AU674533B2 - Novel concentrated aqueous emulsions of neophanes and azaneophanes - Google Patents

Abstract

Concentrated aqueous emulsions of compounds of the general formula I <IMAGE> in which A and B independently of one another represent CH, CR4 or N, X represents CH2, O or S, Y represents CH or N, Z represents H or F, R1 and R4 independently of one another represent H, halogen, (C1-C3)-alkyl, (C1-C3)-haloalkyl, (C1-C3)-alkoxy, (C1-C3 )-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio or R1 and R4 together represent -CH2-O-CH2-; R2 represents H, (C1-C3)-alkyl, ethynyl, vinyl, halogen or cyano, R3 represents H, halogen, (C1-C4)-alkyl, (C1-C3)-alkoxy and M represents C or Si, characterised in that they contain (C12-C14)-fatty alcohols with a low degree of ethoxylation and a narrow range of homologs in combination with an anionic emulsifier and a non-ionic propylene oxide/ethylene oxide block oxyalkylate, have a good shelf life, good pourability and environmentally friendly and user-friendly properties.

Description

t'IUU11 I28'/W1 Regulallon 3.2(2)

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: goof 06 900 :000.

Invention Title: NOVEL CONCENTRATED AQUEOUS EMULSIONS OF NEOPHANES AND

AZANEOPHANES

The following statement is a full description of this invention, including the best method of performing it known to us *0 00 9 0 0 0. 0 0@ 00 Dr. WS/rh HOECHST AKTIENGESELLSCHAFT HOE 92/F 305 Description Novel concentrated aqueous emulsions of neophanes and azaneophanes The present invention relates to novel concentrated aqueous emulsions of compounds of the formula I

CH

3

R

2

R

R- 0

CH

3

Z(I

in which A and B independently of one another are CHi, CR 4 or N, 10 X is CH 2 0 or S, Y is CHlor N, Z is Hor F, R, and R 4 independently of one another are H, halogen,

(C

1

-C

3 -alkyl, (C 1

-C

3 -haloalkyl, (C 1

-C

3 -alkoxy, ~:*l5(C 1

-C

3 )-haloalkoxy, C-C)-alkylthio, haloalkylthio or R, and R 4 together are -CH1 2

-O-CH

2

R

2 is H, (C 1

-C

3 -alkyl, ethynyl, vinyl, halogen or cyano,

R

3 is H, halogen, (C 1

-C

4 -alkyl or (Cl-QC)alox and M is C or Si, which comprise (C 12 -C3.

4 -fatty alcohols with a narrow distribution of homologs and a low degree of lation, in combination with an anionic emulsifier and a non-ionic propylene oxide ethylene oxide block alkoxylate.

_I

2 Alkyl is a straight-chain or branched alkyl radical.

Preferably, A and B are CH or N, X is CH,, Ri is (C 1

-C

3 alkoxy, R 2 is H, R 3 is H or F and M is Si.

A particularly preferred compound of the formula I is that in which M is Si, R, is ethoxy, A and B are CH, X is

CH

2

R

2 is H, Y is CH, Z is F and R 3 is H (Ia).

Active substances from the group of the neophanes and azaneophanes are suitable for controlling animal pests, in particular insects, arachnids and nematodes which are found in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector, while being well tolerated by plants.

They are effective against normally sensitive and resis- 494 tant species and against all or individual development -15 stages (EP-A 0,224,024, EP-A 0,249,015, Er-A 0,288,810).

These documents also describe the conventional types of formulation for insecticides or acaricides.

Besides a broad insecticidal activity, neophanes and azaneophanes of the formula I have an unusually favorable toxicity to warm-blooded species and a very low toxicity to fish and birds.

It was intended to support these positive properties of the active substances by a suitable formulation. The first consideration was to formulate the compounds I, 25 which were in the form of oily liquids and readily soluble in organic solvents, as emulsifiable concentrates

(EC).

H.wever, the preparation of an emulsiL 1ble concentrate requires the use of solvents, which entails a series of disadvantages. In contrast, concentrated aqueous emulsions, which can be prepared without solvents, have the following advantages in comparison with an EC: high flashpoint or none at all, hence safer during transportation and storage; 3 greater safety for the user since the toxicity to the skin and mucous membranes is lower; environmentally friendlier, fewer or no odor problems.

The object was therefore to develop concentrated aqueous emulsions of neophanes and azaneophanes with a sufficient shelf life, good pourability and good technological properties on use.

The preparation of concentrated aqueous emulsions (EW) is described in principle in DE-A 3,009,944, DE-A 3,235,612, EP-A 0,107,023, EP-A 0,160,182 and EP-A 0,297,207.

However, the processes described in these publications cannot be applied advantageously to the active substances to be formulated in the present case since they 15 result in formulations with an insufficient shelf life or in formulations which are unduly viscous.

