PENFLUFEN POLYMER PARTICLES

Abstract

The invention relates to penflufen-containing polymer particles, to penflufen-containing compositions comprising them, to processes for preparing them, and to the use thereof for protecting technical materials, more particularly wood, wood products, and wood-plastic composites.

Claims

1. Penflufen-containing polymer particles prepared by polymerization of at least one ethylenically unsaturated monomer in the presence of: penflufen or its salts and acid addition compounds, and an oil-soluble radical initiator, in an oil-in-water emulsion polymerization.

2. The penflufen-containing polymer particles as claimed in claim 1, wherein the ethylenically unsaturated monomers are neutral, uncharged, ethylenically unsaturated monomers of the type M1 selected from the group consisting of styrene, divinylbenzene, esters of monoethylenically unsaturated monocarboxylic and dicarboxylic acids having 3 to 8 carbon atoms with C.sub.1-C.sub.20 alkanols or with C.sub.5-C.sub.8 cycloalkanols.

3. The penflufen-containing polymer particles as claimed in claim 1, wherein the ethylenically unsaturated monomers are neutral, uncharged, ethylenically unsaturated monomers of type M1 selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 3-propylheptyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate and stearyl methacrylate, divinylbenzene and mixtures of these monomers.

4. The penflufen-containing polymer particles as claimed in claim 1, wherein the ethylenically unsaturated monomers are ethylenically unsaturated monomers having anionic or cationic groups of type M2 selected from the group consisting of ,-ethylenically unsaturated C.sub.3-C.sub.8 monocarboxylic and C.sub.4-C.sub.8 dicarboxylic acids, more particularly acrylic acid, methacrylic acid crotonic acid, maleic acid, fumaric acid and itaconic acid, 2-(N,N,N-trimethylammonium)ethyl acrylate chloride, 2-(N,N,N-trimethylammonium)ethyl methacrylate chloride, 2-(N,N,N-trimethylammonium)ethylmethacrylamide chloride, 3-(N,N,N-trimethylammonium)propylacrylamide chloride, 3-(N,N,N-trimethylammonium)propylmethacrylamide chloride, 2-(N,N,N-trimethylammonium)ethylacrylamide chloride, and also the corresponding methosulfates and sulfates.

5. The penflufen-containing polymer particles as claimed in claim 1, wherein the ethylenically unsaturated monomers are composed of 80 to 99.9 wt % of monomers M1 and 0.1 wt % to 20 wt % of monomers M2, based on the total amount of monomers used, wherein: the monomers M1 are selected from the group consisting of styrene, divinvlbenzene, esters of monoethylenically unsaturated monocarboxylic and dicarboxylic acids having 3 to 8 carbon atoms with C.sub.1-C.sub.20 alkanols or with C.sub.5-C.sub.8 cycloalkanols, vinyl and allyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms, vinyl halides, conjugated diolefins, C.sub.2-C.sub.6 olefins, amides of ethylenically unsaturated carboxylic acids, ethylenically unsaturated nitriles, hydroxyalkyl esters of ,-ethylenically unsaturated C.sub.3-C.sub.8 monocarboxylic acids and of the C.sub.4-C.sub.8 dicarboxylic acids, esters of the aforesaid monoethylenically unsaturated monocarboxylic and dicarboxylic acids with C.sub.2-C.sub.4 polyalkylene glycols, and N-vinyl amides, and mixtures of these monomers; and the monomers M2 selected from the group consisting of ,-ethylenically unsaturated C.sub.3-C.sub.8 monocarboxylic and C.sub.4-C.sub.8 dicarboxylic acids, 2-(N,N,N-trimethylammonium)ethyl acrylate chloride, 2-(N,N,N-trimethylammonium)ethyl methacrylate chloride, 2-(N,N,N-trimethylammonium)ethylmethacrylamide chloride, 3-(N,N,N-trimethylammonium)propylacrylamide chloride, 3-(N,N,N-trimethylammonium)propylmethacrylamide chloride, 2-(N,N,N-trimethylammonium)ethylacrylamide chloride, and also the corresponding methosulfates and sulfates, and mixtures of these monomers.

