DISPOSITIVOS CONTENDO PRINCÍPIOS ATIVOS PARA PLANTAS

Abstract

The invention relates to a composition comprising - at least one biocompatible copolyester capable of being obtained by polycondensation of a diacid and glycerol, with a number-average molar mass within a range extending from 1000 g / mol to 10 000 g / mol, the biocompatible copolyester being chosen from copolyesters of glycerol and of a (C3-C20)alkyl dicarboxylic acid, - from 8% to 40% by weight of the total weight of the composition of a wood flour and - at least 10% by weight of the total weight of the composition of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant. Said composition is most particularly suitable for treating plants by application to the trunk of trees or of shrubs, in particular chosen from the group consisting of heveas, grapevine, olive trees, fruit trees and ornamental plants, preferably heveas.

Description

1 / 20 “DEVICES CONTAINING ACTIVE INGREDIENTS FOR PLANTS” TECHNICAL FIELD

[0001] The present invention falls within the field of compositions intended for the treatment of plants, which are applied to the aerial parts (foliar system or trunk) and which may contain an active ingredient such as, for example, a stimulant, a fertilizer, a pesticide, a fungicide or even a nutrient. STATE OF THE ART

[0002] The Applicant has developed, for plant treatment, a formulation containing, on the one hand, a biocompatible and biodegradable polymer of biological origin, showing some antimicrobial activity, and, on the other hand, a phytosanitary product or biostimulant, particularly a biostimulant, in particular, ethephon (patent application number FR2113693). The polymer material used is poly(glycerol sebacate) or PGS. This formulation contains a certain concentration of active product and allows the targeted application of a defined quantity of this product to the plant, limiting losses to the environment, generally resulting from conventional application techniques and climatic conditions. This formulation also allows the controlled release of the active product over time, ensuring continuous and regular treatment during the application period. The formulation can be applied in paste form to the aerial parts (foliar system or trunk) of trees and shrubs.

[0003] A constant concern is to persist in improving existing devices aimed at treating plants. More particularly, insofar as the plant treatment device developed by the Applicant aims to release the active ingredient contained therein in a controlled and continuous manner over time, it is important to ensure the durability of the device's placement on the aerial parts of the treated trees and shrubs.

[0004] However, it is difficult to use devices with formulations based on poly(glycerol sebacate) containing controlled-release active substances, applied to the aerial parts of treated trees and shrubs, without encountering, on the one hand, problems of adhesion and, on the other hand, dimensional stability (creep or spreading). Petition 870250085443, dated 09 / 22 / 2025, page 15 / 39 2 / 20 of the polymer), especially when the device is exposed to high operating temperatures, which can reach 40°C in tropical or subtropical regions. Indeed, under these operating conditions, what is observed is a marked creep of the controlled-release device containing the poly(glycerol sebacate)-based formulation containing an aqueous solution of a phytosanitary and / or biostimulant active ingredient, particularly when the poly(glycerol sebacate) has an average molar mass greater than 1,000 g / mol. TECHNICAL PROBLEM

[0005] The technical problem that arises, therefore, is to improve the creep resistance of a plant treatment device containing a copolyester, in particular a poly(glycerol sebacate), as well as an aqueous solution of a phytosanitary and / or biostimulant active ingredient.

[0006] One objective of the invention is to improve the creep resistance of such a device when the device is applied to the aerial parts of treated trees and shrubs exposed to the temperatures of tropical or subtropical regions. DISCLOSURE OF THE INVENTION

[0007] The Applicant, continuing its research efforts, surprisingly discovered that the use of a specific plant-based filler, in particular wood flour, in a device carrying a formulation based on poly(glycerol sebacate) containing an aqueous solution of a phytosanitary and / or biostimulant active ingredient, allows addressing the technical problem posed.

[0008] The composition according to the present invention allows for a significant improvement in creep resistance at temperatures simulating natural exposure in tropical or subtropical regions (around 40°C) of a plant treatment device, while preserving its adhesion properties to the wood substrate to which it is applied.

[0009] In view of its properties, the composition according to the invention provides better creep resistance at temperatures in tropical or subtropical regions, without impairing adhesion to the trunk of treated trees and shrubs.

[0010] A first object of the invention is a composition comprising Petition 870250085443, dated 09 / 22 / 2025, page 16 / 39 3 / 20 less a copolyester that can be obtained by the polycondensation of a diacid and glycerol, wood flour as a vegetable filler, and an aqueous solution of at least one active ingredient.