Generally suitable for the preparation of concentrated S* aqueous emulsions are phosphorylated surfactants, such as, for example, phosphorylated ethylene oxide/propylene oxide block copolymers and ethoxylated and phosphorylated styrylsubstituted phenols. The use of these emulsifiers, even in combination with various unphosphorylated surfactants, as they are described in DE-A 3,346,637, DE-A 3,304,677 and i EP-A 0,257,286, was unsuccessful in the case of the com- 25 pounds I: phase separation occurs at storage temperatures between 0°C and 25 0 C. If the percentage of emulsifiers is increased to prevent this phase separation, then this S, results in a greatly increased viscosity which, consequently, means poor pourability and in some cases also *30 results in thickening upon storage under warm conditions to give a waxy appearance.

The use of a combination of an anionic emulsifier, an n-butanol propylene oxide ethylene oxide block alkoxylate and a sodium/magnesium (and/or aluminum) phyllosilicate for the preparation of concentrated C 4aqueous emulsions of compounds of the formula I gives preparations which are storage-stable and have a good pourability in a broad temperature range (Offenlegungsschrift DE 4,005,155 Al).

The disadvantage of these preparations is that two stirring vessels are required for their preparation, since the sodium/magnesium phyllosilicate must be prepared separately by dissolution in water. This aqueous phase is then added to a second stirring vessel, with stirring, in which the solution of the active substance in the emulsifiers has been prepared.

A decisive simplification of the preparation process, in which it would be possible to dispense with an inorganic thickener and to simply add water to the active substance .15 solution in the emulsifiers instead of dissolving a phyllosilicate in water to prepare the emulsion, would be desirable.

Surprisingly, it has been found that the use of a

(C

12

-C

14 )-fatty alcohol with a narrow distribution of 20 homologs and a low degree of ethoxylation allows exceedingly stable emulsions of compounds of the formula I in water to be obtained, so that the use of a thickener can be dispensed with.

This (C 12 -fatty alcohol with a low degree of ethoxylation can be used for dissolving the active substance together with the additional co-emulsifiers. After the active substance has dissolved, water is added, with *stirring, to prepare the concentrated emulsion. The stabilizing effect of the fatty alcohol with a low degree of ethoxylation is not based on an increased viscosity of the aqueous formulation, rather it is caused by optimizing the emulsion.

The degree of ethoxylation of the (C 12

-C

14 )-fatty alcohol is 1-4 mol of ethylene oxide (EO) per mole of (C 12

-C

14 alcohol, preferably 1.5 to 3.0 mol of ethylene oxide, in particular 2.5 mol of ethylene oxide.

I 5 The (C 12

-C.

4 )-fatty alcohol used is, in particular, isotridecanol or (C 12

-C

14 )-coconut fatty alcohol. A (C 12

-C

14 coconut fatty alcohol with a narrow distribution of homologs and 2.5 mol of ethylene oxide (EO) (Arlypon® F, manufactured by HenKel) is preferred.

The proportion of the (C 12

-C

14 )-fatty alcohol with a low degree of ethoxylation is between 1 and 10 by weight of the formulation, preferably 2 5 by weight.

The (CI 2

-C

4 -fatty alcohol with a low degree of ethoxylation is employed for the preparation of concentrated aqueous emulsions of neophanes and azaneophanes of the formula I in combination with other emulsifiers.

For example, the second non-ionic emulsifier components which can be used may be propylene oxide ethylene oxide 15 block alkoxylates, such as, for example, tributylphenol 10 mol of propylene oxide, oxethylated with 30 mol of ethylene oxide (Hoe S 2435, Hoe Hoechst AG) Alfol® 1620 15 mol of propylene oxide, oxethylated with 30 mol of ethylene oxide (Hoe S 2436); polypropylene glycol 3000 40 by weight of ethylene oxide (Hoe S 1816-1); polypropylene glycol 3000 60 by weight of ethylene oxide (Hoe S 1816-2) and n-butanol propylene oxide ethylene oxide block alkoxylate which can be composed of 1 3 by weight of n-butanol, 40-50 by weight of propylene oxide and 50 60 by weight of ethylene oxide.

9 9 9 A block alkoxylate which is preferably employed is composed of 2 by weight of n-butanol, 44 by weight of propylene oxide and 54 by weight of ethylene oxide (Hoe S 3510, Hoechst AG). The formulation contains 0.5 10 by weight, preferably 1.0 6.5 by weight, of block alkoxylate.

The following can be used as anionic emulsifiers: salts of dodecylbenzenesulfonic acid, salts of optionally chlorinated (C 13

-C

8 )-alkanesulfonic acids, and furthermore -r II 6emulsifiers from the group of the (Co 1 -Ci 1 )-alkylmono-to -hexaglycol ether sulfate salts and of the (C 14

-C

19 alkenol sulfate salts. It is particularly favorable to employ the salts of dodecylbenzenesulfonic acid. The term salts represents alkali metal salts, alkaline earth metal salts or ammonium salts, preferably sodium salts or calcium salts. Calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG) is particularly preferred.

