AN INSECTICIDAL COMPOSITION BASED ON SAPONIFIED TALL OIL AND METHOD FOR PRODUCTION THEREOF
20230371522 · 2023-11-23
Inventors
Cpc classification
A01N61/02
HUMAN NECESSITIES
International classification
Abstract
The present invention relates to a composition and a method for producing a composition. The composition comprises a saponified solution of water and lye of sodium hydroxide or potassium hydroxide, and tall oil, wherein the composition comprises particles having a size of between 5 nm and 100 nm, as determined by a dynamic laser light diffraction scattering method using Malvern Zetasizer Nano-ZS. The method comprising: providing a preheated basic solution of water and lye of either sodium hydroxide or potassium hydroxide; and saponification by adding tall oil to the heated basic solution during mixing, to form a saponified solution.
Claims
1. A composition comprising a saponified solution of water and lye of sodium hydroxide or potassium hydroxide, and tall oil, wherein the composition comprises particles having a size of between 5 nm and 100 nm, as determined by a dynamic laser light diffraction scattering method using Malvern Zetasizer Nano-ZS.
2. The composition according to claim 1, wherein the particles have a size of between 10 nm and 40 nm.
3. The composition according to claim 1, having a particle size distribution based on intensity exhibiting a peak between 5 mm and 100 nm, wherein said peak has an intensity of at least 1%.
4. The composition according to claim 3, having a particle size distribution based on intensity exhibiting a first peak below 1 nm, and a second peak in the range of 5 nm to 100 nm.
5. The composition according to claim 4, having a particle size distribution being further characterised by a third peak in the range of 100 nm to 1000 nm.
6. The composition according to claim 1, wherein the saponified solution is undiluted or diluted with water to a concentration of between 10% and 99% defined as the weight ratio of the undiluted solution to the weight of the diluted solution.
7. A composition comprising a saponified solution of water and lye of sodium hydroxide or potassium hydroxide, and tall oil, wherein the composition comprises particles having a size of between 1 nm and 10 nm, as determined by a dynamic laser light diffraction scattering method using Malvern Zetasizer Nano-ZS.
8. The composition according to claim 7, wherein the particles have a size of between 7 nm and 9 nm.
9. The composition according to claim 7, having a particle size distribution based on intensity exhibiting a peak between 1 nm and 10 nm, wherein said peak has an intensity of at least 1%.
10. The composition according to claim 9, having a particle size distribution based on intensity exhibiting a first peak in the range of 1 nm to 10 nm, and a second peak in the range of 100 nm to 1000 nm.
11. The composition according to claim 10, wherein the saponified solution is diluted with water to a concentration below 10% defined as the weight ratio of the undiluted solution to the weight of the diluted solution.
12. (canceled)
13. The composition according to claim 1, wherein the saponified tall oil comprises at least 10 wt % saponified resin acids as compared to the total weight of the tall oil.
14. The composition according to claim 1, wherein the saponified solution comprises between 10 wt % and 25 wt % saponified tall oil.
15. (canceled)
16. The composition according to claim 1, wherein the saponified solution is a saponification of tall oil and a basic solution comprising lye and at least 50 wt % water or deionized water.
17. (canceled)
18. (canceled)
19. A method for producing a composition comprising: providing a preheated basic solution of water and lye of either sodium hydroxide or potassium hydroxide; performing saponification by adding tall oil to the preheated basic solution during mixing, to form a saponified solution; wherein the composition comprises particles having a size of between 5 nm and 100 nm, and/or wherein the composition comprises particles having a size of between 1 nm and 10 nm.
20. The method according to claim 19, wherein the ratio (w/w) of lye to tall oil used for the saponified solution is between 0.2 and 1.5.
21. The method according to claim 19, wherein the tall oil used for the saponified solution comprises at least 10 and wt % resin acids as compared to the total weight of the tall oil.
22. (canceled)
23. (canceled)
24. (canceled)
25. (canceled)
26. The method according to claim 19, comprising: adding at least one of the following to the saponified solution: triethanolamine and propylene glycol, wherein the respective amount of the triethanolamine and propylene glycol is within 0.1 wt % to 2 wt %.
27. (canceled)
28. The method according to claim 19, wherein the preheated basic solution of water and lye is within a temperature interval between 80° C. and 100° C.
29. (canceled)
30. (canceled)
31. (canceled)
32. A method of killing, controlling and/or repelling insects, pests and/or vermin, the method comprising: selecting an object to be treated; applying the composition of claim 1 to kill, control or repel insects, pests and/or vermin on the treated object.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0148] These and other aspects of the present inventive concept will now be described in more detail, with reference to the appended drawings showing an example embodiment of the inventive concept, wherein:
[0149]
[0150]
[0151]
[0152]
[0153]
[0154]
[0155]
DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
[0156] In the present detailed description, various embodiments of the invention are mainly described with reference to method for producing a composition, such as an insecticide. The invention is also described with reference to the use of saponified solution of saponified tall oil and lye as an insecticide, and a method of killing, controlling and/or repelling insects, pests and/or vermin.
