Preparation method of environment-responsive polymer and plant essential oil synergistic pesticide targeting adjuvant

Abstract

The application discloses a preparation method of an environment-responsive polymer and plant essential oil synergistic pesticide targeting adjuvant, and relates to the technical field of bio-based pesticide adjuvant.The application provides the following technical scheme: a graft copolymer is prepared by condensation reaction of a water-soluble biodegradable polymer and a pathogenic fungus specific enzyme response oligosaccharide, a premix liquid is prepared from natural plant essential oil, a cosolvent and an emulsifier, and finally, a core-shell nanomicelle with the essential oil as the core and the modified polymer as the shell is formed through a self-assembly process, and the pesticide targeting adjuvant is obtained through concentration and filtration.A pathogenic fungus specific enzyme response system is constructed, precise drug release at a disease site is realized, the core-shell structure significantly improves the stability, leaf surface adhesion and slow release of the essential oil, and the rainwater washing retention rate is high;the bio-based material, essential oil activity and enzyme response mechanism are fused, and triple synergistic effect is achieved.The whole biodegradable raw material is green and low-toxic, the preparation process is flexible and can be simplified, is suitable for large-scale production, and has both economic value and ecological value.

Description

Technical Field

[0001] This invention relates to the field of bio-based pesticide targeted adjuvant preparation technology, and to a method for preparing an environmentally responsive polymer synergistic with plant essential oils as a pesticide targeted adjuvant. Background Technology

[0002] In agricultural production, chemical pesticides remain the core means of controlling fungal diseases in crops. Pesticide adjuvants, as key supporting materials for improving efficacy and optimizing application effects, suffer from significant technical defects in traditional products. Existing pesticide adjuvants are mostly ordinary surfactants, mineral oils, or simple polymer carriers, lacking targeted recognition capabilities and unable to accurately locate the infection sites of pathogenic fungi. After application, they are easily washed away by rainwater and spread ineffectively in the field, resulting in pesticide utilization rates of less than 30%, low efficacy, and requiring frequent and excessive application to achieve control, significantly increasing agricultural production costs.

[0003] Traditional adjuvants lack stability and are difficult to reliably encapsulate active ingredients such as natural plant essential oils, easily leading to problems such as stratification, sedimentation, and volatilization, resulting in a short shelf life. At the same time, adjuvants have poor biocompatibility, making it difficult to promote the penetration and retention of pesticides on crop leaves. Excessive application of pesticides directly leads to excessive pesticide residues, which not only threatens the quality and safety of agricultural products but also pollutes the soil and water ecological environment, contradicting the concept of green and ecological agriculture development.

[0004] Existing environmentally responsive pesticide adjuvant technologies suffer from high industrialization costs: synthesis relies on high-purity raw materials, and post-processing requires complex processes such as dialysis and freeze-drying, resulting in large equipment investment, high energy consumption, and long production cycles, making large-scale mass production difficult; moreover, the response mechanism is singular, only responding to limited environmental signals, with poor adaptability, and cannot simultaneously meet the requirements of targeting, stability, sustained release, and low-cost production. The industry urgently needs new, efficient, low-consumption, and green pesticide targeting adjuvant technology solutions. Summary of the Invention

