Insect pheromone ink, insect pheromone attractant core, and preparation, application and recycling thereof

Abstract

The present invention relates to the technical field of agricultural pest control, and in particular to an insect pheromone ink, an insect pheromone attractant core, and their preparation, application, and recycling. The insect pheromone ink comprises a thermoplastic biodegradable polymer material, an alcohol plasticizer, a graded volatile organic solvent, and an insect pheromone; it may further comprise a functional modification material; the functional modification material comprises lignin sulfonate and a metal salt. The insect pheromone ink provided by the present invention can be made into an insect pheromone attractant core through 3D printing, and the preparation process is simple and the cost is low. At the same time, the insect pheromone attractant core has a high pheromone encapsulation rate, a long duration of field release, is degradable, recyclable, and is environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of agricultural pest control, and in particular to an insect pheromone ink, an insect pheromone attractant core, and the preparation, application and recovery thereof. Background Art

[0002] Agriculture, a cornerstone of the global economy and human survival, faces the dual challenges of climate change and population growth. At the same time, monoculture practices foster the spread of pests and pathogens, resulting in annual losses of 26% to 80% in agricultural production. Traditional pest management strategies rely on chemical pesticides, which, while effective in the short term, have increasingly negative impacts on the environment and human health. Extensive pesticide use not only pollutes soil and water resources, damages biodiversity, but also increases pest resistance.

[0003] Insect pheromones are chemicals produced by insects, typically released by female insects to attract males of the opposite sex for mating. As an environmentally friendly alternative to traditional pesticides, insect pheromones play a significant role in integrated pest management (IPM) strategies, with applications encompassing monitoring pest populations, trapping, and mating disruption. This approach is not only highly species-specific, ensuring its effectiveness only against specific pests, but also offers highly effective control with minimal application, significantly reducing the burden on the environment.

[0004] Most pheromone components are volatile and chemically unstable. Unless formulated in a controlled-release device, they evaporate quickly. Current carriers used to extend the duration of pheromones (such as rubber and polyethylene plastic) typically use solvents to physically bind the pheromone to the material, resulting in shortcomings such as short duration of effect and poor degradability. In recent years, microcapsules, nanoparticles, and metal-organic frameworks have emerged as promising methods for sustained-release pheromones. While these novel carriers offer significant advantages for controlled pheromone release, they often suffer from low pheromone loading, short duration of release in the field, complex preparation processes, and high costs. Therefore, there is an urgent need for efficient, environmentally friendly, industrially scalable, and cost-effective pheromone carriers. Summary of the Invention

[0005] In view of this, the present invention aims to provide an insect pheromone ink, an insect pheromone attractant core, and their preparation, application, and recycling. The insect pheromone ink provided by the present invention can be made into an insect pheromone attractant core through 3D printing. The preparation process is simple and cost-effective. Furthermore, the insect pheromone attractant core has a high pheromone encapsulation rate, a long duration of field release, and is biodegradable and recyclable, making it environmentally friendly.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides an insect pheromone ink, comprising the following components: a thermoplastic biodegradable polymer material, an alcohol plasticizer, a graded volatile organic solvent and an insect pheromone;

[0008] The graded volatile organic solvents include at least one high volatility organic solvent and at least one low volatility organic solvent;

[0009] The mass content of the thermoplastic biodegradable polymer material in the insect pheromone ink is 12-16%;

[0010] The mass of the alcohol plasticizer is 0.2-3% of the mass of the thermoplastic biodegradable polymer material;

[0011] The mass of the insect pheromone is 0.01-15% of the mass of the thermoplastic biodegradable polymer material.

[0012] Preferably, the method further comprises an aqueous solution of a functional material; the functional material comprises lignin sulfonate and a metal salt; the concentrations of the lignin sulfonate and the metal salt in the aqueous solution of the functional material are independently 0.25 to 1 g / mL;

[0013] The mass of the lignin sulfonate is 0.02-0.5% of the mass of the thermoplastic biodegradable polymer material; the mass of the metal salt is 0.1-2.5% of the mass of the thermoplastic biodegradable polymer material; and the metal salt includes one or more of trivalent iron salt, aluminum salt and divalent copper salt.

[0014] Preferably, the lignin sulfonate comprises sodium lignin sulfonate and / or calcium lignin sulfonate;

[0015] The ferric salt includes ferric chloride; the aluminum salt includes aluminum chloride; and the divalent copper salt includes copper chloride.

[0016] Preferably, the thermoplastic biodegradable polymer material includes one or more of polylactic acid, polycaprolactone, polyhydroxybutyrate and cellulose acetate.

[0017] Preferably, the alcohol plasticizer includes one or more of polyethylene glycol, glycerol and polypropylene alcohol.

[0018] Preferably, the high volatility organic solvent includes at least one of acetone, dichloromethane and ethanol; and the low volatility organic solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0019] The present invention provides an insect pheromone attractant core, which is prepared by 3D printing of the insect pheromone ink described in the above scheme.

[0020] The present invention provides a method for preparing the insect pheromone attractant core described in the above scheme, comprising the following steps: 3D printing the insect pheromone ink described in the above scheme, wherein the 3D printing layer height is 0.8-1.5 mm, the filling density is 70-100%, and the printing speed is 10-20 mm / s.

[0021] The present invention provides the use of the insect pheromone attractant core described in the above scheme in pest control.

[0022] The present invention provides a method for recycling and reusing the insect pheromone attractant core described in the above scheme, comprising the following steps: mixing the recovered insect pheromone attractant core powder and insect pheromone with graded volatile organic solvents to obtain drug-loaded ink, which is reused for 3D printing.