[0157]
[0158] In a step S1, a predetermined amount of water is provided and heated to a temperature within a temperature range T between 90 and 95° C. During the step S1, or in a subsequent separate step S3, lye of potassium hydroxide is added to the water. As a result, a heated basic solution of water and lye of potassium hydroxide is provided in a step S5.
[0159] In a step S7, tall oil is added to the heated basic solution during mixing or stirring. The tall oil comprises between 10% and 25% resin, e.g. about 15% resin, that is between 10 wt % and 25 wt %, e.g. about 15 wt % resin acids. During the step S7, or in a subsequent separate step S9, the heated basic solution with the added tall oil is homogenized, or incubated, by mixing or stirring for a predetermined time of at least 30 minutes, typically 1 hour. As a result, saponification is achieved resulting in a saponified solution.
[0160] The addition of tall oil in step S7 is preferably carried out over a time span of between 5 and 15 minutes, e.g. about 10 minutes. Thus, between 5 and 20% of the tall oil is added every minute (e.g. based on volume of total tall oil added), preferably continuously. Hereby, the risk of agglomeration of the tall oil into lumps is reduced. The mixing or stirring in step S7 is preferably carried out by a stirring means, e.g. a magnetic stirrer or impeller, rotating with 25-75 rpm.
[0161] It should be noted that the temperature of the solution in step S7, and S9, is maintained within the temperature range T. Thus, the temperature of the solution is actively maintained above 90° C. and below 95° C. In other words, the addition of tall oil, and mixing or stirring, is adapted such that the temperature range T is maintained during the saponification.
[0162] In a step S11, the pH of the saponified solution is determined or measured. The pH, at 20° C., should be between 8.5 and 11, for example between 9 and 9.5. Thus, in response of determining that the pH is outside of the specified range, the method may comprise a step S13 of adjusting the pH of the saponified solution. Such an adjustment may comprise adding more tall oil or lye.
[0163] In a step S15, triethanolamine is added to the saponified solution, and in a step S17, propylene glycol is added to the saponified solution (already including the triethanolamine). The triethanolamine and propylene glycol is acting as stabilizer and/or pH adjuster in the saponified solution.
[0164] In a step S19, the saponified solution, including any reactants and products of the added triethanolamine and propylene glycol, is cooled down to a cooled temperature between room temperature and the temperature range T, e.g. to be between 30° C. and 40° C. Preferably, the cooling is carried out by natural cooling, but using an external cooling circuit for forced cooling of the solution is within the scope of the invention.
[0165] In a step S21, UREA is added to the saponified solution at the cooled temperature, whereby the solution is further cooled down to below 30° C., to provide the resulting composition.
[0166] Optionally, depending on the desired viscosity of the composition, a thickener, such as sodium sulphate is added to the composition, preferably subsequent to step 21.
[0167] It should be noted that steps presented herein, need not to, but may according to one example embodiment, be carried out in the consecutive order as represented by the numbering of the steps.
[0168] The amount of respective component in the resulting composition is given in Table 1. Thus, table 1 represents an example embodiment of a composition according to the invention, the composition being a saponified solution of water and lye of potassium hydroxide, and tall oil.
TABLE-US-00001 TABLE 1 Component Amount in wt % Potassium hydroxide 5-15 Tall oil (about 15 wt % resin acids) .sup. 10-25 Triethanolamine (at least 90% pure TEA) 0.1-2 Propylene glycol 0.1-2 UREA 0.1-2 Sodium sulphate .sup. 0-2 Water (deionized, <2° dH) Required amount for achieving 100%
[0169] According to at least one example embodiment, an example composition of the invention comprises 9 wt % potassium hydroxide, 17 wt % tall oil, 1 wt % triethanolamine, 1 wt % propylene glycol, 0.5 wt % UREA and 71.5 wt % water.
[0170] The composition of Table 1 is preferably a pesticide or insecticide or a compound for killing, controlling and/or repelling insects, pests and/or vermin such as plant pests or insects, as will be further described with reference to
[0171]
[0172]
EXAMPLES
[0173] An inventive composition, Composition 1, was produced by the method corresponding to that described with reference to
[0174] The use of Composition 1 as an insecticide was examined by performing the following described tests including analysing the behavior of white flies on tobacco leaves, and bench-marking the results with corresponding tests on immature green/black aphids on elderflower bushes and on European Spruce Bark Beetles from a local infested forest. Composition 1 was diluted to a 10% (w/w) solution (Composition 1A) and a 1% (w/w) solution (Composition 1B), using DDD water.