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present invention provide a method for preparing a pesticide targeting adjuvant that combines environmentally responsive polymers and plant essential oils, which solves the problems of poor targeting, easy loss, low efficacy, high pesticide residue, insufficient stability and high industrialization cost of traditional pesticide adjuvants.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing an environmentally responsive polymer synergistic with plant essential oils as a pesticide targeting adjuvant specifically includes the following steps: S1: Dissolve 1.0-1.5 parts by weight of water-soluble biodegradable polymer matrix in 100-150 parts by volume of buffer solution with a concentration of 0.04-0.06 mol / L and pH=5.5-6.5. Stir at 50-70 rpm until completely dissolved. Then add 0.4-0.5 parts by weight of carbodiimide condensing agent and 0.25-0.3 parts by weight of N-hydroxyimide activator to the solution and activate at room temperature of 20-30°C for 20-40 minutes. Then slowly add 0.2-0.4 parts by weight of pathogenic fungal specific enzyme-responsive oligosaccharide and react at 25±1°C for 12 hours. Finally, after the reaction is completed, transfer the solution to a dialysis bag with a molecular weight cutoff of 6000-10000 Da for dialyzing and freeze-drying to obtain the graft copolymer. S2: Place 1.0~2.0 parts by weight of cosolvent in a reaction vessel and stir continuously at 80~120 rpm for 10~20 minutes. Then slowly add 0.5~1.2 parts by weight of natural plant essential oil and stir continuously at 80~120 rpm for 10~20 minutes until completely mixed. Finally, add 0.5~1.2 parts by weight of nonionic emulsifier and stir continuously at 80~120 rpm for 15~25 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: Place 0.6~0.8 parts by weight of the graft copolymer in S1 in deionized water at 35±2℃ and stir continuously at 50~80 rpm for 1.5~2.5 hours, then let stand for 10~14 hours to obtain a uniform and transparent modified viscous solution. S4: Cool the modified viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.4~0.6mL / min, while stirring at a low speed of 20~60rpm. Detect the absorbance of the solution at a wavelength of 600nm in real time. Stop adding the solution immediately when the absorbance reaches the preset value. Finally, continue stirring for 30 minutes to complete the self-assembly process and obtain the preliminary nanomicelle dispersion. S5: Add deionized water to the preliminary nanomicelle dispersion obtained in S4, adjust to the predetermined concentration of polymer-oligosaccharide graft copolymer and natural plant essential oil in the solution, and finally filter the solution with a 0.40~0.50μm microporous membrane to obtain the final environmentally responsive pesticide targeting adjuvant.

[0007] Preferably, the water-soluble biodegradable polymer substrate in S1 is at least one of polyglutamic acid, polyvinylpyrrolidone-acrylic acid copolymer, sodium carboxymethyl cellulose, hyaluronic acid, chitosan, and sodium alginate.

[0008] Preferably, the pathogenic fungal-specific enzyme-responsive oligosaccharide in S1 is at least one of chitosan oligosaccharide, aminoglucan oligosaccharide, aminocellulose oligosaccharide, β-glucan oligosaccharide, mannan oligosaccharide, and galactose oligosaccharide.

[0009] Preferably, the carbodiimide condensing agent in S1 is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride EDC·HCl, and the N-hydroxyimide activator in S1 is N-hydroxysuccinimide NHS.

[0010] Preferably, the natural plant essential oil mentioned in S2 is at least one of arborvitae essential oil, mugwort oil, and litsea cubeba oil.

[0011] Preferably, the cosolvent in S2 is 1,2-propanediol, and the nonionic emulsifier in S2 is Tween-20.

[0012] Preferably, the concentration of the uniform and transparent modified viscous solution in S3 is 0.8~1.0%.

[0013] Preferably, the preset value in S4 is an absorbance of 0.35 to 0.40.

[0014] Preferably, the concentration of the polymer-oligosaccharide graft copolymer in the adjustment solution in step S5 is 0.05% to 0.07%.

[0015] Preferably, the concentration of the natural plant essential oil in S5 is 0.08~0.12%.

[0016] The technical effects and advantages of the preparation method of the pesticide targeting adjuvant synergistically composed of environmentally responsive polymer and plant essential oil of the present invention are as follows: 1. This invention constructs a pathogenic fungal-specific enzyme response system that can accurately identify chitinase, glucanase, and other enzymes secreted by fungi, enabling targeted release of pesticides only when diseased, avoiding ineffective pesticide loss and non-target exposure, and significantly improving the accuracy of disease control.