[0023] The present invention provides an insect pheromone ink, comprising the following components: a thermoplastic biodegradable polymer material, an alcohol plasticizer, a graded volatile organic solvent, and an insect pheromone; the graded volatile organic solvent comprises at least one high-volatile organic solvent and at least one low-volatile organic solvent; the mass content of the thermoplastic biodegradable polymer material in the insect pheromone ink is 12-16%; the mass of the alcohol plasticizer is 0.2-3% of the mass of the thermoplastic biodegradable polymer material; and the mass of the insect pheromone is 0.01-15% of the mass of the thermoplastic biodegradable polymer material.

[0024] The ink of the present invention uses thermoplastic biodegradable polymer materials as the base material, and the insect pheromone attractant core made after 3D printing has good degradation performance and is environmentally friendly; the insect pheromone is dissolved in the ink, and the content of the insect pheromone can be adjusted according to actual needs, avoiding the defect of low insect pheromone loading in the traditional loading method; in addition, after the ink provided by the present invention is printed, the insect pheromone will be evenly distributed between the cross-linked network of the thermoplastic biodegradable polymer material, achieving a sustained release effect, and the release duration in the field is long. The present invention selects graded volatile organic solvents. At room temperature, the high-volatile organic solvent helps the ink to dry quickly at room temperature, thereby maintaining the molding ability during the printing process, while the residual low-volatile organic solvent helps to maintain the fluidity of the ink, ensuring the smoothness of the printing process.

[0025] Furthermore, the insect pheromone ink provided by the present invention also includes a functional modification material; the functional modification material includes lignin sulfonate and a metal salt. Lignin has UV protection, anti-aging, and flame retardant properties. The present invention introduces lignin sulfonate and metal ions to enhance the ink's UV resistance and cross-linking effect after printing, thereby improving the stability and applicability of the 3D-printed insect pheromone lure.

[0026] The present invention also provides a method for recycling the insect pheromone attractant core, thereby achieving efficient and rapid reuse of the attractant core. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic diagram of the preparation process of the insect pheromone ink of Example 2;

[0028] Figure 2 Photos of CP and CP-SL-Fe ink extrusion molding;

[0029] Figure 3 (a) Viscosity of CP and CP-SL-Fe inks as a function of shear rate, and (b) storage modulus (G′) and loss modulus (G″) as a function of oscillation stress.

[0030] Figure 4 The morphology of CP and CP-SL-Fe cores is shown in Figure 1, where (a, c) are photos of the sample appearance and (b, d) are three-dimensional super-depth-of-field photos.

[0031] Figure 5 Scanning electron microscope images of CP (a, b) and CP-SL-Fe decoy core (c, d);

[0032] Figure 6 This is the iron element spectrum of the CP-SL-Fe decoy core;

[0033] Figure 7 (a) FTIR spectra of CP core, CP-SL-Fe core and CP-SL core modified with lignin only, (b) XRD patterns of CP core, CP-SL core and CP-SL-Fe core, (c) XPS scans of CP core and CP-SL-Fe core, (d) O1s XPS spectrum of CP core, (e) O1s XPS spectrum of CP-SL-Fe core;

[0034] Figure 8 (a) TGA thermogravimetric curves of CP-K, CP, and CP-SL-Fe lures, (b) stress-strain curves of CP and CP-SL-Fe lures, (c) UV-visible diffuse reflectance of CP and CP-SL-Fe lures, (d) water contact angles of CP and CP-SL-Fe lures, (e) soil degradation weight loss rates of CP lures, CP-SL-Fe lures, and commercial rubber plug lures (CK), (f) soil degradation experimental photos of CP lures, CP-SL-Fe lures, and commercial rubber plug lures.

[0035] Figure 9(a) Laboratory release curves of CP and CP-SL-Fe lures, (b) Field trapping photos of 3D-printed lures, (c) Average weekly field catches of CP, CP-SL-Fe, and commercially available rubber plug lures, (d) Cumulative field catches (6 weeks) of CP, CP-SL-Fe, and commercially available rubber plug lures (CK);

[0036] Figure 10 The drug release kinetics model analysis results of CP decoy core and CP-SL-Fe decoy core;

[0037] Figure 11 (a) Green processing roadmap, (b) recycling experiment photos, (c, d) photos of the printing smoothness and plasticity of the recycled ink, (e) SEM morphology of rCP-SL-Fe, (f) EDS spectrum of iron element of rCP-SL-Fe lure, (g) FTIR spectrum of rCP-SL-Fe lure, (h) encapsulation efficiency comparison of CP-SL-Fe and rCP-SL-Fe lure, (i) stress-strain comparison of CP-SL-Fe and rCP-SL-Fe lure. DETAILED DESCRIPTION

[0038] The present invention provides an insect pheromone ink, comprising the following components: a thermoplastic biodegradable polymer material, an alcohol plasticizer, a graded volatile organic solvent and an insect pheromone;

[0039] The graded volatile organic solvents include at least one high volatility organic solvent and at least one low volatility organic solvent;

[0040] The mass content of the thermoplastic biodegradable polymer material in the insect pheromone ink is 12-16%;

[0041] The mass of the alcohol plasticizer is 0.2-3% of the mass of the thermoplastic biodegradable polymer material;

[0042] The mass of the insect pheromone is 0.01-15% of the mass of the thermoplastic biodegradable polymer material.