[0011] A further object of the invention consists of a method for treating plants comprising applying a composition according to the invention to the aerial parts of trees or shrubs. DESCRIPTION OF THE FIGURES

[0012] Figure 1: Results table with photographs taken during the tests with the compositions specified in Table 6.

[0013] Figure 2: Results table with photographs taken during the tests with the compositions specified in Table 7.

[0014] Figure 3: Results table with photographs taken during the tests with the compositions specified in Table 8. DEFINITIONS

[0015] Biocompatible means something that is tolerated by an organism, particularly in this case something that is tolerated by plants.

[0016] A plant protection product, plant protection product or plant protection product is a substance or mixture of substances of a chemical or organic nature (of natural or synthetic origin) used in agriculture, horticulture or forestry to protect cultivated plants against bioaggressors (pests, phytopathogenic agents, parasitic plants, adventitious plants) or to optimize crops by favoring the growth of cultivated plants and treating the environment (especially the soil).

[0017] A biostimulant is understood to be a substance that stimulates the plant nutrition process, regardless of the nutrients it contains, seeking to improve one or more of the following characteristics of plants or the rhizosphere: nutrient utilization efficiency, tolerance to abiotic stress, qualitative characteristics, availability of nutrients confined in the soil or rhizosphere (in accordance with EU Regulation 2019 / 1009).

[0018] Biostimulants can be some natural preparations that are not very effective. Petition 870250085443, dated 09 / 22 / 2025, page 17 / 39 4 / 20 concerning (PNPP). The PNPP are: - natural substances for biostimulant use (SNUB). - basic substances.

[0019] Basic substances are defined by Article 23 of Regulation (EC) No 1107 / 2009. These are substances of phytosanitary interest but whose main use does not involve plant protection (e.g., food products).

[0020] Glycerol follows the general formula below. OH HO-^Λ^OH SUMMARY OF THE INVENTION

[0021] The invention, described in more detail below, relates to at least one of the embodiments listed in the items below: 1. Composition comprising: - at least one biocompatible copolyester, obtainable by polycondensation of a diacid and glycerol, with a number-average molar mass (Mn) in the range of 1,000 g / mol to 10,000 g / mol, wherein the biocompatible copolyester is selected from copolyesters of glycerol and a (C3-C20) alkyl diacarboxylic acid, - from 8% to 40% by weight of the total weight of the composition of a vegetable filler, where the vegetable filler is wood meal and - at least 10% by weight of the total weight of the composition of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant. 2. Composition, according to the previous embodiment, which is in paste form. 3. Composition, according to any of the preceding embodiments, wherein the diacid is selected from among the (C8-C15) alkyl carboxylic diacids. 4. Composition, according to any of the preceding embodiments, in which the copolyester is poly(glycerol sebacate) (PGS). 5. Composition, according to any of the preceding embodiments, in which the copolyester has a number-average molar mass (Mn) in the range of 1.000 Petition 870250085443, dated 09 / 22 / 2025, page 18 / 39 5 / 20 g / mol to 5,000 g / mol. 6. Composition, according to any of the previous embodiments, in which the percentage of copolyester varies in the range of 20% to 90% by weight relative to the total weight of the composition. 7. Composition, according to any of the previous embodiments, in which the percentage of copolyester varies in the range of 30% to 90% by weight, more preferably 40% to 90% by weight relative to the total weight of the composition. 8. Composition, according to any of the previous embodiments, in which the percentage of plant load varies in the range of 8% to 30% by weight, in relation to the total weight of the composition. 9. Composition, according to any of the embodiments 1 to 7 in which the percentage of vegetable load varies in a range of 10% to 40% by weight, preferably 15% to 30% by weight, relative to the total weight of the composition. 10. Composition, according to any of the previous embodiments, in which the plant material has an average particle size between 20 and 700 microns. 11. Composition, according to any of the previous embodiments, in which at least one phytosanitary or biostimulant active ingredient is an ethylene precursor, preferably ethephon. 12. Composition, according to any of the previous embodiments, intended for the controlled release of at least the phytosanitary active ingredient and / or the biostimulant. 13. A composition, according to any of the previous embodiments, that should be applied to the trunk of shrubs and trees. 14. A method for treating plants comprising applying a composition, as defined in any of the preceding embodiments, to the trunks of trees or shrubs. 15. Method for treating plants, according to the previous embodiment, in which trees and shrubs are selected from the group consisting of rubber trees, vines, olive trees, fruit trees and ornamental plants, preferably rubber trees. Petition 870250085443, dated 09 / 22 / 2025, page 19 / 39 6 / 20 16. Use of wood flour in a device containing a copolyester of glycerol and a (C3-C20) alkyl dicarboxylic acid, preferably poly(glycerol sebacate), and an aqueous solution of a phytosanitary and / or biostimulant active ingredient, to improve the creep resistance of said device. DETAILED DESCRIPTION OF THE INVENTION