6. The penflufen-containing polymer particles as claimed in claim 1, wherein the oil-soluble initiators are selected from the group consisting of 2,2-azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, 1,1-azobis(1-cyclohexanecarbonitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(N,N-dimethyleneisobutyroamidine)dihydrochloride, 2,2-azobis(2-amidinopropane) dihydrochloride, diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis(o-toluoyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleinate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxi-2-ethylhexanoate, diisopropyl peroxidicarbamate, and mixtures of these compounds.

7. The penflufen-containing polymer particles as claimed in claim 1, wherein an amount of penflufen or its salts and acid addition compounds is between 0.5 to 15 wt %, based on the total amount of monomers used.

8. The penflufen-containing polymer particles as claimed in claim 1, additionally comprising further antimicrobially active compounds selected from fungicides, bactericides, herbicides and insecticides.

9. The penflufen-containing polymer particles as claimed in claim 1, wherein the particles have a diameter of 100 nm to 1 m.

10. A penflufen-containing composition comprising penflufen-containing polymer particles as claimed in claim 1, and at least one solvent or diluent.

11. A process for preparing the penflufen-containing polymer particles of claim 1, the process comprising polymerizing the at least one ethylenically unsaturated monomer in the presence of: penflufen or its salts and acid addition compounds, and an oil-soluble radical initiator, in an oil-in-water emulsion polymerization.

12. The process for preparing penflufen-containing polymer particles as claimed in claim 11, wherein the polymerization is carried out at a temperature of 50 C. to 90 C.

13. The process for preparing the penflufen-containing polymer particles as claimed in claim 11, wherein the polymerization is conducted in the presence of costabilizers comprising long-chain, linear or branched or cyclic, aliphatic hydrocarbons selected from the group consisting of C.sub.14-C.sub.25 alkanes and C.sub.14-C.sub.25 cycloalkanes, and mixtures thereof.

14. A method for protecting technical materials against destruction by microorganisms, the method comprising incorporating the penflufen-containing polymer particles as claimed in claim 1 into technical materials.

15. The method as claimed in claim 14, wherein the technical material is wood, wood-plastic composites, and/or a wood product.

16. The penflufen-containing polymer particles as claimed in claim 5, wherein: the oil-soluble initiators are selected from the group consisting of 2,2-azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, 1,1-azobis(1-cyclohexanecarbonitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(N,N-dimethyleneisobutyroamidine)dihydrochloride, 2,2-azobis(2-amidinopropane) dihydrochloride, diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis(o-toluoyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleinate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxi-2-ethylhexanoate, diisopropyl peroxidicarbamate, and mixtures of these compounds; an amount of penflufen or its salts and acid addition compounds is 0.5 to 15 wt %, based on the total amount of monomers used; and an amount of initiators is 0.1 wt % to 5 wt %, based on the total amount of monomers used.

17. The penflufen-containing polymer particles as claimed in claim 16, wherein: the initiators are 2,2-azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile) or mixtures thereof; and an amount of the initiators is 0.1 wt % to 3 wt %, based on the total amount of monomers.

Description

EXAMPLES

[0198] All reported particle sizes were carried out using a Beckmann Coulter LS 13320 particle measuring apparatus with PIDS module in accordance with ISO 13320-1.

Example 1

[0199] A solution of 2.88 g of SDS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 300 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 4.3 g of penflufen, 3.84 g of hexadecane, 1.92 g of benzyl alcohol and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and the mixture is treated with an Ultraturrax (IKA T 25 digital, 11 000 rpm) for 30 minutes in order to produce an emulsion. The resulting emulsion is transferred to a 500 ml stainless steel beaker and ultrasonicated using an ultrasound probe with stirring and coding (ice bath) for 30 minutes (Hielscher Ultrasonics; Ultrasound processor UP200St with S26d7 sonotrode, amplitude 90%). After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. After cooling, a highly mobile, whitish blue suspension is obtained which has a penflufen content of 1.02% (HPLC).