[0175] The tests were carried out using a standardised exposure protocol utilizing fine spraying of the respective composition. Biocidal activity was assessed using observation (photography and filming where appropriate), with semi quantitative (subjective) estimation of lethality following agitation of the bearer substratum (leaves and stalks), with voluntary and/or provoked movement.
[0176] The test insects were exposed in a Perspex box with lid measuring 25×25×15 cm, which corresponds to a volume of 9.4 L. White flies and aphids were exposed in situ on the leaves and stalks they were collected on, whereas European Spruce Bark Beetles were exposed “in the open”. Between exposures, the Perspex box was wiped clean three times with water and dried, to prevent cross-contamination.
[0177] A rigid protocol was defined as follows. The test insect sample was placed on the floor of the box, with a 5-minute acclimatization period. The insects were then sprayed with a single burst of fine mist from a standard height above the box (approximate 15 cm), allowing the spray to distribute across the entire surface area of the bottom of the box. The insects were then observed during a 10-minute period, observations recorded and then subjected to agitation. In the case of aphids, the branches were tapped on the floor of the box and the dislodged insects observed for movement. In the case of European Spruce Bark Beetles, the insects were observed on the box floor. Individual tests were repeated three times. The ambient temperature of the room was 27° C. −28° C. over the two test days and relative humidity was 68-70%.
[0178] Calibration of the spray mist delivery nozzle revealed that a single continuous depression of the nozzle delivered 1.4+/−0.05 mL material, irrespective of composition (n=12 on all observation). Rough calculations therefore revealed the following delivery of Composition 1 to the boxes: For Composition 1A (10%)=0.14 mL, and for Composition 1B (1%)=0.014 mL. Assuming the volume of the box is 1/100 of 1 m3, this corresponds to delivery of 14 mL/m3 for Composition 1A and 1.4 mL/m3 for Composition 1B.
[0179] Result 1: White Flies
[0180] Control exposure to DDD water caused no direct changes in movement behavior on the leaves. On agitation, the flies either moved or left the leaf freely.
[0181] Treatment with Composition 1B resulted in spontaneous repulsion from the leaf and a visible lack of movement and lack of flight from the substratum from the remaining few individuals after 10 minutes.
[0182] The effect of Composition 1B was even more pronounced when Composition 1A was applied. The biocidal effect appears after 1-2 minutes, resulting in increased residual numbers of flies, which were all immotile on agitation.
[0183] Result 2: Aphids
[0184] It was clearly seen that treatment with DDD water resulted in lack of direct effect on immature aphids, as judged by continued movement, both in situ on the stalk and after “tapping” clean onto the floor of the box.
[0185] Treatment with Composition 1B reduced the spontaneous motor activity of the aphids, but they continued to move.
[0186] Treatment with Composition 1A resulted in total lack of movement on the substratum and an almost complete lack of movement following mechanical agitation/harvesting.
[0187] Result 3: European Spruce Bark Beetles
[0188] Direct application of DDD water control was without effect on the beetle's motility. The test animals moved easily around the bottom of the test rig.
[0189] When Composition 1A was applied, a progressive biocidal effect (lack of voluntary or forced movement, retracted appendages, lack of righting reflex) began after approximately 30 seconds, which was considerable after 5 minutes and total after 10 minutes, indicating 100% lethality under the conditions of exposure.
[0190] Treatment was also performed with a Composition 2 which was based on the same components as Composition 1, but was produced by simply mixing the components without the heating and stirring as for Composition 1. Composition 2 was diluted to a 10% (w/w) solution (Composition 2A) and a 1% (w/w) solution (Composition 2B), using DDD water. Application of Composition 2 corresponded to that described for Composition 1.
[0191] For application of Composition 2B, voluntary movement was still present in the beetles (placed on the back for ease of observation), indicating a lack of toxicity/lethality. This was also the case for application of Composition 2A. The test insects were still highly motile.
[0192] The above results clearly show the beneficial effect of using Composition 1 as an insecticide. It is believed that the overall size of the spiracle structure correlates to the size of the insect (Arcaz A et al (2016). Desiccation tolerance in Anopheles coluzzii: The effects of spiracle size and cuticular hydrocarbons, The Journal of Experimental Biology, 219, DOI 10.1242/jeb.135665). Without being bound by any theory, the use of Composition 1 results in an interference with the gas exchange capacity of the respiratory systems of the insects, e.g. such that the spiracles of the smaller insects “clog” more effectively and quicker than those of larger insects, up to a certain exposure concentration.