[0022] The invention relates to a controlled-release composition comprising a biocompatible copolyester that can be obtained by the polycondensation of a diacid and glycerol, an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant, and wood flour as a vegetable filler. COPOLYESTERS

[0023] The composition according to the invention comprises at least one biocompatible copolyester that can be obtained by the polycondensation of a diacid and glycerol, with a number-average molar mass (Mn) in the range of 1,000 g / mol to 10,000 g / mol, wherein the biocompatible copolyester is selected from copolyesters of glycerol and a (C3-C20) alkyl carboxylic acid.

[0024] Copolyesters according to the invention are polyesters composed of at least two different units, derived from at least one diacid, selected from (C3-C20) alkyl diacids, and glycerol.

[0025] According to a preferred embodiment, the diacid is selected from among the (C8-C15) alkyl carboxylic diacids.

[0026] Diacids are preferentially selected from among diacids bearing two terminal carboxylic acid functions.

[0027] Preferably, 0 diacid is 0 sebacic acid which has the general formula below. THE THE

[0028] The biocompatible and biodegradable copolyester is advantageously poly(glycerol sebacate) (PGS) and its derivatives, more preferably poly(glycerol Petition 870250085443, dated 09 / 22 / 2025, page 20 / 39 7 / 20 sebacate) which has the general formula below. THE

[0029] The polyol monomer to diacid monomer ratio is advantageously between 0.3:1 and 1:0.3.

[0030] Poly(glycerol sebacate) can be obtained by a two-step synthesis: a first esterification step and a second polycondensation step, and possibly a third crosslinking step. The first step consists of an esterification reaction between an acid function of sebacic acid and an alcohol function of glycerol. Preferably, the terminal alcohol functions react. The second step consists of lengthening the chains to obtain a PGS resin.

[0031] After that, different strategies can be employed to adjust the polymer properties, such as long thermal crosslinking by esterification of the pendant secondary alcohol functions (frequently at high temperature and low pressure), or crosslinking by means of post-functionalization (such as, for example, functionalization of the polymer matrix with acrylates or methacrylates, followed by radical crosslinking or crosslinking with isocyanates such as, for example, hexamethylenediamine diisocyanate). It is also possible to perform a copolymerization of PGS with blocks of other linear polymers, for example, with polylactic acid (PLA), poly(lactic-co-glycolic) (PLGA), polycaprolactone (PCL) or poly(butyl succinate) (PBS). The copolyesters resulting from such copolymerizations are block copolymers with at least one PGS block and at least one other block of another linear polymer.

[0032] In the sense of the present invention, all these compounds are grouped under the name poly(glycerol sebacate) and its derivatives.

[0033] For example, document WO2015 / 184313A1 describes the synthesis of PGS. In addition, PGS is commercially available, in particular under the name Regenerez® Poly(glycerol sebacate) resin.

[0034] Preferably, the biocompatible copolyester is of organic origin.

[0035] According to certain modalities, copolyester preferably has a Petition 870250085443, dated 09 / 22 / 2025, page 21 / 39 8 / 20 average molar mass in number (Mn) ranging from 1,000 g / mol to 5,000 g / mol.

[0036] Mn values ​​can be adjusted in a simple and known way by modifying the stoichiometry of the monomers, in particular the glycerol / sebacic acid ratio.

[0037] Mn is measured by size exclusion chromatography (SEC) described in the examples below.

[0038] A person skilled in the art understands that the weight quantity of copolyester is at most the complement up to 100% of the sum of the weight quantities of wood flour and the aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant, expressed as a % by weight of the total weight of the composition. In other words, according to the invention, the composition comprises at most 82% by weight of the total weight of the biocompatible copolyester composition that can be obtained by the polycondensation of a diacid and glycerol.

[0039] According to certain variants, the amount of copolyester is preferably at least 20% by weight of the total weight of the composition, preferably at least 30% by weight, more preferably at least 40% by weight. VEGETABLE LOAD

[0040] The composition according to the invention contains wood flour as a vegetable filler.

[0041] According to one embodiment of the invention, the wood flour consists of particles with a median size of less than one millimeter. Preferably, according to this embodiment of the invention, the wood flour consists of particles with a median size in the range of 20 to 700 microns.

[0042] Thus, the wood flour used as vegetable filler is finely ground to this particle size using known grinding methods.

[0043] The great advantage of using this type of plant-based cargo is its lower impact on the environment and its biodegradability under natural conditions.

