FORMULATION OF INSECTICIDES COMPRISING PROPYLENE CARBONATE

Abstract

The invention relates to insecticidal active ingredient formulations comprising at least one active ingredient or a combination of active ingredients in solid form having good storage stability at high and low temperatures and high active ingredient penetration, to a process for production thereof and to the use thereof for application of the active ingredients present.

Claims

1. A composition comprising: a) at least one active ingredient solid at room temperature, b) at least one ammonium salt, c) at least one dispersant from the class of the alkyl propoxylate ethoxylates, d) optionally one or more surfactants, e) at least one water-insoluble filler, f) at least one solvent from the group of the carbonate esters, and g) optionally one or more further adjuvants, where active ingredient a) is insoluble or only slightly soluble in solvent f).

2. The composition according to claim 1, wherein d) is obligatory.

3. The composition according to claim 1, wherein a) is selected from the group of the active insecticidal ingredients having a solubility in the chosen solvent 0 of not more than 5 g/l, further optionally not more than 4 g/l, optionally not more than 2.5 g/l, and optionally not more than 1 g/l.

4. The composition according to claim 1, wherein a) is selected from the group consisting of diamide insecticides, spinosyns (IRAC Group 5), mectins (IRAC Group 6), ethiprole, triflumuron, deltamethrin and tetronic acid or tetramic acid derivatives (IRAC Group 23.

5. The composition according to claim 1, wherein a) is selected from the group of the tetronic acid or tetramic acid derivatives (IRAC Group 23).

6. The composition according to claim 1, wherein a) is a tetramic acid derivative of formula (I) ##STR00031## wherein W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine, X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which they are bonded are C3-C6-cycloalkyl substituted by an optionally C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl-substituted alkylenedioxy group that forms a 5-membered or 6-membered ketal together with the carbon atom to which it is bonded, G is hydrogen (a) or is one of the groups ##STR00032## wherein E is a metal ion or an ammonium ion, M is oxygen or sulfur, R1 is straight-chain or branched C1-C6-alkyl, R2 is straight-chain or branched C1-C6-alkyl.

7. The composition according to claim 1, wherein a) is a compound of formula (I-2) ##STR00033##

8. The composition according to claim 1, wherein b) is selected from the group consisting of ammonium carbonate, ammonium hydrogensulfate, ammonium sulfate (AMS), ammonium hydrogencarbonate, ammonium carbonate and diammonium hydrogen-phosphate (DAHP).

9. The composition according to claim 1, wherein c) is selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compound of formula (III-a)
R—O-A-B—H   (III-a) where R is a C1-C4 fragment, optionally a C3-C4 fragment, optionally a C4 fragment, A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), optionally consisting of 15-35 PO units, optionally consisting of 20-30 PO units, B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units (formula III-c) together with 0-10 propylene glycol (PO) units, optionally consisting of 20-40 EO units together with 0-8 PO units, optionally consisting of 30-40 EO units together with 0-5 PO units, ##STR00034## and alkyl polypropylene glycol-polyethylene glycol compounds of formula (IIId)
R—O—(C.sub.mH.sub.2mO).sub.x—(C.sub.nH.sub.2nO).sub.y—R′  (IIId) wherein R and R′ are independently hydrogen, a linear C.sub.1- to C.sub.5-alkyl radical or a branched C.sub.3- or C.sub.4-alkyl radical; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, where one radical n or m has the meaning of 2 and the other radical n or m has the meaning of 3.

10. The composition according to claim 1, wherein d) is a surfactant selected from the group consisting of polycarboxylate types, salts of sulfated formaldehyde condensation products with alkylaromatics, salts of sulfated formaldehyde condensation products with ditolyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignosulfonates and salts thereof.

11. The composition according to claim 1, wherein e) is selected from the group consisting of comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silicas, attapulgites and fillers based on synthetic polymers.

12. The composition according to claim 1, wherein e) is selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and isomers thereof, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate and octylene carbonate.

13. The composition according to claim 1, wherein components are present as follows: a) 1-30% by weight b) 1-40% by weight c) 1-40% by weight d) 0-10% by weight e) 0.1-15% by weight g) 0-10% by weight f) to one litre.

14. The composition according to claim 1, wherein components are present as follows: a) 2-15% by weight b) 15-30% by weight c) 10-30% by weight d) 0.5-2.5% by weight e) 1-10% by weight g) 0.05-6% by weight f) to one litre.