[0017] 2. This invention forms core-shell nanomicelles through polymer self-assembly, with plant essential oil as the core and modified polymer as the shell, which greatly improves the stability and slow-release properties of essential oil, while enhancing the adhesion and penetration ability of adjuvants on plant leaves, resulting in high retention rate when washed away by rainwater and a significantly extended duration of effectiveness.

[0018] 3. This invention integrates the strong adhesion of biodegradable polymers, the antibacterial and insecticidal activity of natural plant essential oils, and the enzyme response enrichment mechanism, resulting in a significant triple synergistic effect. It can reduce pesticide usage by 30% to 40% while improving disease control by 50% to 60%, thereby reducing pesticide residues and environmental pressure.

[0019] 4. This invention uses fully biodegradable raw materials, which are non-toxic, have low residues, and are environmentally friendly; the preparation process is flexible and controllable, which can simplify post-processing steps such as dialysis and freeze-drying, and is suitable for large-scale industrial production. It has low energy consumption and production costs, and has both economic value and universal applicability. Attached Figure Description

[0020] Figure 1 This is a flowchart of a method for preparing an environmentally responsive pesticide targeting adjuvant that synergizes with plant essential oils, as proposed in this invention. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0022] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0023] Example 1 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Polyglutamic acid (γ-PGA), arborvitae essential oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), chitosan oligosaccharide.

[0024] Experimental objective: A chitinase-responsive core-shell nanomicelle environmentally responsive polymer synergistic with plant essential oils was prepared as a pesticide targeting adjuvant.

[0025] Experimental steps: S1: 1.2 kg of linear polyglutamic acid was dissolved in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. The solution was stirred at 60 rpm until completely dissolved. Then, 0.45 kg of EDC・HCl and 0.27 kg of NHS were added to the solution in sequence and activated at room temperature of 25 °C for 30 minutes. Then, 0.3 kg of chitosan oligosaccharide was slowly added and reacted at 25±1 °C for 12 hours. Finally, after the reaction was completed, the solution was transferred to a dialysis bag with a molecular weight cutoff of 8000 Da for dialyzing and freeze-drying to obtain a white flocculent γ-PGA-g-chitosan oligosaccharide graft copolymer. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of arborvitae essential oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: Place 0.7 kg of the γ-PGA-g-chitidine oligosaccharide graft copolymer obtained in S1 in deionized water at 35±2℃ and stir continuously at 50-80 rpm for 2 hours, then let stand for 12 hours to obtain a uniform and transparent modified polyglutamic acid viscous solution with a concentration of 0.8-1.0%. S4: Cool the modified polyglutamic acid viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm until the solution turns into a microemulsion blue. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain a preliminary core-shell nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of γ-PGA-g-chitosan oligosaccharide to 0.06% and the concentration of arborvitae essential oil to 0.1%. Finally, filter the solution through a 0.45μm microporous membrane to obtain the final chitinase-responsive pesticide targeting adjuvant.

[0026] Experimental results: See Table 1 for details.

[0027] Table 1: Test Results of Example 1

[0028] The core innovation of this invention lies in the pioneering grafting of chitosan oligosaccharides onto polyglutamic acid molecular chains, constructing an intelligent response system sensitive only to chitinase secreted by plant pathogenic fungi, achieving precise targeting with drug release only when diseased. Simultaneously, utilizing the amphiphilic nature of modified polyglutamic acid, nanomicelles spontaneously form in aqueous solution, with hydrophobic arborvitae essential oil as the core and hydrophilic modified polyglutamic acid as the shell, significantly improving the stability, slow-release properties, and adjuvant penetration ability of the essential oil on plant leaves. Ultimately, through the triple synergistic effect of the strong adhesion of modified polyglutamic acid, the natural antibacterial and insecticidal activity of arborvitae essential oil, and the chitinase-responsive enrichment mechanism, pesticide usage is reduced by more than 40%, while the control effect is improved by more than 60%.