[0044] The composition according to the invention comprises from 8% to 40% by weight relative to the total weight of the wood flour composition. Indeed, in Petition 870250085443, dated 09 / 22 / 2025, page 22 / 39 9 / 20 range of 8% to 40% by weight of wood flour, there is a significant improvement in creep resistance of the composition according to the invention comprising a biocompatible copolyester that can be obtained by the polycondensation of a diacid and glycerol, and at least 10% by weight of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant.

[0045] According to certain preferred embodiments, the composition preferably comprises 8% to 30% by weight of wood flour in relation to the total weight of the composition.

[0046] According to certain embodiments, the percentage of wood flour is advantageously 10% to 40% by weight, more preferably 15% to 30% by weight, relative to the total weight of the composition. Indeed, a composition comprising a glycerol copolyester according to the invention, in particular when the copolyester is a PGS, and at least 10% by weight of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant, then exhibits low flow. Low means here that a composition according to the present invention exhibits a weight loss percentage of 5% or less under the test conditions specified below. Aqueous solution of at least one active ingredient.

[0047] The composition according to the invention comprises at least 10% by weight of the total weight of the composition of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant.

[0048] Those skilled in the art will understand that the amount of aqueous solution in the composition according to the invention depends primarily on the dilution rate of the active ingredient in the solution and the desired amount of active ingredient in the composition. PLANT PROTECTION AND / OR BIOSTIMULANT ACTIVE INGREDIENTS

[0049] The composition according to the invention comprises at least one phytosanitary active ingredient and / or a biostimulant dissolved in the aqueous solution. The active ingredient is preferably selected from the group consisting of stimulants, fertilizers, pesticides, fungicides, nutrients, bactericides, insecticides, growth regulators. Petition 870250085443, dated 09 / 22 / 2025, page 23 / 39 10 / 20

[0050] Preferably, the composition according to the invention comprises a phytosanitary active ingredient and / or a biostimulant precursor of ethylene, preferably ethephon. ADDITIVES

[0051] The composition according to the invention may comprise one or more additives. These include, in particular, stabilizers, compatibilizing agents, modeling agents, active ingredient release regulators, antioxidants, etc. FORM

[0052] The composition according to the invention may advantageously be in paste form. This paste may be shaped in different ways depending on its application. Advantageously, for application to the trunk of trees or shrubs, this paste may be shaped, for example, using molding or calendering, or it may be transferred by application with a brush, spatula, knife, etc., or by extrusion.

[0053] When the composition according to the present invention is in paste form, the percentage of biocompatible copolyester that can be obtained by the polycondensation of a diacid and glycerol in the composition according to the invention varies advantageously in a range of up to 90% by weight, preferably from 20% to 90% by weight, more preferably from 30% to 90% by weight, and most preferably from 40% to 90% by weight.

[0054] Those skilled in the art will understand that the composition according to the present invention comprises glycerol copolyester in an amount by weight of at most one complement to 100% of the sum of the amounts by weight of the vegetable filler and the aqueous solution of at least one active ingredient, expressed as a % by weight of the total weight of the composition. In other words, the composition comprising at least 8% by weight of wood flour and at least 10% by weight of an aqueous solution of at least one active ingredient comprises at most 82% by weight of the total weight of the biocompatible copolyester composition that can be obtained by the polycondensation of a diacid and glycerol. Thus, when it Petition 870250085443, dated 09 / 22 / 2025, page 24 / 39 11 / 20 is in paste form, the composition preferably comprising 20% ​​to 82% by weight, more preferably 30% to 82% by weight, most preferably 40% to 82% by weight of the biocompatible copolyester that can be obtained by polycondensation of a diacid and glycerol.

[0055] When the composition according to the present invention is in paste form, it advantageously comprises 10% to 50% by weight, preferably 10% to 40% by weight, and particularly preferably 10% to 30% by weight of an aqueous solution of at least one active ingredient. PREPARATION METHOD

[0056] Various methods of preparing the composition according to the invention comprising the copolyester, the plant feedstock and the phytosanitary active ingredient and / or the biostimulant may be employed. These include, but are not limited to, a mixture of molten copolyester with the plant feedstock and the aqueous solution.

[0057] This mixture may be carried out in a conventional stirred reactor at relatively mild temperatures to limit the risks of degradation of the phytosanitary active ingredient and / or the biostimulant, preferably <100°C, using conventional mixers. The mixing method may be batch, semi-batch or continuous. APPLICATION METHOD

[0058] According to the present invention, the composition according to the invention is preferably applied to at least one part of the plants, preferably to one or more aerial part(s).

