name is 907), placing the mixture into a photochemical reaction instrument with the power of 800W, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 3-mercapto-2-butanol to the chitosan grafted oleic acid copolymer is 4:1, the amount of the 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone (the trade name is 907) is 1.0 percent of the total mass of the system, and the stirring speed is 700 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated potassium chloride solution to remove unreacted 3-mercapto-2-butanol, drying by using anhydrous calcium chloride, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the oleic acid-chitosan-based polyol.
3) The preparation of the oleic acid-chitosan fluopyram nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing an aqueous solution with the mass solubility of 3.0% by using the oleic acid-chitosan-based polyol prepared in the step 2), adding lysine diisocyanate, wherein the molar ratio of hydroxyl of the oleic acid-chitosan-based polyol to the lysine diisocyanate is 2:1, then adding cobalt octoate accounting for 1.5% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at the temperature of 65 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding pesticide fluopyram into organic solvent acetone to prepare pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 3 hours, then adding 2.0% of chain extender 1, 6-hexanediol, and continuously stirring and reacting for 4 hours at 65 ℃ to obtain the oleic acid-chitosan-based fluopyram nano microcapsule pesticide.
Example 8 eleostearic acid-chitosan-based bifenthrin nano microcapsule pesticide
The preparation method of the eleostearic acid/chitosan-based bifenthrin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted eleostearic acid copolymer:
29.85g of eleostearic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 139 ℃ to react for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red brown tung oil anhydride liquid, drying, sealing and storing;
weighing the mixture with viscosity-average molecular weight of 1.2 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol and vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding tung oil anhydride and pyridine, wherein the molar ratio of the tung oil anhydride to the chitosan amino reaction is 3:1, the molar ratio of the pyridine to the tung oil anhydride reaction is 3:1, vigorously stirring to enable the mixture to be uniformly mixed, reacting for 10 hours at 70 ℃, soaking with acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying for 48 hours at 50 ℃ to obtain the chitosan grafted tung oil acid.
2) Preparing eleostearic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted eleostearic acid copolymer obtained in the step 1) with 6-mercaptohexane-1-ol and a photoinitiator methyl benzoylformate (trade name is MBF), placing the mixture in a 500W photochemical reaction instrument, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 6-mercaptohexane-1-ol to the chitosan grafted eleostearic acid copolymer is 3:1, the amount of the photoinitiator methyl benzoylformate (trade name is MBF) is 2% of the total mass of the system, and the stirring speed is 600 r/min. After the reaction is finished, diluting with a solvent dichloromethane, washing for 3-4 times by using a saturated sodium chloride solution to remove unreacted 6-mercaptohexan-1-ol, drying by using anhydrous magnesium sulfate, filtering, finally removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the eleostearic acid-chitosan-based polyol.
3) The preparation method of the eleostearic acid-chitosan bifenthrin nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 2% by using the eleostearic acid-chitosan based polyol prepared in the step 2), adding toluene diisocyanate, wherein the molar ratio of hydroxyl of the eleostearic acid-chitosan based polyol to the toluene diisocyanate is 2:1, then adding dibutyltin dilaurate accounting for 1.5% of the total mass of the system as a catalyst, and carrying out magnetic stirring reaction for 8 hours in a constant-temperature water bath kettle at the temperature of 60 ℃ at the stirring speed of 600r/min to obtain a prepolymer;
adding bifenthrin as a pesticide into acetone as an organic solvent to prepare a pesticide with the mass concentration of 2%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 3:1, adding the prepolymer into an emulsifier containing 3% of tween-80 under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 2 hours, then adding 2% of diethylene glycol as a chain extender, and continuously stirring and reacting for 3 hours at the temperature of 60 ℃ to obtain the eleostearic acid-chitosan-based bifenthrin nano microcapsule pesticide.
Example 9 linoleic acid-Chitosan-based Imidacloprid Nanofulp Pest
The preparation method of the linoleic acid/chitosan-based clothianidin nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 92% in 30mL of glacial acetic acid 1% (v/v) aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 2-mercapto-3-propanol and a photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 2-mercapto-3-propanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 2-mercapto-3-propanol, drying by using phosphorus pentoxide, filtering, removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
3) The preparation of the linoleic acid-chitosan-based imidacloprid nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 3.0% by using the linoleic acid-chitosan based polyol prepared in the step 2), adding dicyclohexylmethane diisocyanate, adding iron caprylate with the total mass of 1.5% of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at the temperature of 65 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding imidacloprid serving as a pesticide into acetone serving as an organic solvent to prepare a pesticide with the mass concentration of 2.5%, uniformly mixing the imidacloprid serving as the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the imidacloprid serving as the pesticide into an emulsifier containing 2% of fatty acid polyoxyethylene ether under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 3 hours, adding ethylene diamine serving as a chain extender of 2.0%, and continuously stirring and reacting for 4 hours at 65 ℃ to obtain the linoleic acid-chitosan-based imidacloprid nano microcapsule pesticide.