[0029] Example 2 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Polyvinylpyrrolidone-acrylic acid copolymer (PVP-co-AA, acrylic acid molar content 10%-20%, molecular weight 40,000-60,000 Da), Artemisia argyi oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), and amino-modified dextran oligosaccharides (molecular weight 3000-5000 Da).

[0030] Experimental objective: A pesticide targeting adjuvant synergistic with plant essential oils was prepared using an environmentally responsive polymer of dextranase-responsive core-shell nanomicelles.

[0031] Experimental steps: S1: 1.2 kg of polyvinylpyrrolidone-acrylic acid copolymer was dissolved in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. The solution was stirred at 60 rpm until completely dissolved. Then, 0.45 kg of EDC・HCl and 0.27 kg of NHS were added to the solution in sequence and activated at room temperature of 25 °C for 30 minutes. Then, 0.3 kg of amino-glucan oligosaccharide was slowly added and reacted at 25±1 °C for 12 hours. Finally, after the reaction was completed, the solution was transferred to a dialysis bag with a molecular weight cutoff of 8000 Da for dialyzing and freeze-drying to obtain a white flocculent PVP-co-AA-g-glucan oligosaccharide graft copolymer. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of Artemisia argyi oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: Place 0.7 kg of the PVP-co-AA-g-glucan oligosaccharide graft copolymer obtained in S1 in deionized water at 35±2℃ and stir continuously at 50-80 rpm for 2 hours. Then let it stand for 12 hours to obtain a uniform and transparent viscous solution of modified polyvinylpyrrolidone copolymer with a concentration of 0.8-1.0%. S4: Cool the viscous solution of the modified polyvinylpyrrolidone copolymer obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain the nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of PVP-co-AA-g-glucan oligosaccharide in the solution to 0.06% and the concentration of Artemisia argyi oil to 0.1%. Finally, filter the solution with a 0.45 μm microporous membrane to obtain the final glucanase-responsive pesticide targeting adjuvant.

[0032] Experimental results: See Table 2 for details.

[0033] Table 2: Test Results of Example 2

[0034] The core innovation of Example 2 lies in the pioneering grafting of dextran oligosaccharides onto the molecular chain of polyvinylpyrrolidone-acrylic acid copolymer, constructing an intelligent response system sensitive only to dextranase secreted by plant pathogenic fungi, achieving precise targeting of drug release only when disease occurs; simultaneously, utilizing the amphiphilicity of modified polyvinylpyrrolidone, nanomicelles spontaneously form in aqueous solution with hydrophobic Artemisia argyi oil as the core and hydrophilic modified polyvinylpyrrolidone as the shell, significantly improving the stability, slow-release properties of the essential oil, and the penetration ability of adjuvants on plant leaves; ultimately, through the triple synergistic effect of the strong film-forming properties of modified polyvinylpyrrolidone, the broad-spectrum insecticidal and antibacterial activity of Artemisia argyi oil, and the dextranase-responsive enrichment mechanism, pesticide usage is reduced by more than 35%, while the control effect is improved by more than 55%.

[0035] Example 3 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Sodium carboxymethyl cellulose (CMC-Na, degree of substitution 0.7-0.9, molecular weight approximately 90,000 Da), Litsea cubeba oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), and amino-modified cellulose oligosaccharides (molecular weight 3000-5000 Da).

[0036] Experimental objective: A cellulase-responsive core-shell nanomicelles environmentally responsive polymer synergistic with plant essential oils was prepared as a pesticide targeting adjuvant.