[0043] In the present invention, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0044] The insect pheromone ink provided by the present invention comprises a thermoplastic biodegradable polymer material. In the present invention, the thermoplastic biodegradable polymer material preferably comprises one or more of polylactic acid, polycaprolactone, polyhydroxybutyrate, and cellulose acetate, with cellulose acetate being more preferred. In the present invention, the number average molecular weight (Mn) of the cellulose acetate is preferably 40,000 to 60,000 g / mol, and in specific embodiments, it can be 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, or 60,000 g / mol. The acetyl content of the cellulose acetate is preferably 35 to 45 wt%. In the present invention, the weight content of the thermoplastic biodegradable polymer material in the insect pheromone ink is 12 to 16%, and in specific embodiments, it can be 12%, 13%, 14%, 15%, or 16%. In the present invention, the thermoplastic biodegradable polymer material serves as the base material of the insect pheromone ink.

[0045] The insect pheromone ink provided herein includes an alcohol plasticizer. The alcohol plasticizer comprises 0.2-3% of the mass of the thermoplastic biodegradable polymer material, and in specific embodiments, may be 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%. In the present invention, the alcohol plasticizer preferably comprises one or more of polyethylene glycol, glycerol, and polypropylene alcohol, with polyethylene glycol being more preferred. In the present invention, the number average molecular weight (Mn) of the polyethylene glycol is preferably 4000-8000 g / mol, and in specific embodiments, may be 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, or 8000 g / mol. In the present invention, the alcohol plasticizer can improve the mechanical properties of the 3D-printed insect pheromone attractant core, increasing its flexibility and ductility. This helps maintain the material's morphology during the 3D printing process and may also improve the adaptability of the insect pheromone attractant core in practical use. When the alcohol plasticizer is polyethylene glycol (PEG), it also has the following effects: PEG has good solubility in solvents and can help dissolve other components, especially for some poorly soluble compounds, it can provide a good dissolution environment, facilitating the preparation and uniform distribution of insect pheromone attractants; in addition, PEG can also regulate the release performance of the attractant. It affects the release rate of sex pheromones by changing the physical properties of the attractant, thereby improving the effect and duration of the attractant.

[0046] The insect pheromone ink provided by the present invention includes graded volatile organic solvents. The graded volatile organic solvents include at least one high-volatile organic solvent and at least one low-volatile organic solvent; the high-volatile organic solvent preferably includes at least one of acetone, dichloromethane and ethanol; the low-volatile organic solvent preferably includes at least one of N,N-dimethylformamide and dimethyl sulfoxide. In the present invention, the volume percentage of the high-volatile organic solvent in the graded volatile organic solvent is preferably 70-80%. The present invention selects graded volatile organic solvents. At room temperature, the high-volatile organic solvent helps the ink dry quickly at room temperature, thereby maintaining the molding ability during the printing process, while the residual low-volatile organic solvent helps maintain the fluidity of the ink, ensuring smoothness during the printing process.

[0047] The insect pheromone ink provided by the present invention includes an insect pheromone, the mass of which is 0.01% to 15% of the mass of the thermoplastic biodegradable polymer material. Persons skilled in the art can adjust this mass based on actual needs. In embodiments of the present invention, the mass of the insect pheromone can be 0.01%, 0.2%, 1%, 3%, 5%, 6%, 8%, 10%, 12%, 14%, or 15% of the mass of the thermoplastic biodegradable polymer material, and the examples are not exhaustive here. The present invention does not specifically limit the specific type of insect pheromone, and it can be selected based on actual needs, such as the sex pheromone of the pear borer or the sex pheromone of the striped stem borer.

[0048] As a preferred embodiment, the insect pheromone ink provided by the present invention further comprises an aqueous solution of a functional material; the functional material preferably comprises a lignin sulfonate and a metal salt; the lignin sulfonate preferably comprises sodium lignin sulfonate and / or calcium lignin sulfonate; and the metal salt preferably comprises one or more of a ferric salt, an aluminum salt, and a divalent copper salt. In the present invention, the ferric salt preferably comprises ferric chloride, more preferably anhydrous ferric chloride; the aluminum salt preferably comprises aluminum chloride, more preferably anhydrous aluminum chloride; and the divalent copper salt preferably comprises copper chloride, more preferably anhydrous copper chloride.

[0049] In the present invention, the concentrations of the lignin sulfonate and metal salt in the aqueous solution of the functional material are preferably independently 0.25-1 g / mL. In specific embodiments, they can be 0.25 g / mL, 0.5 g / mL, 0.75 g / mL, or 1 g / mL. In the present invention, the mass of the lignin sulfonate is preferably 0.02-0.5% of the mass of the thermoplastic biodegradable polymer material. In specific embodiments, it can be 0.02%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%. The mass of the metal salt is preferably 0.1-2.5% of the mass of the thermoplastic biodegradable polymer material. In specific embodiments, it can be 0.1%, 0.5%, 1%, 1.5%, 2%, or 2.5%. The present invention introduces lignin sulfonate and metal ions to enhance the UV resistance and cross-linking effect of the 3D-printed insect pheromone attractant core, improving the attractant's stability and applicability.

[0050] By controlling the amount of each component, the insect pheromone ink obtained by the present invention has good rheological properties, which helps the ink to pass through the printing nozzle smoothly for 3D printing.

[0051] The present invention provides a method for preparing the insect pheromone ink described in the above scheme, comprising the following steps: dissolving an alcohol plasticizer in a graded volatile organic solvent, and sequentially adding an insect pheromone and a thermoplastic biodegradable polymer material to the obtained solution to obtain the insect pheromone ink.