[0059] According to one embodiment, the composition according to the invention is to be applied to the trunk of shrubs and trees. Therefore, the composition is presented in particular in paste form, as explained above.

[0060] According to one embodiment, the method for treating plants according to the invention involves trees or shrubs, and the composition is applied to the trunk.

[0061] The trees or shrubs are preferably selected from the group consisting of rubber trees, grapevines, olive trees, fruit trees and plants Petition 870250085443, dated 09 / 22 / 2025, page 25 / 39 12 / 20 ornamental.

[0062] When the composition according to the present invention is in paste form, preferably it is sticky and can be spread with a spatula or with a mastic gun-type application device, which allows the controlled application of a mass to the plant.

[0063] It is also possible to consider a device composed of a “hard” layer in contact with a pre-cut adhesive-type “sticky” layer with suitable dimensions. It can be attached to one or more aerial parts of the plant, for example to the trunk or, for example, to leaves or fruits.

[0064] The following examples illustrate the invention without limiting its scope. EXAMPLES SIZE EXCLUSION CHROMATOGRAPHY (SEC) ANALYSIS METHOD

[0065] The PGS samples were dissolved at a concentration of approximately 1.5 gl-1 in THF, and then shaken for 2 hours before being injected.

[0066] The analysis conditions used are described in Table 1 below: TABLE 1 Eluent THF Injection volume 100 μL Concentration ~ 1.5 g / L Temperature 35°C Detector RI Waters Mobile phase flow rate 1 ml / min Columns 2 Mixed D + 2 Mixed E standard Polystyrene (PS)

[0067] The analyzable mass range is between 162 g / mol and 7,500,000 g / mol. The number-average molecular weight (Mn) is expressed in g / mol in PS equivalents, similarly the weight-average molecular weight (Mw) is expressed in g / mol in Petition 870250085443, dated 09 / 22 / 2025, page 26 / 39 13 / 20 equivalent PS. The dispersivity D is defined by the ratio Mw / Mn. COPOLYESTERS: SUMMARY OF PGS:

[0068] Three PGS samples were prepared by mixing glycerol with sebacic acid, observing the following operating procedures: PGS 1:

[0069] In a 500 ml double-shell reactor, covered by a distillation column set up for total reflux and a condenser connected to a distillate recovery vessel, glycerol (124 g, 1.5 molar equivalents) is mixed with water (24 g) at room temperature with a nitrogen flow (0.1 l / min). Gentle stirring (50 rpm) follows for 5 min. After the glycerol dissolves, sebacic acid (182 g, 1 molar equivalent) is added to the aqueous mixture in the reactor. Finally, the remaining water (24 g) is added to the medium. The reactor tank is then heated to a shell temperature of 140°C. Stirring is gradually increased to 100 rpm and then to 150 rpm as the acid melts and solubilizes. When the medium in the tank becomes transparent (around 95°C), the agitation is set to a final value of 200 rpm, and the medium is kept under reflux.When the temperature of the vapors at the top of the distillation column reaches 98°C, and after an equilibration time of 15 min, the column configuration is tilted for complete stripping. Esterification of the medium is carried out over a period of 26 hours. The distilled water collected during the test is recovered in a dedicated insulated recovery vessel.

[0070] Next, a vacuum system is connected to the distillation condenser and a pressure lower than atmospheric pressure is applied to the reactor contents. The pressure is reduced slowly and in stages (about 10 to 15% per stage) over about 30 minutes to a target value of less than 10 mbar.

[0071] Once the pressure in the reaction vessel stabilizes at 5 mbar, the medium continues to react at 150°C for a further 4 hours. During this polycondensation step, the stirring speed is reduced to 115 rpm to account for the increased viscosity of the mixture. Petition 870250085443, dated 09 / 22 / 2025, page 27 / 39 14 / 20

[0072] The PGS produced is transferred from the reactor tank to a container after the plant returns to atmospheric pressure and allowed to cool to room temperature. The product is then transferred to a freezer and stored. It remains in the freezer for at least about 24 hours before analysis.