[0037] Experimental steps: S1: Dissolve 1.2 kg of sodium carboxymethyl cellulose in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. Stir at 60 rpm until completely dissolved. Then, add 0.45 kg of EDC・HCl and 0.27 kg of NHS to the solution sequentially and activate at room temperature of 25 °C for 30 minutes. Then, slowly add 0.3 kg of amino-modified cellulose oligosaccharide and react at 25±1 °C for 12 hours. Finally, after the reaction is completed, transfer the solution to a dialysis bag with a molecular weight cutoff of 8000 Da for dialyzing and freeze-drying to obtain a white flocculent CMC-g-cellulose oligosaccharide graft copolymer. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of Litsea cubeba oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: Place 0.7 kg of the CMC-g-cellulose oligosaccharide graft copolymer obtained in S1 in deionized water at 35±2℃ and stir continuously at 50-80 rpm for 2 hours, then let stand for 12 hours to obtain a uniform and transparent modified carboxymethyl cellulose viscous solution with a concentration of 0.8~1.0%. S4: Cool the modified carboxymethyl cellulose viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain a nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of CMC-g-cellulose oligosaccharide in the solution to 0.06% and the concentration of Litsea cubeba oil to 0.1%. Finally, filter the solution with a 0.45μm microporous membrane to obtain the final cellulase-responsive pesticide targeting adjuvant.

[0038] Experimental results: See Table 3 for details.

[0039] Table 3: Test Results of Example 3

[0040] The core innovation of Example 3 lies in the pioneering grafting of cellulose oligosaccharides onto the modified carboxymethyl cellulose molecular chain, constructing an intelligent response system sensitive only to cellulase secreted by plant pathogenic fungi, achieving precise targeting of drug release only when disease occurs; simultaneously, utilizing the amphiphilicity of modified carboxymethyl cellulose, nanomicelles spontaneously form in aqueous solution with hydrophobic Litsea cubeba oil as the core and hydrophilic modified carboxymethyl cellulose as the shell, significantly improving the stability, slow-release properties of the essential oil, and the penetration ability of adjuvants on plant leaves; ultimately, through the triple synergistic effect of the thermogel film-forming properties of modified carboxymethyl cellulose, the potent bactericidal activity of Litsea cubeba oil, and the cellulase-responsive enrichment mechanism, pesticide usage is reduced by more than 30%, while the control effect is improved by more than 50%.

[0041] Example 4 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Polyglutamic acid (γ-PGA), arborvitae essential oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), chitosan oligosaccharide.

[0042] Experimental objective: A simplified post-processing method was developed to prepare an environmentally responsive polymer and plant essential oil synergistic pesticide targeting adjuvant.

[0043] Experimental steps: S1: 1.2 kg of linear polyglutamic acid was dissolved in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. The solution was stirred at 60 rpm until completely dissolved. Then, 0.45 kg of EDC・HCl and 0.27 kg of NHS were added to the solution in sequence and activated at room temperature of 25 °C for 30 minutes. Then, 0.3 kg of chitosan oligosaccharide was slowly added and reacted at 25±1 °C for 12 hours to obtain γ-PGA-g-chitosan oligosaccharide graft copolymer. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of arborvitae essential oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: The graft copolymer obtained in S1 is placed in deionized water at 35±2℃ and stirred continuously at 50-80 rpm for 2 hours, and then allowed to stand for 12 hours to obtain a uniform and transparent modified polyglutamic acid viscous solution with a concentration of 0.8-1.0%. S4: Cool the modified polyglutamic acid viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain a nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of γ-PGA-g-chitosan oligosaccharide to 0.06% and the concentration of arborvitae essential oil to 0.1%. Finally, filter the solution through a 0.45μm microporous membrane to obtain the final chitinase-responsive pesticide targeting adjuvant.

[0044] Experimental results: See Table 4 for details.

[0045] Table 4: Test Results of Example 4

[0046] This embodiment substantially eliminates the post-processing steps of dialysis and freeze-drying in the original embodiment 1, and directly uses the grafting reaction solution for the subsequent self-assembly process, shortening the production cycle from 84 hours to 18 hours and reducing energy consumption by more than 60%. At the same time, it fully retains the chitinase-specific response mechanism and core-shell nanomicelle structure. Ultimately, through the triple synergistic effect of the strong adhesion of modified polyglutamic acid, the natural antibacterial and insecticidal activity of arborvitae essential oil, and the chitinase response enrichment mechanism, the amount of pesticide used is reduced by more than 37%, while the control effect is improved by more than 58%, making it particularly suitable for large-scale continuous industrial production.

