Method for producing aqueous active substance compositions of active substances that are hardly soluble in water

• US 8,974,806 B2
• Filed: 08/03/2005
• Issued: 03/10/2015
• Est. Priority Date: 08/04/2004
• Status: Expired due to Fees

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Amrhein, Patrick, Schpke, Holger, Kleist, Gunnar, Kluge, Michael
• Primary Examiner(s): Klinkel, Kortney L
• Application Number:
  US11/658,472
• Publication Number:
  US 20080213326A1
• Time in Patent Office: 3,506 Days
• US Class Current: 424/405
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A01N 25/26 in coated particulate form
• CPC Class Codes: A01N 25/28 Microcapsules or nanocapsules
• CPC Class Codes: A01N 43/36 five-membered rings
• CPC Class Codes: A01N 43/653 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• CPC Class Codes: A01N 53/00 Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
• CPC Class Codes: B27K 3/007 employing compositions comprising nanoparticles
• CPC Class Codes: B27K 3/15 Impregnating involving polymerisation including use of polymer-containing impregnating agents macromolecular compounds derived from lignocellulosic materials C08H; compositions of lignin-containing materials C08L97/02
• CPC Class Codes: C08L 33/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C08L 35/02 Homopolymers or copolymers of esters C08L35/06, C08L35/08 take precedence
• CPC Class Codes: C08L 97/02 Lignocellulosic material, e.g. wood, straw or bagasse manufacture of articles made from lignocellulosic material by dry processes B27N

Abstract

The present invention relates to a process for preparing aqueous active compound compositions of active compounds which are poorly soluble in water, in particular of active compounds for the protection of crops and materials. Moreover, the invention relates to the active compound compositions obtainable by the process and to their use for controlling harmful organisms in plants and in the protection of materials.

The process comprises the following steps:

• • a) provision of an aqueous suspension of solid active compound particles of at least one active compound having a solubility in water of not more than 5 g/l at 25° C./1013 mbar, comprising, for stabilizing the active compound particles, at least one surfactant, where the active compound particles in the suspension have a mean particle size, determined by dynamic light scattering, of not more than 1200 nm,
  • b) emulsion polymerization of a first monomer composition M1 in the aqueous suspension of the active compound, where the monomer composition M1 comprises at least 95% by weight, based on its total weight, of at least one neutral, monoethylenically unsaturated monomer M1.1 having a solubility in water of not more than 30 g/l at 25° C./1013 mbar, giving an aqueous dispersion of polymer/active compound particles, and
  • c) emulsion polymerization of a second monomer composition M2 in an aqueous dispersion of the polymer/active compound particles obtained in step b), where the monomer composition M2 comprises at least 60% by weight, based on its total weight, of at least one neutral, monoethylenically unsaturated monomer M2.1 having a solubility in water of not more than 30 g/l at 25° C./1013 mbar.

Claims

1. A process for preparing an aqueous active compound composition for the protection of crops or materials, which process comprises the following steps:

a) providing an aqueous suspension of (1) solid active compound particles of at least one active compound having a solubility in water of not more than 5 g/l at 25°

C./1013 mbar, and at least one surfactant, wherein the active compound particles in the suspension have a mean particle size, determined by dynamic light scattering, of 20 to 1200 nm, where the preparation of the suspension of the solid active compound particles comprises comminution of the solid active compound in the presence of the at least surfactant, or precipitating the active compound from a solution of the active compound in the presence of the at least one surfactant,

b) adding a first monomer composition M1 to the suspension of solid active compound particles and initiating an emulsion polymerization of said first monomer composition M1 in the aqueous suspension of the active compound, wherein the monomer composition M1 comprises at least 95% by weight, based on its total weight, of at least one neutral, monoethylenically unsaturated monomer M1.1 having a solubility in water of not more than 30 g/l at 25°

C./1 013 mbar, giving an aqueous dispersion of polymer/active compound particles, and

c) conducting emulsion polymerization of a second monomer composition M2 in an aqueous dispersion of the polymer/active compound particles obtained in step b), wherein the monomer composition M2 comprises at least 60% by weight, based on its total weight, of at least one neutral, monoethylenically unsaturated monomer M2.1 having a solubility in water of not more than 30 g/l at 25°