[0052] When the insect pheromone ink also includes an aqueous solution of a functional material, the method for preparing the insect pheromone preferably includes the following steps: dissolving an alcohol plasticizer in a graded volatile organic solvent, and sequentially adding an aqueous solution of the functional material, the insect pheromone, and a thermoplastic biodegradable polymer material to the resulting solution to obtain the insect pheromone ink.

[0053] In the present invention, after each raw material is added, the present invention preferably stirs evenly. The present invention has no special requirements on the speed and time of stirring, as long as stirring evenly is sufficient.

[0054] In the present invention, in order to remove bubbles, the insect pheromone ink is preferably sealed in a sealed container and left to stand for 12 hours.

[0055] The present invention provides an insect pheromone attractant core, which is prepared by 3D printing of the insect pheromone ink described in the above scheme.

[0056] The present invention provides a method for preparing the insect pheromone attractant core described in the above scheme, comprising the following steps: 3D printing the insect pheromone ink described in the above scheme, wherein the 3D printing layer height is 0.8-1.5 mm, the filling density is 70-100%, and the printing speed is 10-20 mm / s.

[0057] In a specific embodiment, the layer height of the 3D printing can be 0.8 mm, 1 mm, 1.2 mm or 1.5 mm, more preferably the layer height of the first layer is 0.8 mm and the heights of the remaining layers are 1 mm.

[0058] In specific embodiments, the filling density of the 3D printing can be 70%, 75%, 80%, 85%, 90%, 95% or 100%.

[0059] In a specific embodiment, the printing speed of the 3D printing can be 10 mm / s, 15 mm / s or 20 mm / s.

[0060] In the present invention, the nozzle diameter of the 3D printing is preferably 0.8 mm or 1.2 mm.

[0061] The present invention does not impose any special restrictions on the printing model used for the 3D printing, and can be set according to actual needs. For example, a cylindrical shape with a bottom radius of 5-20 mm and a height of 5-15 mm can be selected; or a cubic shape with a length and width of 10-30 mm and a height of 5-15 mm.

[0062] The present invention provides the use of the insect pheromone attractant core described in the above scheme in pest control.

[0063] The present invention provides a method for recycling and reusing the insect pheromone attractant core described in the above scheme, comprising the following steps: mixing the recovered insect pheromone attractant core powder and insect pheromone with graded volatile organic solvents to obtain drug-loaded ink, which is reused for 3D printing.

[0064] In the present invention, the mixing preferably comprises: dissolving the insect pheromone in a graded volatile organic solvent, adding the recovered insect pheromone attractant powder to the obtained solution, and stirring.

[0065] The insect pheromone ink, insect pheromone attractant core, preparation, application and recycling of the present invention are described in detail below with reference to the examples. However, these examples should not be construed as limiting the scope of protection of the present invention.

[0066] The following examples and comparative examples are used in the following raw materials:

[0067] Cellulose acetate (CA, Mn = 60,000 g / mol, acetyl content = 39.5 wt%); polyethylene glycol (PEG, Mn = 4,000 g / mol); acetone (purity greater than 99.8%); N,N-dimethylformamide (DMF); anhydrous ferric chloride (FeCl3); and sodium lignin sulfonate (SLS). Analytical-grade chemicals and reagent-grade solvents were used in this invention without further purification. Pear borer sex pheromone ((Z,E)-8-dodecenyl ethyl ester).

[0068] Example 1

[0069] At room temperature (25°C), polyethylene glycol (2% by weight of the ink) was dissolved in a mixture of acetone and N,N-dimethylformamide (4:1, v / v). Subsequently, 0.2% of the weight of the ink was added to the mixture, and the mixture was stirred on a magnetic stirrer at 500 rpm for 30 minutes until the solution became homogeneous. Subsequently, 15% of cellulose acetate (by weight of the ink) was added, and the mixture was mechanically stirred at 800 rpm for 5 minutes to obtain a semi-solid insect pheromone ink. To remove air bubbles, the resulting ink was sealed in a sealed container and allowed to stand for 12 hours. It was then sealed and stored in a refrigerator at 4°C until ready for use. This was designated as CP ink.

[0070] Example 2

[0071] The difference from Example 1 is that an aqueous solution of sodium lignin sulfonate and anhydrous ferric chloride is used for modification. The specific steps are as follows:

[0072] At room temperature (25°C), polyethylene glycol (2% by mass of CA) was dissolved in a mixed solvent of acetone and N,N-dimethylformamide (4:1, v / v); then, an aqueous solution of sodium lignin sulfonate and anhydrous ferric chloride was added (the concentrations of sodium lignin sulfonate and anhydrous ferric chloride were both 0.5 g / mL, the mass of sodium lignin sulfonate was 0.1% by mass of CA, and the mass of anhydrous ferric chloride was 0.5% by mass of CA), followed by the addition of pear borer sex pheromone (0.2% by mass of CA), and stirring at 500 rpm on a magnetic stirrer for 30 minutes until the solution was uniform. Subsequently, 15% cellulose acetate (by mass in the ink) was added, and mechanical stirring was carried out at 800 rpm for 5 minutes to finally obtain a semi-solid insect pheromone ink. To remove bubbles, the obtained ink was sealed in a sealed container and allowed to stand for 12 h, then sealed and stored in a refrigerator at 4°C for future use, and was recorded as CP-SL-Fe ink. The preparation flow chart of Example 2 is shown in the figure below. Figure 1 shown.