[0047] Example 5 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Polyvinylpyrrolidone-acrylic acid copolymer (PVP-co-AA, acrylic acid molar content 10%-20%, molecular weight 40,000-60,000 Da), Artemisia argyi oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC・HCl), and amino-modified dextran oligosaccharides (molecular weight 3000-5000 Da).

[0048] Experimental objective: A one-step synthesis method was developed for a dextranase-responsive core-shell nanomicelle pesticide targeting adjuvant, eliminating post-processing steps to reduce production costs.

[0049] Experimental steps: S1: Dissolve 1.2 kg of polyvinylpyrrolidone-acrylic acid copolymer in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. Stir at 60 rpm until completely dissolved. Then, add 0.45 kg of EDC・HCl and 0.27 kg of NHS to the solution sequentially and activate at room temperature of 25 °C for 30 minutes. Then, slowly add 0.3 kg of amino-modified dextran oligosaccharide and react at 25±1 °C for 12 hours to obtain a white flocculent PVP-co-AA-g-dextran oligosaccharide graft copolymer reaction solution. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of Artemisia argyi oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: The graft copolymer reaction solution obtained in S1 is placed in deionized water at 35±2℃ and stirred continuously at 50-80 rpm for 2 hours, and then allowed to stand for 12 hours to obtain a uniform and transparent viscous solution of modified polyvinylpyrrolidone copolymer with a concentration of 0.8-1.0%. S4: Cool the modified polyvinylpyrrolidone viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain a nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of PVP-co-AA-g-glucan oligosaccharide in the solution to 0.06% and the concentration of Artemisia argyi oil to 0.1%. Finally, filter the solution with a 0.45 μm microporous membrane to obtain the final glucanase-responsive pesticide targeting adjuvant.

[0050] Experimental results: See Table 5 for details.

[0051] Table 5: Test Results of Example 5

[0052] This embodiment substantially eliminates the post-processing steps of dialysis and freeze-drying in the original embodiment 2, and directly uses the grafting reaction solution for the subsequent self-assembly process, reducing production costs by more than 45%. At the same time, it fully retains the specific response mechanism of dextranase and the core-shell nanomicelle structure. Ultimately, through the triple synergistic effect of the strong film-forming properties of modified polyvinylpyrrolidone, the broad-spectrum insecticidal and antibacterial activity of Artemisia argyi oil, and the dextranase response enrichment mechanism, the amount of pesticide used is reduced by more than 32%, while the control effect is improved by more than 53%, making it particularly suitable for large-scale application in economic crops such as wheat and corn.

[0053] Example 6 This embodiment provides a method for preparing a pesticide targeting adjuvant that combines an environmentally responsive polymer with plant essential oils. The specific implementation steps include: Experimental materials: Sodium carboxymethyl cellulose (CMC-Na, degree of substitution 0.7-0.9, molecular weight approximately 90,000 Da), Litsea cubeba oil, 1,2-propanediol, Tween-20, N-hydroxysuccinimide (NHS), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl), and amino-modified cellulose oligosaccharides (molecular weight 3000-5000 Da).

[0054] Experimental objective: To investigate the impact of simplified production processes on product performance.