C./1013 mbar,

wherein the monomer M1.1 is selected from the group consisting of vinylaromatic monomers and the esters of α

,β

-ethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 carbon atoms with C₁-C₁₀-alkanols or C₃-C₁₀-cycloalkanols,

wherein the monomer M2.1 is selected from the group consisting of vinylaromatic monomers and the esters of α

,β

-ethylenically unsaturated C₃-C₁₀-monocarboxylic and C₃-C₁₀-dicarboxylic acids with C₁-C₁₀-alkanols or C₃-C₁₀-cycloalkanols, and

wherein the active compound is a solid at a temperature of 50°

C. and selected from the group consisting of herbicides, fungicides, insecticides, acaricides, nematicides, bactericides, algicides, molluscicides, plant growth regulators and biocides.

2. The process according to claim 1, wherein the aqueous suspension of solid active compound particles comprises at least one nonionic surfactant.

3. The process according to claim 2, wherein the weight ratio of nonionic surfactant to active compound is in the range from 2:

1 to 1;

50.

4. The process according to claim 1, wherein the suspension of the solid active compound particles in step a) is provided by comminuting solid active compound in a mixture of the active compound with the surfactant and then dispersing the mixture obtained in this manner in an aqueous medium.

5. The process according to claim 1, wherein the monomer composition M1 corresponds to a polymer 1 having a theoretical glass transition temperature according to Fox T_g of 30 to 180°

C.

6. The process according to claim 1, wherein at least 70% by weight of the monomers M1.1 are selected from the group consisting of vinylaromatic monomers, esters of methacrylic acid with C₂-C₄-alkanols and tert-butyl acrylate.

7. The process according to claim 1, wherein the weight ratio of active compound to the monomers in the monomer composition M1 is in the range from 10:

1 to 1;

50.

8. The process according to claim 1, wherein at least 70% by weight of the monomers M1 are initially charged in the aqueous suspension of the active compound and the polymerization is then initiated in the monomer/active compound emulsion obtained in this manner.

9. The process according to claim 1, wherein the polymerization in step b) is carried out in the presence of an anionic emulsifier.

10. The process according to claim 1, wherein the polymerization of the monomers M1 is initiated by a Redox initiator.

11. The process according to claim 1, wherein the weight ratio of the total amount of monomer mixtures M1 and M2 to active compound is in the range from 1:

9 to 100;

1.

12. The process according to claim 1, wherein the monomers M2 comprise at least one monomer M2.2 in an amount of from 0.5 to 40% by weight, based on the total amount of the monomers M2, which monomer M2.2 is selected from the group consisting of

monoethylenically unsaturated monomers M2.2a having at least one acid group or at least one anionic group;

monoethylenically unsaturated neutral monomers M2.2b having a solubility in water of at least 50 g/l at 25°

C.; and

monoethylenically unsaturated monomers M2.2c having at least one cationic group and/or at least one group which can be protonated in aqueous medium.

13. The process according to claim 1, wherein the active compound is selected from the group consisting of conazole fungicides, strobilurins and arylpyrrols.

14. An aqueous active compound composition obtained by a process according to claim 1.

15. The active compound composition according to claim 14, wherein the active compound is present in an amount of from 0.5 to 30% by weight, based on the total weight of the composition.

16. The active compound composition according to claim 14 comprising at least one fungicidally active compound.

17. The active compound composition according to claim 14 comprising at least one insecticidally active compound.

18. A method for protecting materials against infestation by harmful organisms and for treating materials infested by a harmful organism which comprises treating the material with an active compound composition according to claim 14, wherein the composition comprises at least one active compound from the group consisting of insecticides, acaricides, algicides, biocides, bactericides and fungicides.

19. The method as claimed in claim 18 for protecting wood against infestation by wood-damaging organisms.

20. A method for crop protection which comprises applying to a crop plant an active compound composition according to claim 14, wherein the active compound composition comprises at least one active compound from the group of the insecticides, acaricides, herbicides, plant growth regulators and fungicides.