15. The composition according to claim 1, comprising a) compound having formula (I-2) having the following structure: ##STR00035## b) at least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogenphosphate (DAHP), c) at least one dispersant comprising alkyl polypropylene glycol-polyethylene glycol compound of formula (III-a)
R—O-A-B—H   (III-a) where R is a C1-C4 fragment, optionally a C3-C4 fragment, optionally a C4 fragment, A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), optionally consisting of 15-35 PO units, optionally consisting of 20-30 PO units, B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units (formula III-c) together with 0-10 propylene glycol (PO) units, optionally consisting of 20-40 EO units together with 0-8 PO units, optionally consisting of 30-40 EO units together with 0-5 PO units, ##STR00036## and alkyl polypropylene glycol-polyethylene glycol compounds of formula (IIId)
R—O—(C.sub.mh.sub.2mO).sub.x—(C.sub.nH.sub.2nO).sub.y—R′  (IIId) in which wherein the individual radicals and indices have the following definitions: R and R′ are independently hydrogen, a linear C.sub.1- to C.sub.s-alkyl radical or a branched C.sub.3- or C.sub.4-alkyl radical; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, where one radical n or m has the meaning of 2 and the other radical n or m has the meaning of 3, d) at least one surfactant selected from the group comprising polycarboxylate types, e) at least one filler selected from the group comprising fumed silicas and attapulgites, f) at least one solvent selected from the group comprising propylene carbonate, g) optionally one or more further adjuvants.

16. A product comprising a composition according to claim 1 for controlling insects.

Description

EXAMPLE I

[0363] All formulation constituents according to the experiments described in Tables Ia-c are combined in a 25 ml PE screwtop bottle, and 10 g of glass beads (size 1-1.25 mm) are added. The bottle is closed, clamped in an agitator apparatus (Retsch MM301) and treated at 30 Hz for 40 minutes; in the course of this, the samples heat up. After the time has elapsed, the samples are cooled down to room temperature and the consistency of the formulation is assessed. Subsequently, by means of a microscope (Zeiss transmitted light microscope, 40-fold magnification) the presence of agglomerates is evaluated, and the particle size is determined by laser dispersion. A very small particle size indicates good grindability, while the presence of agglomerates is a sign of poor dispersion characteristics.

TABLE-US-00010 TABLE 1 (figures in % by weight) Example No. 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 I-2 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 SAG 1572 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 DAHP [% w/w] 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 AMS [% w/w] 20.00 20.00 20.00 Geropon T36 1.00 5.00 1.00 1.00 1.00 1.00 1.00 Morwet D-425 5.00 1.00 1.00 1.00 1.00 1.00 Soprophor 3D33 5.00 Soprophor FLK 5.00 Rhodacal 60 BE 5.00 Borresperse NA 5.00 Emulsogen EL 400 5.00 Antarox B/848 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Atlas G5002L 20.00 20.00 Lucramul HOT 5902 20.00 20.00 Propylene carbonate 56.90 52.90 52.90 52.90 52.90 52.90 52.90 52.90 57.90 55.90 55.90 55.90 55.90 55.90 Concentrate fluid fluid fluid fluid fluid fluid fluid fluid fluid fluid fluid fluid fluid fluid Particle size [d90/50, μm] 3/1 5/2 5/2 6/3 5/2 8/3 3/2 30/15 32/16 8/2 2/1 4/1 5/2 3/1 Agglomerates [yes/no] yes no no partial partial no no no yes no no no no no

[0364] Evaluation of the Experiments:

[0365] The formulations based on I-2, ammonium salt and propylene carbonate with different amounts of surfactants (experiment 1-1, 1-2) show basic grindability of the respective ammonium salts and of I-2 under the experimental conditions specified, but significant agglomeration of the salt crystals in the concentrate is observed under the microscope, unless sufficient surfactant (>1%) is present in the formulation, meaning that the individual particles are dispersed very inadequately, if at all, in the liquid phase. Only certain surfactants are able to properly disperse the ammonium salt and I-2 (e.g. 1-3, 1-6, 1-7), and alkyl propoxylate ethoxylates are not able to do this on their own, as can be seen by the coarse size of the sample milled only with Antarox B/848 (1-9), as well as the presence of the agglomerates.

[0366] Most effective and surprising is the combination of two different surfactants in small amounts (experiments 1-10 to 1-14). This combination (Geropon T-36 and Morwet D-425) is particularly surprising because 1.00% of each surfactant is most effective in milling and stabilizing DAHP or AMS, than 5.00% of each of the surfactants alone.

EXAMPLE II

[0367] For the purpose of testing suitable thickeners in the presence of suitable dispersing aids, all formulation constituents as specified in Table 2 are combined and homogenized with a colloidal mill. Subsequently, bead grinding is conducted (Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding for 40 min) and the resultant formulation is analysed. Subsequently, a storage test is conducted at elevated temperature and then a qualitative/quantitative assessment of appearance, phase separation, rheological properties and dispersion stability after storage (e.g. viscosity) is performed

[0368] The assessment of appearance takes place analogously to DIN 10964 “Sensory analysis—Simple descriptive test”. For this purpose, the samples to be examined are examined visually and, if required, by means of shaking and tilting, for shape, state of matter and colour and further peculiarities (especially, for example, lumps, caking, sediment formation, subsequent thickening, marbling of the sediment etc.).