[0200] Average particle size (measured by laser diffraction) 0.091 m; 90% of the particles (vol %) are smaller than 0.128 m.

Example 2

[0201] A solution of 2.88 g of SDS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 200 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 1.92 g of divinylbenzene, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and run (in circulation) through an Ultraturrax (IKA T 25 digital, 10 800 rpm) for 15 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. After cooling, a highly mobile, white suspension is obtained, containing 1.81% of penflufen (HPLC).

[0202] Average particle size (measured by laser diffraction) 0.571 m; 90% of the particles (vol %) are smaller than 1.193 m.

Example 3

[0203] A solution of 2.88 g of SDS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 200 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 1.92 g of divinylbenzene, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and run (in circulation) through an Ultraturrax (IKA T 125 digital/attachment DK 25.11; 10 800 rpm) for 15 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. After cooling, a highly mobile, whitish suspension is obtained which has a penflufen content of 1.51% (HPLC).

[0204] Average particle size (measured by laser diffraction) 0.571 m; 90% of the particles (vol %) are smaller than 1.193 m.

Example 4

[0205] A solution of 2.88 g of SDS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 200 g of water is admixed with an organic solution consisting of 45.85 g of methyl methacrylate. 45.85 g of n-buthyl methacrylate, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and run (in circulation) through an Ultraturrax (IKA T 25 digital/attachment DK 25.11; 10 800 rpm) for 15 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. After cooling, a highly mobile, whitish blue suspension is obtained which has a penflufen content of 1.44% (HPLC).

[0206] Average particle size (measured by laser diffraction) 0.365 m; 90% of the particles (vol %) are smaller than 0.881 m.

Example 5

[0207] A solution of 2.88 g of SOS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 200 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and treated with an Ultraturrax (IKA T 25 digital/attachment DK 25.11; 6600 rpm) for 30 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. After cooling, a highly mobile, whitish suspension is obtained which has a penflufen content of 1.48% (HPLC).

[0208] Average particle size (measured by laser diffraction) 0.574 m; 90% of the particles (vol %) are smaller than 1.290 m.

Example 6

[0209] A solution of 2.88 g of SDS (Na dodecyl sulfate) and 0.163 g of sodium hydrogen carbonate in 200 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and treated through an Ultraturrax (IKA T 25 digital/attachment DK 25.11; 14 000 rpm) for 30 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. It is stirred at this temperature for a further 15 h. Alter cooling, a highly mobile, whitish suspension is obtained which has a penflufen content of 1.49% (HPLC).

[0210] Average particle size (measured by laser diffraction) 0.151 m; 90% of the particles (vol %) are smaller than 0.364 m.

[0211] Comparative Experiment 1 (With Water-Soluble Radical Initiator)

[0212] A solution of 1.15 g of SDS (Na dodecyl sulfate), 0.163 g of sodium hydrogen carbonate and 1.63 g of sodium peroxodisulfate in 144 g of water is admixed with an organic solution consisting of 87.4 g of methyl methacrylate and 8.6 g of penflufen and treated with an Ultraturrax (11 000 rpm) for 30 minutes in order to produce an emulsion. After transfer to a 1000 ml three-neck flask, the emulsion is scrubbed with N.sub.2 and heated slowly with stirring to 70 C. After about 4 hours, the resulting suspension underwent thickening, and penflufen crystallized out. Visible under the microscope is a mixture of very coarse particles of agglutinated polymer and crystallized penflufen.

[0213] An experiment conducted under identical conditions with AIBN (azobis(isobutyronitrile)), an oil-soluble radical initiator, leads to a finely divided suspension without crystallization of penflufen.