[0073] The polymer obtained has the following characteristics, as shown in Table 2: TABLE 2 Number-average molecular weight (Mn, g / mol) 1.316 Weight-average molecular weight (Mw, g / mol) 2.297 Polydispersity index D 1.7 PGS 2

[0074] In a 500 ml double-shell reactor covered by a distillation column configured for total reflux and a condenser connected to a distillate recovery vessel, glycerol (112 g, 1.3 molar equivalents) is mixed with water (25 g) at room temperature with a nitrogen flow (0.1 l / min). Gentle stirring (50 rpm) follows for 5 min. After the glycerol dissolves, sebacic acid (189 g, 1 molar equivalent) is added to the aqueous mixture in the reactor. Finally, the remaining water (25 g) is added to the medium. The reactor tank is then heated to the shell temperature of 140°C. Stirring is gradually increased to 100 rpm and then to 150 rpm as the acid melts and solubilizes. When the medium in the tank becomes transparent (at around 95°C), the agitation is increased to a final value of 200 rpm and the medium is allowed to reflux.When the vapor temperature at the top of the distillation column reaches 98°C, and after an equilibration time of 15 min, the column configuration is tilted for complete stripping. Esterification of the medium is carried out over a period of 26 hours. The distilled water collected during the test is recovered in a dedicated insulated recovery vessel. Petition 870250085443, dated 09 / 22 / 2025, pp. 28 / 39 15 / 20

[0075] Next, a vacuum system is connected to the distillation condenser and a pressure lower than atmospheric pressure is applied to the reactor contents. The pressure is reduced slowly and in stages (about 10 to 15% per stage) for about 30 minutes to a target value of less than 10 mbar.

[0076] Once the pressure in the reaction vessel stabilizes at 5 mbar, the medium continues to react at 150°C for a further 5 hours. During this polycondensation step, the stirring speed is reduced to 115 rpm to account for the increased viscosity of the mixture.

[0077] The PGS produced is transferred from the reactor tank to a container after the plant returns to atmospheric pressure and allowed to cool to room temperature. The product is then transferred to a freezer and stored. It remains in the freezer for at least about 24 hours before analysis.

[0078] The polymer obtained has the following characteristics, as shown in Table 3 below: TABLE 3 Number-average molecular weight (Mn, g / mol) 1.659 Weight-average molecular weight (Mw, g / mol) 3.455 Polydispersity index D 2.1 PGS 3

[0079] In a 10-liter capacity double-walled stainless steel reactor covered by an instrumented distillation column configured for total reflux and a condenser connected to a distillate recovery vessel, glycerol (1.94 kg, 1 molar equivalent) is mixed with water (0.56 kg) at 40°C under a nitrogen flow (0.5 l / min). Gentle stirring (20 rpm) follows for 5 min. After the glycerol dissolves, sebacic acid (4.25 kg, 1 molar equivalent) is added to the aqueous mixture in the reactor. Finally, the remaining water (0.56 kg) is added to the medium. The reactor tank is then gradually heated following a progressive temperature ramp with intermediate stages, until the Petition 870250085443, dated 09 / 22 / 2025, pp. 29 / 39 The 16 / 20 casing reaches a temperature of 172°C 5 hours later, corresponding to a medium temperature of 170°C, measured with an immersion probe. Agitation is increased to 80 rpm when the medium temperature exceeds 90°C. The medium is kept under reflux at the beginning of the test. When the vapor temperature at the top of the distillation column reaches 98°C, and after an equilibration time of 15 min, the column configuration is tilted for complete stripping in order to selectively recover the water produced during the reaction.

[0080] Esterification of the medium is carried out over a total period of 8 hours and 30 minutes, considering as the starting point the moment of the beginning of the distillation, that is, about 30 minutes after the introduction of the reagents. The distilled water during the test is recovered in a dedicated insulating recovery vessel.

[0081] Next, a vacuum system is connected to the distillation condenser and a pressure lower than atmospheric pressure is applied to the reactor contents. The pressure is reduced slowly and in stages (about 10 to 15% per stage) over about 30 minutes to a target value of less than 30 mbar.

[0082] Once the pressure in the reaction vessel stabilizes at 28 mbar, the medium continues to react at 170°C for another 4 hours. During this polycondensation step, the stirring speed is maintained at 80 rpm.

[0083] The PGS produced is transferred from the reactor tank to a container and allowed to cool to room temperature. The product is then transferred to a freezer and stored. It remains in the freezer for at least about 24 hours before analysis.

[0084] The polymer obtained has the following characteristics, as shown in Table 4: TABLE 4 Number-average molecular weight (Mn, g / mol) 2.656 Weight-average molecular weight (Mw, g / mol) 16.520 Polydispersity index D 6.2

[0085] The PGS obtained has the characteristics summarized in Table 5. Petition 870250085443, dated 09 / 22 / 2025, pages 30 / 39 17 / 20 TABLE 5 PGS 1 PGS 2 PGS 3 Mn 1,316 1,659 2,656 ip 1.7 2.1 6.2 TESTS WITH DIFFERENT COMPOSITIONS ACCORDING TO THE INVENTION FORMULATION OF THE COMPOSITIONS:

[0086] A sample of PGS is introduced into a suitably sized container and heated in a water bath at 50°C until it reaches a viscous texture. After homogenizing the PGS with a spatula, an aqueous solution with 50% by mass of ethephon is added to the PGS outside the water bath and incorporated, being mixed with a spatula. If necessary, wood flour is also added to the mixture, fractionating the additions as needed. The composition is mixed with the spatula until a homogeneous paste is obtained. The mixture is then cooled to room temperature and kept in a freezer.