[0369] Phase separation directly after storage is reported either as sediment content and calculated from the quotient H1 [level of the interface layer between sediment phase and supernatant] divided by HO [total fill height of the sample], or as done here by the supernatant content:

Sediment content=(H1/H0)*100 [%] or

Supernatant content=100−sediment content [%]

[0370] The assessment of viscosity is performed as per the CIPAC MT192; “Viscosity of Liquids by rotational viscometry” method.

[0371] Dispersion stability in 2% aqueous dilution is determined by analysing the amount of residue deposited after a certain amount of time according to the CIPAC MT 180 Method “Dispersion stability of suspo-emulsions”.

TABLE-US-00011 TABLE 2 (figures in % w/w) Example No. 2-1* 2-2* 2-3* 2-4* 2-5* 2-6* I-2 2.00 2.00 2.00 2.00 2.00 2.00 Geropon T36 1.00 1.00 1.00 1.00 1.00 1.00 Morwet D-425 1.00 1.00 1.00 1.00 1.00 1.00 Antarox B/848 20.00 20.00 20.00 20.00 20.00 20.00 Aerosil 200 3.00 3.00 Aerosil 380 3.00 3.00 Aerosil R812S 3.00 Aerosil R805 3.00 Diammonium Hydrogen 20.00 20.00 20.00 20.00 20.00 20.00 Phosphate SAG 1572 0.10 0.10 0.10 0.10 0.10 0.10 Dibutyl Carbonate 52.90 Dimethyl Carbonate 52.90 Propylene carbonate 52.90 52.90 52.90 52.90 Appearance of Concentrate Appearance Concentrate fluid Milling not separated highly viscous fluid Milling not possible due phases possible due to very high to very high viscosity viscosity Agglomerates [yes/no] no n/a no no no n/a Syneresis/Phase Separation Supernatant after 98 n/a 36 96 97 n/a 4 w at 54 [%] Characterization Compact sediment. n/a Compact Compact sediment. fluid n/a of the sediment Formulation is sediment Formulation is after storage at solid, and becomes solid, and becomes 54 for 4 w liquid upon shaking liquid upon shaking Rehomogenizability bad n/a moderate moderate good n/a after storage at 54° C. for 4 w Supernatant after 77 n/a 80 98 96 n/a 4 w at RT [%] Characterization fluid n/a n/a Compact sediment. fluid n/a of the sediment Formulation is after storage at solid, and becomes RT for 4 w liquid upon shaking Rehomogenizability bad n/a bad moderate good n/a after storage at RT for 4 w Viscosity Dynamic viscosity @ 35 n/a 49 76 101 n/a 8.9 1/s fresh sample [mPa .Math. s] Dynamic viscosity @ 28 n/a 43 72 67 n/a 109 1/s fresh sample [mPa .Math. s] Dynamic viscosity @ 1637 n/a 66 576 145 n/a 8.9 1/s after 4 W @ 54° C. [mPa .Math. s] Dynamic viscosity @ 224 n/a 54 142 86 n/a 109 1/s after 4 W @ 54° C. [mPa .Math. s] Dynamic viscosity @ 409 n/a 52 614 436 n/a 8.9 1/s after 4 W @ RT [mPa .Math. s] Dynamic viscosity @ 85 n/a 46 143 119 n/a 109 1/s after 4 W @ RT [mPa .Math. s] Dispersion Stability (2% formulation, CIPAC C Water, RT) Dispersion stability 12 n/a 12 10 0.2 n/a after 1 h fresh sample [mL] Dispersion stability 10 n/a 15 15 5 n/a after 1 h after 4 W @ 54° C. [mL] Dispersion stability 10 n/a 15 0 0.1 n/a after 1 h after 4 W @ RT [mL] *inventive example

[0372] Evaluation of the Experiments:

[0373] Without use of additional dispersing aids, using particular insoluble fillers such as Aerosil 200, Aerosil 380 or Aerosil R812S it is possible to produce stable formulations having different viscosities (Recipes 2-1, 2-3, 2-4, 2-5). Particularly important it is to choose the right combination of filler and solvent, in order to avoid a situation where the formulation becomes extremely viscous and not processable (Recipes 2-2, 2-6).

[0374] After storage for four weeks at room temperature, all processable formulations (Recipes 2-1, 2-3, 2-4, 2-5) have only small phase separation and in some cases moderate to good redispersibility. After storage for four weeks at 54° C. almost all processable formulations (Recipes 2-1, 2-3, 2-4, 2-5) have small phase separation and in most cases moderate to good redispersibility.

[0375] A further factor for ascertaining formulation stability is the dispersion stability of the formulation in aqueous dilution. It is found that all processable formulations (Recipes 2-1, 2-3, 2-4, 2-5) are dispersable in water, and after storage at room temperature or at 54° C. in some cases the phase separation is relatively small (<=5 mL).