[0055] Experimental steps: S1: Dissolve 1.2 kg of sodium carboxymethyl cellulose in 120 L of Tris buffer solution with a concentration of 0.05 mol / L and pH=6.0. Stir at 60 rpm until completely dissolved. Then, add 0.45 kg of EDC・HCl and 0.27 kg of NHS to the solution in sequence and activate at room temperature of 25 °C for 30 minutes. Then, slowly add 0.3 kg of amino-modified cellulose oligosaccharide and react at 25±1 °C for 12 hours to obtain a white flocculent CMC-g-cellulose oligosaccharide graft copolymer reaction solution. S2: Place 1.5 kg of 1,2-propanediol in a reaction vessel and stir continuously at 100 rpm for 15 minutes. Then slowly add 0.8 kg of Litsea cubeba oil and stir continuously at 100 rpm for 15 minutes until completely mixed. Finally, add 0.6 kg of Tween-20 and stir continuously at 100 rpm for 20 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: The graft copolymer reaction solution obtained in S1 was placed in deionized water at 35±2℃ and stirred continuously at 50-80 rpm for 2 hours, and then allowed to stand for 12 hours to obtain a uniform and transparent viscous solution of modified carboxymethyl cellulose with a concentration of 0.8~1.0%. S4: Cool the modified carboxymethyl cellulose viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.5mL / min, while stirring at a low speed of 30-50rpm. When the absorbance of the solution at a wavelength of 600nm reaches 0.35~0.40, stop adding immediately and continue stirring for 30 minutes to complete the self-assembly process and obtain a nanomicelle dispersion. S5: Add deionized water to the nanomicelle dispersion obtained in S4 to adjust the concentration of CMC-g-cellulose oligosaccharide in the solution to 0.06% and the concentration of Litsea cubeba oil to 0.1%. Finally, filter the solution with a 0.45μm microporous membrane to obtain the final cellulase-responsive pesticide targeting adjuvant.

[0056] Experimental results: See Table 6 for details.

[0057] Table 6: Test Results of Example 6

[0058] This embodiment substantially omits the post-processing steps of dialysis and freeze-drying in the original embodiment 3, directly using the grafting reaction solution for the subsequent self-assembly process, greatly simplifying the production process and eliminating the need for large-scale freeze-drying equipment; at the same time, it fully retains the cellulase-specific response mechanism and core-shell nanomicelle structure, and ultimately achieves a reduction of pesticide dosage by more than 27% and an improvement in control efficacy by more than 49% through the triple synergistic effect of the thermal gelation film-forming properties of modified carboxymethyl cellulose, the potent bactericidal activity of Litsea cubeba oil, and the cellulase-responsive enrichment mechanism, making it particularly suitable for the production and promotion of small and medium-sized pesticide enterprises.

[0059] Comparing the various examples, Example 1 achieved the optimal balance between response specificity, leaf adhesion, sustained-release properties of essential oils, and synergistic effects. The precise self-assembly of chitinase-responsive core-shell nanomicelles ingeniously improved pesticide targeted delivery efficiency and disease control performance, making it suitable for precision disease control in high-value-added vegetables, fruits, and other economic crops. While Example 2 had slightly lower synergistic coefficients and rainwater runoff retention rates than Example 1, its excellent film-forming properties and broad-spectrum insecticidal activity of Artemisia argyi oil made it more effective in scenarios involving both pest and disease control. Example 3 used sodium carboxymethyl cellulose with thermogel properties as the polymer substrate, but its enzyme response sensitivity and leaf adhesion performance were slightly inferior to the polyglutamic acid and polyvinylpyrrolidone system. Example 4 employed a simplified post-processing method that omitted dialysis and freeze-drying, but its product purity and long-term storage stability were slightly lower than those of Example 1 prepared using the complete process. Example 5 used a simplified post-processing method to reduce production costs, but its particle size distribution uniformity and active ingredient retention rate decreased. Example 6 uses a simplified production process adapted to small and medium-sized enterprises, but its overall prevention and control effect is slightly lower than that of other examples.

[0060] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims.

[0061] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an environmentally responsive polymer synergistic with plant essential oils as a pesticide targeting adjuvant, characterized in that, Specifically, the following steps are included: S1: Dissolve 1.0-1.5 parts by weight of water-soluble biodegradable polymer matrix in 100-150 parts by volume of buffer solution with a concentration of 0.04-0.06 mol / L and pH=5.5-6.