[0087] The proportions of the different constituents, expressed as a percentage by weight relative to the total weight of the composition, are indicated in Tables 6 and 7, respectively, with respect to the compositions based on Mn 1300 g / mol PGS and the compositions based on Mn 1660 g / mol PGS. TABLE 6 Constituent Compositions MP5 (control le) MP5+10 MP15 (control Ιθ) MP15+5 MP15+1 0 MP15+1 5 MP15+2 0 PGS 1 (1316g / mol) 95 85 85 80 75 70 65 Aq. sol. 50% ethephon 5 5 15 15 15 15 15 Wood flour (*) 0 10 0 5 10 15 20 Total weight 100 100 100 100 100 100 100 • Wood meal from the Sylvadec company, medium size, 200 microns Petition 870250085443, dated 09 / 22 / 2025, pp. 31-39 18 / 20 TABLE 7 Constituent Compositions HP15 (control) HP15+5 HP15+10 HP15+15 HP15+20 PGS 2 (1659g / mol) 85 80 75 70 65 Aq. Sol. 50% ethephon 15 15 15 15 15 Wood flour (*) 0 5 10 15 20 Total weight 100 100 100 100 100 • Wood flour from the Sylvadec company, medium size, 200 microns

[0088] In the notation MPY+X and HPY+X, Y should be understood as the percentage of aqueous solution and X as the percentage of wood flour. MANUFACTURING OF COMPOSITION TABLETS:

[0089] The preparation is removed from the freezer. Two silicone sheets are taken and 10 g of the desired formulation is placed between them. The mixture is calendered with a cylindrical tool between the two 3 mm silicone sheets and then the tablets are cut with a cutter: thickness = 3 mm, diameter = 40 mm, mass approximately 4 g.

[0090] Laminated poplar boards measuring 8 cm x 5 cm are prepared with a 1 cm x 1 cm x m grid and oven-dried at 40°C for 72 hours. A pad is applied by pressure to each wood specimen, the grid is completed over the pad, and the specimen is weighed.

[0091] The poplar board / adhesive assemblies for each composition are placed vertically in a 40°C oven (without humidity control). The evolution of the cutouts is monitored daily through photos and weighings.

[0092] These tests aim to show the effect of plant load on the flow of a composition containing PGS and an aqueous solution of a phytosanitary and / or biostimulant active ingredient such as ethephon. RESULTS

[0093] The results shown in Figure 1 and Figure 2 result from measurements and observations relevant to mass loss and size variation (by photographs). Petition 870250085443, dated 09 / 22 / 2025, pages 32 / 39 19 / 20 of each wood specimen after 96 hours in an oven at 40°C.

[0094] Thus, it is observed that, in relation to the control compositions, respectively, MP5, MP15 and HP15, the addition of wood flour to these compositions (respectively, where MP5+X, MP15+X and HP15+X, X is the percentage of wood flour) reduces creep at 40°C, even strongly reducing creep at 40°C when X is at least equal to 10 (i.e., 10% by weight of wood flour), without interfering with adhesion to the wood substrate after 96 hours.

[0095] Thus, it can be seen, according to the examples of the invention described herein, that by introducing a proportion of a vegetable filler of the wood flour type, creep can be avoided, and at the same time the good adhesion properties of a composition based on poly(glycerol sebacate) and an aqueous solution of ethephon on a wood surface can be preserved. Essays on the Nature of the Load FORMULATION OF THE COMPOSITIONS:

[0096] The following tests aim to show the effect of plant loading on the flow of a composition containing PGS and an aqueous solution compared to other loadings.

[0097] In these tests, a sample of Mn 2656 g / mol PGS is introduced into a suitably sized container and heated in a water bath at 50°C until it reaches a viscous texture. After homogenizing the PGS with a spatula, water is added to the PGS outside the water bath. To incorporate, the water is mixed with a spatula. After that, a filler is added to the mixture, fractionating the additions as needed. The composition is mixed with a spatula until a homogeneous paste is obtained. The mixture is then cooled to room temperature and stored in a freezer.