[0073] Application Examples

[0074] To improve lure preparation efficiency, this method used a cubic model measuring 20 mm × 20 mm × 10 mm. This was modeled using SOLIDWORKS software and sliced ​​using Repetier-Host software. The insect pheromone ink was printed using an extrusion-based 3D printer (Foodbot-D1, Timeprint Technology). The parameters were as follows: nozzle diameter of 0.8 mm, layer height of 1 mm, with the first layer height of 0.8 mm; infill density of 90%; and print speed of 15 mm / s. The printing parameters for the inks in Examples 1 and 2 were identical, and both were directly extruded and printed at room temperature (25°C). The lure prepared in Example 1 is referred to as the CP lure, and the lure prepared in Example 2 is referred to as the CP-SL-Fe lure.

[0075] Figure 2 Photos of the extrusion molding of CP and CP-SL-Fe inks, showing that both inks have good printability and excellent molding ability.

[0076] Comparative Example 1

[0077] Preparation of pheromone lure with only lignin and no iron (named CP-SL lure):

[0078] In order to compare the effect of metal ions in the modification process, the present invention only adds sodium lignin sulfonate without adding anhydrous ferric chloride during the modification process. The other preparation and printing operations are consistent with Example 2 and the application example. The obtained lure is referred to as CP-SL lure.

[0079] Comparative Example 2

[0080] Preparation of unmodified empty vector (named CP-K empty vector):

[0081] At room temperature (25°C), polyethylene glycol (2% by weight of CA) was dissolved in a mixture of acetone and N,N-dimethylformamide (4:1, v / v). The mixture was stirred on a magnetic stirrer at 500 rpm for 30 minutes until the solution was homogeneous. Next, 15% cellulose acetate (by weight of the ink) was added and mechanically stirred at 800 rpm for 5 minutes to obtain a semi-solid, drug-free ink. The ink was sealed in a sealed container and allowed to stand for 12 hours before printing. Printing parameters were the same as in the application example, resulting in an unmodified empty carrier, referred to as CP-K empty carrier.

[0082] Structure and performance characterization

[0083] (1) Characterization of ink rheological properties

[0084] The rheological properties of the ink were analyzed using a rheometer (MCR502, Anton Paar, Austria). The rheological tests included shear viscosity tests and oscillatory stress sweep tests, both of which were performed using PP25 parallel plates (25 mm diameter, 1 mm gap) at a constant temperature of 25°C. -1 The shear viscosity analysis was performed under the conditions of . The oscillatory stress sweep analysis was performed under the conditions of a constant frequency of 10 rad / s and a strain range of 1% to 1000% to obtain the storage modulus (G′) and loss modulus (G″) of the ink. The test results are shown in Figure 3 , where (a) is the functional relationship between the viscosity of the two inks and the shear rate, and (b) is the relationship between the storage modulus (G′) and loss modulus (G″) and the oscillation stress.

[0085] Depend on Figure 3 It can be seen that both CP and CP-SL-Fe exhibit shear thinning behavior when the shear rate continues to increase ( Figure 3 (a)), at 0.1 s -1 The viscosity under shear rate increases from 1.46 MPa∙s of CP ink to 1.62 MPa∙s of CP-SL-Fe ink. 3+ The introduction of CA, SLS and Fe 3+ The shear thinning behavior is crucial for DIW 3D printing because it enables the ink to be extruded through the nozzle at a relatively low pressure. As the shear rate increases to 100 s -1 When the ink is heated to 400 rpm, the viscosity of both inks drops to about 700 Pa∙s, which helps the ink pass through the printing nozzle smoothly.

[0086] In addition, the modulus of the ink is also important to control the shape fidelity of the printed structure. Figure 3 As shown in (b), both inks have a solid-like texture, which can be confirmed by the storage modulus (G′) being significantly higher than the loss modulus (G″) (more than 8 times). It is obvious that the storage modulus (G′) and loss modulus (G″) of the modified CP-SL-Fe ink are both higher than those of the CP ink, which further confirms the strengthening effect after modification. The intersection of the G′ and G″ curves shows that the yield stress (τy) of the CP ink is approximately 237 Pa, while the yield stress of the CP-SL-Fe ink is 194 Pa. This shows that the extrusion smoothness of the CP-SL-Fe ink is better than that of the CP ink. Nevertheless, both inks can be printed smoothly during printing.

[0087] (2) Characterization of 3D printed lure core surface morphology

[0088] 3D printed lure cores must not only meet the requirements of green agriculture such as slow release and biodegradability, but also have excellent morphology and structure to ensure stability during transportation and application, and be able to adapt to complex field environments. This invention successfully printed lure core small pieces CP and CP-SL-Fe ( Figure 4 (a) and (c)), and the surface morphology of the printed lure core was observed using a three-dimensional super-depth microscope ( Figure 4 (b) and (d)). The results show that the lines on the surface of the printed lure have a regular arrangement of high and low undulations, and no obvious defects are found.

[0089] The surface morphology of the 3D printed CP lure and CP-SL-Fe lure was analyzed by scanning electron microscopy (SEM). Figure 5 .exist Figure 5 It can be clearly observed in (a) and (c) that cellulose ether forms a clumping bonding structure under the action of organic solvent and PEG, which can confirm that the ink forms a tight cross-linking under the action of shear force during the printing process. Figure 5 Compared with (b), the surface of CP-SL-Fe lure shows obvious wrinkle structure (see Figure 5 This phenomenon can be attributed to the coordination cross-linking effect between iron ions and polymers (CA, PEG, and SLS).