[0193] Particle Size Distribution Measurements
[0194] The particle size distribution of Composition 1 was analysed by a dynamic laser light diffraction scattering method using Malvern Zetasizer Nano-ZS. For Composition 1, seven diluted solutions of 0.5%, 1%, 3% 10%, 20%, 30% and 40% (all w/w) in deionized water (Type III) were prepared, stirred overnight, and analysed. The following procedure and settings were used: At least three repetitive measurement were made on each 1 ml sample taken from the solutions with a pipette. The instrument incorporates non-invasive back scatter (NIBS) optics. The scattered light is detected at an angle of 173° and this optics maximizes the detection of scattered light while maintaining signal quality. This provides exceptional sensitivity that is required for measuring the size of nanoparticles, such as surfactant micelles, at low concentrations. The instrument contains a 4 mW He—Ne laser operating at a wavelength of 633 nm and an avalanche photodiode (APD) detector. Samples were measured at 20° C.
[0195] The particle size distribution of the Composition 1 and Composition 2 were furthermore analysed by a dynamic laser light diffraction scattering method using Malvern Zetasizer Ultra. For each one of Composition 1 and Composition 2, one diluted solution of 50% (all w/w) in deionized water (Type III) was prepared, stirred overnight, and analysed. The following procedure and settings were used: Three repetitive measurement were made on a 1 ml sample taken from the solution with a pipette. The instrument incorporates non-invasive back scatter (NIBS) optics. The scattered light is detected at an angle of 173° and this optics maximizes the detection of scattered light while maintaining signal quality. This provides exceptional sensitivity that is required for measuring the size of nanoparticles, such as surfactant micelles, at low concentrations. The instrument contains a 4 mW He—Ne laser operating at a wavelength of 633 nm and an avalanche photodiode (APD) detector. Samples were measured at 20° C.
[0196] For the measurements, material refractive index was 1.333. Viscosity of the solutions was measured separately with a glass capillary viscometer.
[0197] The particle size distribution (based on intensity) for Composition 1 using Malvern Zetasizer Nano-ZS is shown in
[0198] As can be derived from
[0199] As can be derived from
[0200] As can be derived from
[0201] As can be derived from
[0202] As can be derived from
[0203] When the concentration of Composition 1 is reduced below 1%, which is believed to be the critical micelle concentration (cmc), the particle size distribution changes drastically. Interesting, the peak related to the small particles below 1 nm for the 10% to 40% solutions, and between 1 nm and 10 nm for the 1% to 3% solutions, seem to move towards larger sizes as the concentration of Composition 1 is reduced. This may indicate that the small particles related to such peak are micelles.
[0204] Without being bound by any theory, it is believed that the particular particle size distribution of Composition 1 shown in
[0205] According to another theory, micelles or agglomerations of the size 10 nm to 100 nm is particularly relevant for the insecticidal effect. This may for example be derived based on a comparison with the particle size distribution for Composition 2, as shown in
[0206] Surface Tension, Turbidity and Solubility Measurements
[0207] The surface tension, turbidity and solubility of dye of Composition 1 were also analysed in to determine inter alia the critical micelle concentration (cmc). For these analyses, a series of eight samples including samples with reduced concentrations (w/w) of Composition 1 were made using deionized water (Sample 1-8 extending from 0.001% (w/w) to 100% (w/w) Composition 1). The samples were stirred at room temperature overnight. The surface tension and turbidity were measured at the current room temperature, 24° C. The surface tension was measured by the Wilhelmy plate method using a tensiometer Krüss K100SF, a first surface tension measurement 101 (Surf. Tens 1) and a second surface tension measurement 102 (Surf. Tens 2) were carried out (
TABLE-US-00002 TABLE 2 Surface tension Turbidity Sample Concentration [mN/m] [NTU] 1 0.001% 60.8 0.2 Composition 1 2 0.002% 48.9 0.9 Composition 1 3 0.005% 41.2 6.4 Composition 1 4 0.01% 40.5 12.6 Composition 1 5 0.02% 36.9 25 Composition 1 6 0.1% 30.1 43.5 Composition 1 7 1% 26.3 1.2 Composition 1 8 100% 31.3 1.4 Composition 1
[0208] At the lowest concentration the surface tension is high close to the surface tension of water (72 m N/m). The surface tension decreases as the concentration of Composition 1 is increased. Above a certain concentration the surface tension does not change and reaches approximately a constant value (31 mN/m). This concentration is the critical micelle concentration (cmc). Above the cmc any added additional surfactant forms larger aggregates (micelles) in the bulk solution which do not affect the surface tension.
[0209] Even though the invention has been described with reference to specific exemplifying embodiments thereof, many different alterations, modifications and the like will become apparent for those skilled in the art. For example, the invention is applicable to outdoor treatments of plant pests or insects by application of the composition or insecticide on an object, e.g. a plant or the soil, as well as indoor treatment of pests and/or vermin by application of the insecticide or composition on an object, e.g. an interior wall. Additionally, variations to the disclosed embodiments can be understood and effected by the skilled person in practicing the claimed inventive concept, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.