[0098] These tests show that a single plant load allows for a reduction in the flow of a composition based on PGS and water.

[0099] The proportions of the different constituents, expressed as a percentage by weight in relation to the total weight of the composition, are given in Table 8. TABLE 8 Petition 870250085443, dated 09 / 22 / 2025, pages 33 / 39 20 / 20 Constituent Compositions HP0 HP1 HP2 HP3 HP4 PGS 3 (2656 g / mol) 100 80 80 80 80 Wood flour (1) 20 CO charge (2) 20 CaCO3 charge (3) 20 Kaolin charge (4) 20 Total by weight 100 100 100 100 100 (1) Wood flour from Sylvadec company, medium size 200 microns (2) Eggshell powder from Lunderland company, medium size 17 microns (3) Calcium carbonate powder, medium size 6 microns (4) Natural kaolin, Argirec B24 grade from IMERYS company, medium size 200 microns. MANUFACTURING OF COMPOSITION TABLETS:

[00100] The sample tablets are manufactured following the protocol described above. RESULTS

[00101] The results shown in Figure 3 are derived from measurements and observations relating to mass loss and size change (by photographs) in each wood specimen after 96 hours in an oven at 40°C.

[00102] It is noted, therefore, unlike compositions HP2, HP3 and HP4 containing, respectively, an eggshell, calcium carbonate and kaolin filler, that the HP1 composition of the invention containing wood flour exhibits reduced creep at 40°C, without interfering with adhesion to the wood substrate after 96 hours.

[00103] Thus, it is possible to see that the introduction of a vegetable filler proportion of the wood flour type allows for a significant reduction in creep at 40°C, while at the same time preserving the good adhesion properties of a poly(glycerol sebacate) and water-based composition to a wood surface. Petition 870250085443, dated 09 / 22 / 2025, pp. 34 / 39

Claims

1 / 2 CLAIMS 1. Composition characterized by comprising: - at least one biocompatible copolyester, obtainable by polycondensation of a diacid and glycerol, with an average molar mass in number ranging from 1,000 g / mol to 10,000 g / mol, the biocompatible copolyester being selected from copolyesters of glycerol and a (C3-C20) alkyl carboxylic acid, - from 8% to 40% by weight of the total weight of the composition of a wood flour, and - at least 10% by weight of the total weight of the composition of an aqueous solution of at least one phytosanitary active ingredient and / or a biostimulant.

2. Composition according to claim 1, characterized in that the diacid is selected from among the (C8-C15) alkyl carboxylic diacids.

3. Composition according to claim 1 or 2, characterized in that the copolyester is poly(glycerol sebacate) (PGS).

4. Composition, according to any one of claims 1 to 3, characterized in that the copolyester has a number-average molar mass (Mn) in the range of 1,000 g / mol to 50,000 g / mol.

5. Composition, according to any one of claims 1 to 4, characterized in that the percentage of copolyester varies in the range from 20% to 90% by weight, preferably from 30% to 90% by weight, more preferably from 40% to 90% by weight, relative to the total weight of the composition.

6. Composition, according to any one of claims 1 to 5, characterized in that the percentage of wood flour varies in a range from 8% to 30% by weight relative to the total weight of the composition.

7. Composition, according to any one of claims 1 to 6, characterized in that the vegetable filler has an average particle size between 20 and 700 microns.

8. Composition, according to any one of claims 1 to 7, characterized in that at least one phytosanitary or biostimulant active ingredient is a precursor of ethylene, preferably ethephon.

9. Composition, according to any one of claims 1 to 8, characterized by serving for the controlled release of at least the phytosanitary active ingredient and / or the biostimulant.

10. Composition, according to any one of claims 1 to 9, characterized in that it is intended to be applied to the trunk of shrubs and trees.

11. A method for treating plants, characterized by comprising the application to the trunk of trees or shrubs of a composition as defined in any one of claims 1 to 10.

12. A method for treating plants, according to claim 11, characterized in that the trees and shrubs are selected from the group consisting of rubber trees, grapevines, olive trees, fruit trees and ornamental plants, preferably rubber trees.

13. Use of wood flour in a device comprising a copolyester of glycerol and a (C3-C20) alkyl dicarboxylic acid, and an aqueous solution of a phytosanitary and / or biostimulant active ingredient, characterized by being for improving the creep resistance of said device.

14. Use according to claim 13, characterized in that the copolyester of glycerol and a (C3-C20) alkyl diacarboxylic acid is poly(glycerol sebacate) (PGS). Petition 870250085443, dated 09 / 22 / 2025, pp. 36 / 39

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