[0090] In addition, the distribution of Fe in the CP-SL-Fe lure was observed by energy dispersive spectroscopy (EDS). Figure 6 . Figure 6 This indicates that the introduced Fe ions are evenly distributed on the CP-SL-Fe core, further verifying that the material was successfully modified and has good uniformity and stability.

[0091] (3) 3D printing core chemistry and crystal structure characterization

[0092] In order to detect the chemical structure of the pheromone lure prepared by 3D printing, FTIR tests were performed on the CP lure, CP-SL-Fe lure and CP-SL lure modified with SLS only (preparation method see Comparative Example 1). The results are shown in Figure 7 (a) In all 3D printed lures, the FTIR spectra at 1700 cm -1 The characteristic peak of the acetate group is at 2920cm, which is related to C=O stretching. -1 The peak at 1498 cm -1An absorption peak appeared at 3414 cm-1, indicating that there are aromatic ring vibrations in both CP-SL and CP-SL-Fe. Compared with the CP and CP-SL decoys, the −OH peak in the CP-SL-Fe decoy moved from 3414 cm-1 to 3414 cm-1. -1 Displacement to 3446 cm -1 , that is, after the addition of iron ions, the −OH peak shifts to the left. This may be due to the fact that Fe 3+ The coordination bond interaction with the -OH groups in the material is enhanced, weakening the hydrogen bonds between the molecular chains. The above phenomenon can preliminarily prove that the modified CP-SL-Fe core forms a more complex cross-linked structure at the chemical level through hydrogen bonds and coordination bonds.

[0093] XRD was used to further analyze the changes in the crystal structure of CP core, CP-SL core and CP-SL-Fe core before and after the coordination crosslinking reaction. Figure 7 (b) Characteristic diffraction peaks of cellulose I crystal structure are observed at scattering angles of 2θ = 14.1° and 24.5° for the CP and CP-SL cores, whereas the characteristic peak at 2θ = 14.1° disappears for the CP-SL-Fe core. This is likely due to the introduction of metal ions, which affects the intermolecular interactions within the composite, thereby reducing crystallinity. This reduced crystallinity and increased internal amorphous regions or disordered structures may facilitate drug loading and sustained release.

[0094] In addition, X-ray photoelectron spectroscopy (XPS) was used to track the chemical structure evolution of the 3D printed lure before and after modification. Compared with the CP lure, the XPS data of the CP-SL-Fe lure ( Figure 7 Figures (c), (d), and (e) show a significant increase in the content of C–O groups, while the content of C=O groups decreases slightly. This may be due to the addition of sodium lignosulfonate, which adds more hydroxyl and ether groups to the material. Alternatively, it may be due to the coordination of Fe³⁺ with oxygen-containing functional groups (such as hydroxyl and ether groups) in the SLS molecules, thereby enhancing the crosslinking effect. This SLS-Fe³⁺ coordination not only improves the stability of the material but also may alter the distribution and properties of surface functional groups.

[0095] (4) Research on the physical properties of 3D printed lure cores

[0096] Thermogravimetric analysis experiments were conducted on a HITACHI STA200 thermogravimetric analyzer (TGA). The experiments were conducted under a nitrogen atmosphere, with the temperature range increasing from 30°C to 600°C at a heating rate of 10°C / min. By comparing the thermogravimetric curves of the unmodified empty carrier (CP-K, preparation method see Comparative Example 2), the unmodified pheromone-carrying attractant core (CP), and the modified pheromone-carrying attractant core (CP-SL-Fe), the thermal stability of different samples during the heating process and their differences were analyzed. The results are shown in Figure 8Middle (a).

[0097] TGA analysis results ( Figure 8 Figure (a) shows that at 120°C, the empty carrier (CP-K) exhibits a 27% weight loss, while the drug-loaded attractants (CP and CP-SL-Fe) both experience weight losses of around 30%. This is likely due to the thermal decomposition and volatilization of the pheromone. Compared to CP-K and CP, the decomposition temperature of the CP-SL-Fe attractant increased from 215°C to 229°C, indicating that the modified material has an increased degree of cross-linking, which in turn improves the thermal stability of the attractant. Furthermore, the CP-SL-Fe attractant decomposes more rapidly at 300°C, likely due to the decomposition of sodium lignin sulfonate.

[0098] The prepared 3D printed lure core was placed on an electronic universal testing machine for a standard compression test with a loading rate set at 0.5 mm / min. The stress-strain curve was plotted and the results are shown in Fig. Figure 8 (b) The maximum compressive strength σ of the 3D printed lure is further calculated based on the compression strength formula and the elastic modulus formula. max and elastic modulus .

[0099] Compression test data showed that the CP had a compressive strength of 51.06 MPa and a compression modulus of 1.47 GPa; the CP-SL-Fe had a compressive strength of 87.96 MPa and a compression modulus of 1.87 GPa, indicating that the lure can meet the transportation and field application requirements under certain strength and pressure. In addition, the compressive strength of the CP-SL-Fe lure is better than that of the CP, indicating that it has stronger compression resistance and deformation resistance, and exhibits higher stability. By comparing the stress-strain curves before and after modification ( Figure 8 In (b), it can be found that the curves of the two are similar, indicating that although the compressive strength and compression modulus have increased, the deformation modes of the two are basically the same.

[0100] The diffuse reflectance test of the surface of the 3D printed sample was carried out using a Shimadzu UV-3600 UV / Vis / NIR spectrometer with a test wavelength range of 200 nm to 800 nm. Through the test, the reflectance (R%) curve of the 3D printed sample before and after modification was obtained. The results are shown in Figure 8 Middle (c).