5. Stir at 50-70 rpm until completely dissolved. Then add 0.4-0.5 parts by weight of carbodiimide condensing agent and 0.25-0.3 parts by weight of N-hydroxyimide activator to the solution and activate at room temperature of 20-30°C for 20-40 minutes. Then slowly add 0.2-0.4 parts by weight of pathogenic fungal specific enzyme-responsive oligosaccharide and react at 25±1°C for 12 hours. Finally, after the reaction is completed, transfer the solution to a dialysis bag with a molecular weight cutoff of 6000-10000 Da for dialyzing and freeze-drying to obtain the graft copolymer. S2: Place 1.0~2.0 parts by weight of cosolvent in a reaction vessel and stir continuously at 80~120 rpm for 10~20 minutes. Then slowly add 0.5~1.2 parts by weight of natural plant essential oil and stir continuously at 80~120 rpm for 10~20 minutes until completely mixed. Finally, add 0.5~1.2 parts by weight of nonionic emulsifier and stir continuously at 80~120 rpm for 15~25 minutes to obtain a homogeneous and transparent essential oil-cosolvent-emulsifier premix. S3: Place 0.6~0.8 parts by weight of the graft copolymer in S1 in deionized water at 35±2℃ and stir continuously at 50~80 rpm for 1.5~2.5 hours, then let stand for 10~14 hours to obtain a uniform and transparent modified viscous solution. S4: Cool the modified viscous solution obtained in S3 to 25±1℃, and then slowly add the essential oil-cosolvent-emulsifier premix obtained in S2 at a speed of 0.4~0.6mL / min, while stirring at a low speed of 20~60rpm. Detect the absorbance of the solution at a wavelength of 600nm in real time. Stop adding the solution immediately when the absorbance reaches the preset value. Finally, continue stirring for 30 minutes to complete the self-assembly process and obtain the preliminary nanomicelle dispersion. S5: Add deionized water to the preliminary nanomicelle dispersion obtained in S4, adjust to the predetermined concentration of polymer-oligosaccharide graft copolymer and natural plant essential oil in the solution, and finally filter the solution with a 0.40~0.50μm microporous membrane to obtain the final environmentally responsive pesticide targeting adjuvant.

2. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The water-soluble biodegradable polymer substrate mentioned in S1 is at least one of polyglutamic acid, polyvinylpyrrolidone-acrylic acid copolymer, sodium carboxymethyl cellulose, hyaluronic acid, chitosan, and sodium alginate.

3. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The pathogenic fungal specific enzyme-responsive oligosaccharide mentioned in S1 is at least one of chitin oligosaccharide, amino-modified dextran oligosaccharide, amino-modified cellulose oligosaccharide, β-glucan oligosaccharide, mannan oligosaccharide, and galactose oligosaccharide.

4. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The carbodiimide condensing agent mentioned in S1 is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride EDC·HCl, and the N-hydroxyimide activator mentioned in S1 is N-hydroxysuccinimide NHS.

5. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The natural plant essential oil mentioned in S2 is at least one of the following: arborvitae essential oil, mugwort oil, and litsea cubeba oil.

6. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The cosolvent mentioned in S2 is 1,2-propanediol, and the nonionic emulsifier mentioned in S2 is Tween-20.

7. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The concentration of the uniform and transparent modified viscous solution described in S3 is 0.8~1.0%.

8. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The preset value mentioned in S4 is an absorbance of 0.35~0.

40.

9. The preparation method of the pesticide targeting adjuvant synergistically combining environmentally responsive polymer and plant essential oil as described in claim 1, characterized in that, The concentration of the polymer-oligosaccharide graft copolymer in the solution described in S5 is 0.05%~0.07%.

10. The preparation method of an environmentally responsive polymer synergistic with plant essential oils as described in claim 1, characterized in that, The concentration of the natural plant essential oils mentioned in S5 is 0.08~0.12%.

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