Example 10 Linoleic acid-Chitosan-based Chlorfenapyr Nannocapsule pesticide
The preparation method of the linoleic acid-chitosan-based chlorfenapyr nano microcapsule pesticide comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 120 ℃ for reaction for 5 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red brown linolenic acid anhydride liquid, drying, sealing and storing;
weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linolenic acid and pyridine, wherein the reaction molar ratio of linolenic acid to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linolenic acid is 4:1, and vigorously stirring to enable the linolenic acid and the pyridine to be uniformly mixed; reacting at 80 deg.C for 8h, soaking in acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 deg.C for 24h to obtain chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1), 3-mercapto-1-propanol and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-1-propanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) is 1.5 percent of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with a solvent isopropanol, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 3-mercapto-1-propanol, drying by using anhydrous calcium sulfate, filtering, removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
3) The preparation of the linoleic acid-chitosan-based chlorfenapyr nano microcapsule pesticide comprises the following steps:
adopting an interfacial polymerization method, taking a polyisocyanate-polyol system as a wall material of a microcapsule, preparing a water solution with the mass solubility of 2.5% by using the linoleic acid-chitosan based polyol prepared in the step 2), adding diphenylmethane diisocyanate (MDI), adding tetraisobutyl titanate with the total mass of 1.0% of the system as a catalyst, and carrying out magnetic stirring reaction for 6 hours in a constant-temperature water bath kettle at 70 ℃ at the stirring speed of 800r/min to obtain a prepolymer;
adding pesticide chlorfenapyr into organic solvent acetone to prepare pesticide with the mass concentration of 2.5%, uniformly mixing the pesticide with the prepolymer, wherein the mass ratio of the prepolymer to the pesticide is 2:1, adding the prepolymer and the pesticide into an emulsifier containing 2% of sodium dodecyl sulfate under the conditions of heating and stirring to form an oil-in-water emulsion system, continuously reacting for 2.5 hours, then adding 1.5% of chain extender neopentyl glycol, and continuously stirring and reacting for 3 hours at 70 ℃ to obtain the linoleic acid-chitosan-based chlorfenapyr nano microcapsule pesticide.
The appearance morphology of the nano microcapsule pesticides prepared in examples 1 to 10 was tested by using a field emission scanning electron microscope of Hitachi S4800;
the vegetable oleic acid-chitosan-based polyol prepared in examples 1 to 10 was structurally characterized by using an AVATAR 360FT-IR type Fourier infrared spectrometer manufactured by Nicolet corporation, USA, and a Bruker AV 600 nuclear magnetic resonance spectrometer manufactured by Bruker Biospine AG corporation, Switzerland.
FIGS. 1(A) - (C) are scanning electron microscope images of linoleic acid-chitosan-based clothianidin nano-microcapsule pesticide of example 1 at different magnifications, wherein the magnification of FIG. 1(A) is 500 times, the magnification of FIG. 1(B) is 1000 times, and the magnification of FIG. 1(C) is 2000 times. As can be seen from figure 1, the prepared linoleic acid-chitosan-based clothianidin nano microcapsule is spherical, has a smooth surface and no clustering phenomenon, has an average particle size of about 285nm, and can be observed to be in a spherical regular structure without holes.
The detection proves that the linoleic acid-chitosan-based clothianidin nano microcapsule pesticide is obtained.
FIG. 2 is a comparison graph of IR spectra of linoleic acid and linoleic acid-chitosan based polyols of example 1, wherein a and b are linoleic acid and linoleic acid-chitosan based polyols, respectively; as can be seen from the figure, the absorption peak of the spectrogram a at 3016cm < -1 > is a stretching vibration peak of an unsaturated double bond in a linoleic acid long chain; and the stretching vibration peak at 3016cm-1 in the spectrogram b disappears, and a wide and strong absorption peak appears at 3405cm-1, which is the stretching vibration absorption peak of-OH, and indicates that the linoleic acid is grafted by chitosan.
FIG. 3 is a graph comparing the nuclear magnetic hydrogen spectra of linoleic acid and linoleic acid-chitosan based polyol in example 1, wherein a and b are linoleic acid-chitosan based polyol and linoleic acid, respectively; as can be seen from the figure, the characteristic peak of chemical shift δ ═ 5.3 to 5.5ppm in spectrum b is the C ═ C double bond in the linoleic acid long chain, while the characteristic peak of double bond at this point in spectrum a disappears, and new absorption peaks appear in spectrum a at chemical shifts δ ═ 2.5 to 2.7ppm, δ ═ 2.7 to 2.8ppm and δ ═ 3.7 to 3.8ppm, where δ ═ 2.5 to 2.7ppm belongs to hydrogen on the tertiary carbon connected to thiol, δ ═ 2.7 to 2.8ppm and δ ═ 3.7 to 3.8ppm respectively belong to hydrogen of two methylene groups on the grafted 2-mercaptoethanol, that is, the characteristic peak of two methylene groups in the thiol molecule grafted on the linoleic acid double bond by click reaction.