[0101] UV-visible diffuse reflectance ( Figure 8Figure (c) shows that the reflectivity of the CP core to ultraviolet and visible light is higher than that of the CP-SL-Fe core. Sodium lignin sulfonate itself has light-absorbing properties, and its introduction may enhance the light absorption capacity of the material, especially in the ultraviolet region. Therefore, the addition of sodium lignin sulfonate may replace the reflection effect by improving the material's ability to absorb ultraviolet light. In general, whether by reflecting or absorbing ultraviolet light, the surface of the material can play a role in protecting the internal drugs to a certain extent. It is worth noting that the water contact angle of the surface of the modified material is significantly improved ( Figure 8 In (d), the angle of attraction increases from 29.4° for the original CP core to 56.6° for the CP-SL-Fe core. This change indicates that the modification of the surface microstructure of the material plays an important role in improving the hydrophobicity.

[0102] (5) Characterization of degradation performance of 3D printed lure core

[0103] To evaluate the biodegradability of 3D-printed lures, pre- and post-modification 3D-printed lures (CP and CP-SL-Fe) were compared with commercially available rubber stoppers (CK). Both the commercial rubber stoppers and the 3D-printed lures were loaded with 1 mg of the pear borer sex pheromone. The rubber stoppers were loaded by dissolving the pheromone in n-hexane to a 1 g / 200 mL stock solution. 200 μL of this solution was then dripped onto the rubber stoppers. The rubber stoppers then absorbed the pheromone through solvent permeation and then physically adsorbed it. The samples were buried at a depth of 10 cm in natural soil. Sample weights were recorded every 30 days, and the weight loss rate was calculated. Soil temperature and humidity were also recorded. Three replicates were used for each experiment.

[0104] like Figure 8 As shown in (f), the biodegradability of the 3D printed bait was tested in a natural soil environment. Figure 8 Figure (e) shows that the weight loss rate of the 3D-printed lure gradually increased with the test time, while the mass of the commercial rubber stopper remained virtually unchanged. The weight loss rates of CP and CP-SL-Fe after 105 days were 17.65% and 20.35%, respectively. The main microorganisms degrading the 3D-printed lure were fungi, bacteria, and actinomycetes, which are specialized decomposers of cellulose and lignin structures. These results indicate that the 3D-printed lure exhibits certain biodegradability compared to commercially available rubber stoppers.

[0105] (6) Characterization of 3D printed lure encapsulation effect and release performance

[0106] Drug encapsulation and release performance are also key factors in the development of sex attractants. Testing showed that the encapsulation efficiencies of CP and CP-SL-Fe were 95.39% and 96.21%, respectively, indicating that the drug was well encapsulated in the material.

[0107] The 3D printed drug-loaded blocks before and after modification were placed in a fume hood at room temperature of 25±2°C (well ventilated, no directional airflow). Samples were taken at different time points and the residual pheromone content was analyzed by gas chromatography (GC). Three replicates were used for each group. Figure 9 Middle (a). Results showed that by the second week, pheromone release from the modified lure was 41.9% (CP lure) and 57.17% (CP-SL-Fe lure), respectively. Both experienced an initial burst release followed by a slow release period that lasted for over six weeks. It is speculated that the 3D-printed lure may have two phases: rapid release from the surface layer and slow release from the inner layer. During the latter slow release phase, the surface layer material provided better protection for the inner layer. Furthermore, the release rate of the CP-SL-Fe lure began to slow after two weeks and was slower than that of the CP lure. Its cumulative release rate on day 47 was 84.43%, while that of the CP lure was 90.57%. These results suggest that the sustained release mechanism of the pheromone may rely on enhanced intermolecular interactions (such as coordination and hydrogen bonds) between the polymers within the 3D-printed lure, resulting in a denser structure that tightly encapsulates the pheromone within the cross-linked structure, slowing its release rate.

[0108] In order to further study the release behavior of pheromones in 3D printed lures, commonly used drug release kinetic models, including zero-order model, first-order model, Higuchi model and Ritger-Peppas model, were used for simulation. Figure 10 , comparing the four models, the two 3D printed lure cores have a coefficient of determination R after fitting the first-order release model 2 The highest value is [missing value], indicating that the pheromone release behavior is closer to the first-order release kinetic model. Preliminary research on indoor release experiments shows that insect pheromone attractants prepared using 3D printing technology have the potential to achieve long-term pest control effects in the field.

[0109] (7) Field trapping ability test

[0110] In the research on relevant hormonal lures, field trapping data is relatively limited. Despite the more complex and variable field environment, it remains an important means of testing lure performance and biological activity. This part of the invention will promote further development of 3D printing technology in this field. Figure 9 (b) shows the actual application of the 3D printed lure combination trap in the field. Figure 9 Figure (c) shows that the 3D printed lures exhibited excellent trapping effectiveness. The CP-SL-Fe lure performed better overall than the CP lure, and its duration of effectiveness was comparable to that of commercially available lures. It is noteworthy that the CP-SL-Fe lure performed better than the commercially available rubber plug lure in the first three weeks, which is consistent with its rapid release characteristics in the early stages. Meanwhile, the cumulative number of traps ( Figure 9 Figure (d) also shows that the CP-SL-Fe lure trapped a greater number of pear borer moths over a six-week period. These trapping results fully demonstrate the effectiveness of 3D-printed lures and their persistence in complex field environments. Furthermore, this study further demonstrates that CP-SL-Fe, through complex cross-linking mechanisms such as hydrogen and coordination bonds, can better encapsulate the drug, resulting in superior performance in both indoor release and field trapping. This provides a strong basis for further research on sustained-release lures.

[0111] (8) Research on the recyclable and reusable characteristics of 3D printed lure cores

[0112] 3D-printed lures were recycled and reused after field use. First, the recycled 3D-printed lure cores (CP-SL-Fe) were pulverized into powder by physical grinding. A certain amount of pheromone (0.2% by weight of the recovered powder, representing the sex pheromone of the pear borer) was then fully dissolved in a mixed organic solvent, specifically a mixture of acetone and DMF (4:1, v / v). A certain amount of the recycled powder, representing 15% by weight of the insect pheromone ink, was then added to the mixed solvent. Mechanical stirring was performed at 800 rpm for 5 minutes to prepare the recycled insect pheromone ink, which was then reprinted using the same printing steps and parameters as in the previous application example. The lure cores were designated rCP-SL-Fe lures. To validate the effectiveness of this recycling strategy, the surface morphology, drug encapsulation efficiency, Fourier transform infrared spectroscopy (FTIR), mechanical properties, and wettability of the reprinted lure cores were systematically evaluated. The printing process and parameters were the same as previously described.

[0113] The results showed that after simple treatment, the material can be recycled and reused for 3D printing to make pheromone-loaded attractant cores (rCP-SL-Fe). Figure 11 (a) and (b) show the process of recycling materials from the field to making printing ink, which only requires physical grinding and solvent dissolution. Figure 11 The recovered ink shown in (c) and (d) has good extrusion effect and plasticity. SEM-ESD results ( Figure 11 Figures (e) and (f) show that the surface of the re-printed lure core presents a tightly cross-linked, regularly arranged structure with evenly distributed iron elements, showing surface morphology similar to that of the first-printed lure core. The characteristic peaks shown in FTIR analysis are consistent with the results of the previous study ( Figure 11 (g)). The encapsulation efficiency of the lure core was 92.8%, indicating that the encapsulation efficiency of the insect pheromone remained at a high level ( Figure 11(h)). It is worth noting that the compression strength and compression modulus of the recycled and reprinted pheromone lure are 124.28MPa and 2.03GPa respectively, and the surface water contact angle is 84.51°. From the stress-strain curve ( Figure 11 Based on the results of (i) and water contact angle data, the rCP-SL-Fe lure exhibits superior properties to the CP-SL-Fe lure. This is likely due to the enhanced cross-linking structure during the secondary dissolution process, resulting in a denser structure. These experimental results demonstrate the feasibility of recycling and reusing 3D-printed lure cores. This method combines the simplicity of the process with the efficient molding process of 3D printing, providing a promising avenue for the efficient and rapid reuse of lure cores.

[0114] The above results demonstrate that the present invention has successfully produced two insect pheromone inks with excellent printing properties. The 3D-printed pheromone lures exhibited favorable surface morphology, excellent physical and chemical properties, and good encapsulation and release characteristics. After modification, the overall performance of the lures was enhanced. Furthermore, the 3D-printed insect pheromone lures demonstrated excellent results in terms of preparation, field application, and green sustainability, demonstrating significant potential for development. With the continued development of agricultural technology and the advancement of interdisciplinary research, the application prospects of 3D printing technology in agriculture will be even broader.

[0115] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. An insect pheromone lure, characterized in that: The insect pheromone ink is prepared by 3D printing; the insect pheromone ink includes the following components: a thermoplastic biodegradable polymer material, an alcohol plasticizer, a graded volatile organic solvent, an insect pheromone, and an aqueous solution of a functional material; The graded volatile organic solvents include at least one high volatility organic solvent and at least one low volatility organic solvent; The mass content of the thermoplastic biodegradable polymer material in the insect pheromone ink is 12-16%; The mass of the alcohol plasticizer is 0.2-3% of the mass of the thermoplastic biodegradable polymer material; The mass of the insect pheromone is 0.01-15% of the mass of the thermoplastic biodegradable polymer material; The thermoplastic biodegradable polymer material is cellulose acetate; The functional material contains lignin sulfonate and a metal salt; the concentrations of the lignin sulfonate and the metal salt in the aqueous solution of the functional material are independently 0.25 to 1 g / mL; The mass of the lignin sulfonate is 0.02-0.5% of the mass of the thermoplastic biodegradable polymer material; the mass of the metal salt is 0.1-2.5% of the mass of the thermoplastic biodegradable polymer material; the metal salt is ferric chloride; and the lignin sulfonate is sodium lignin sulfonate; The alcohol plasticizer is polyethylene glycol; The high-volatility organic solvent is at least one of acetone, dichloromethane and ethanol; the low-volatility organic solvent is at least one of N,N-dimethylformamide and dimethyl sulfoxide.

2. The method for preparing the insect pheromone lure according to claim 1, characterized in that: The method comprises the following steps: performing 3D printing on insect pheromone ink to obtain the insect pheromone attractant core; the 3D printing layer height is 0.8-1.5 mm, the filling density is 70-100%, and the printing speed is 10-20 mm / s.

3. Use of the insect pheromone attractant according to claim 1 in pest control.

4. The method for recycling and reusing the insect pheromone lure core according to claim 1, characterized in that: The following steps are involved: The recovered insect pheromone attractant powder and insect pheromone are mixed with graded volatile organic solvents to obtain drug-loaded ink, which is then used again for 3D printing.

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