The detection results show that under the condition of UV light, the linoleic acid-chitosan-based polyol can be prepared by using a photoinitiator as a catalyst through a click reaction.
The shape of the nano microcapsule pesticide obtained in examples 2 to 10 is the same as that of example 1, and the characteristic peak of the vegetable oleic acid-chitosan-based polyol prepared in examples 2 to 10 is the same as that of example 1, and thus the description thereof is omitted.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (10)

1. The plant oleic acid-chitosan-based nano microcapsule pesticide is characterized in that a polymer formed by plant oleic acid-chitosan-based polyol and polyisocyanate is used as a wall material, the pesticide is used as a core material, the core material is embedded in the wall material, and the mass ratio of the wall material to the core material is 1: 1-5: 1;
the vegetable oleic acid-chitosan-based polyol is prepared by the following method: mixing the chitosan grafted vegetable oleic acid copolymer with mercaptan, a photoinitiator and a solvent, and magnetically stirring for 0-5 h and more than 0h at 100-1000 r/min under the irradiation of 100-1000W UV light, wherein the structural formula is as follows:
Figure FDA0003066443270000011
wherein n, k is 0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16.
2. The vegetable oleic-chitosan based nano-microcapsule pesticide according to claim 1, wherein the pesticide is at least one of abamectin, thymol, fluopyram, lambda-cyhalothrin, fenpropathrin, bifenthrin, clothianidin, fosthiazate, imidacloprid, chlorfenapyr or chlorantraniliprole.
3. The vegetable oleic-chitosan based nano-microcapsule pesticide according to claim 2, wherein the polyisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate.
4. The phytooleic-glycan-based nano-microcapsule pesticide as claimed in claim 3, wherein said phytooleic acid is at least one of ricinoleic acid, eleostearic acid, linoleic acid or oleic acid; the viscosity average molecular weight of the chitosan is 1.2 multiplied by 103～2.5×105The deacetylation degree is more than or equal to 90 percent.
5. The method for preparing the vegetable oleic acid-chitosan based nano microcapsule pesticide as claimed in any one of claims 1 to 4, is characterized by comprising the following steps:
1) preparing plant oleic acid-chitosan-based polyol into aqueous solution, adding polyisocyanate into the aqueous solution of the plant oleic acid-chitosan-based polyol, adding a catalyst, and reacting to obtain prepolymer;
2) adding a pesticide into acetone to prepare a pesticide solution, mixing the pesticide solution with the prepolymer obtained in the step 1), then adding the pesticide solution into an aqueous solution containing an emulsifier, adding a chain extender, and reacting at a constant temperature of 60-80 ℃ for 2-4 h to obtain the vegetable oleic acid-chitosan-based nano microcapsule pesticide.
6. The preparation method according to claim 5, wherein the vegetable oleic acid-chitosan-based polyol has a mass concentration of 1.0% to 5.0% in step 1); the amount of the catalyst is 1-2% of the total mass of the system, and preferably at least one of dibutyltin dilaurate, stannous octoate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate or triethylenediamine or tetraisobutyl titanate.
7. The preparation method according to claim 6, wherein the amount of the chain extender in the step 2) is 1 to 3% of the total mass of the system, and preferably at least one of 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, ethylenediamine or N, N-dihydroxy (diisopropyl) aniline; the emulsifier is preferably at least one of tween-80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty acid polyoxyethylene ether or cetyl trimethyl ammonium bromide.
8. The preparation method according to claim 7, wherein the mass concentration of the pesticide in the pesticide solution in the step 2) is preferably 1-5%; the stirring speed is preferably 100-2000 r/min; the mass ratio of the prepolymer to the pesticide is preferably 1: 1-5: 1.
9. The method according to any one of claims 5 to 8, wherein the vegetable oleic acid-chitosan-based polyol is prepared by: mixing the chitosan grafted plant oleic acid copolymer with mercaptan, a photoinitiator and a solvent, magnetically stirring for 0-5 h at 100-1000 r/min under the irradiation of 100-1000W UV light, then diluting with a first organic solvent, washing with a saturated inorganic salt solution, drying with a drying agent, filtering, finally removing the first organic solvent through a rotary evaporator, and placing the product in a vacuum drying oven for drying to obtain the plant oleic acid-chitosan-based polyol.
10. The use of the plant oleic acid-chitosan based nano-microcapsule pesticide as claimed in any one of claims 1 to 4 for the control of diseases and insect pests of tropical commercial crops.
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