The finished formulation contains 0.5 to 7.0 by weight, preferably 1.0 to 4.0 by weight, of the anionic emulsifier.

The amount of the mixture of two non-ionic and one anionic emulsifier is 4 to 15 by weight, in particular 5 to 12 by weight.

*15 Besides the abovementioned emulsifiers, the formulations according to the invention can comprise other conventional formulation auxiliaries. Antifreeze agents are, for example: monohydric or polyhydric alcohols, glycol ethers or urea, in particular glycerol, isopropanol, propylene glycol monomethyl ether, di- or tripropylene glycol monomethyl ether or cyclohexanol. These antifreeze agents amount to between 0.2 and 20 by weight.

Preservatives which can be added to the aqueous formulations are the following: formaldehyde or hexahydrotriazine derivatives, such as, for example, Mergal® KM 200 by Riedel de Haen or Cobate C by Rh8ne Poulenc, isothiazolinone derivatives, such as, for example, Mergal® K9N by Riedel de Haen or Kathon® CG by Rohm und Haas, 1,2benzisothiazolin-2-ones, such as, for example, Nipacide BIT 20 by Nipa Laboratorien GmbH or Mergal® K10 by Riedel de Haen or 5-bromo-5-nitro-l,3-dioxane (Bronidox® L by Henkel).

These preservatives amount to between 0.0005 and 2 To prepare the formulations descr.ned herein, active substance and emulsifers are first stirred at 25 to 45 0

C

LI 7until a solution has formed. As a rule, this requires 1 to 2 hours. The calculated amount of water is then added dropwise to the active substance/emulsifier solution, with stirring, and the mixture is subsequently stirred for a further 2 to 5 hours at 25 to 300C. This gives emulsions with particle sizes of 50 0.36 0.44 Am.

Equally, the reverse procedure may be followed, by first introducing water and adding the organic solution of emulsifiers and active substance dropwise with stirring.

Identical stirring times and temperatures are applied, the result being emulsions with particle sizes of 50 0.34 0.40 im.

In this way, compounds of the formula I can be formulated to give aqueous emulsions which are storage-stable and S15 have good pourability (suitable viscosity) within a broad i.: temperature range. Moreover, the aqueous emulsions according to the invention have the abovementioned environmentallyand user-friendly properties. The total amount of emulsifiers can be kept extraordinarily low, and the use of solvents is not required, so that the formulations comprise a small amount of environmentally hazardous substances.

*0 0 The concentrations of active substances of the formula I in the above-described formulations can be between 0.1 and 70 as desired and as required by the market, but concentrations between 5 and 45 are preferred.

0 e The invention is illustrated, but not restricted, by the following Preparation Examples: the particle size was determined by means of a Malvern Master Sizer MS20R (by Malvern).

the viscosity was measured using a Rheomat 115, by Contraves.

I

8 Example 1 Based on the finished formulation, a) 40.00 by weight of a compound of the formula I, 1.52 by weight of calcium dodecylbenzenesulf nate (Phenylsulfonat-Ca, Hoechst AG), 2.62 by weight of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510) and 3.53 by weight of isotridecanol with 3 EO (Genapol® X-030, Hoechst AG) are stirred for 2 hours at 40 0 C until a solution has formed.

*oe a.

a'.a b) 52.33 by weight of water is then added dropwise 15 to solution with stirring.

After the dropwise addition, the mixture is stirred for a further 3 hours at 25 30 0 C. An emulsion with a particle size of 50 0.36 im forms.

Example 2 *:20 Based on the finished formulation, a) 41.00 by weight of a compound of the formula I, 1.52 by weight of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG), *25 2.62 by weight of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510) and 3.53 by weight of C 12

-C

14 -coconut fatty alcohol with 2.5 EO (Arlypon® F by Henkel) are stirred for 2 hours at 40 0 C until a solution has formed. This organic phase is added dropwise, with stirring, to b) 51.33 by weight of water.

9 The mixture is subsequently stirred for a further 3 hours at 25 30 0 C. An emulsion with a particle size of 50 0.38 Am forms.

Example 3 Based on the finished formulation, a) 43.00 by weight of a compound of the formula I, 1.32 by weight of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG), 0 2.62 by weight of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510) and 4.03 by weight of C 12

-C,

1 -fatty alcohol with 2 EO (Genapol® X-020, Hoechst 1 9 .99.

99 9 999 9 1 .9 9 9 9 999 9999 *le I Ill 5 AG) are stirred for 2 hours at 400C until a solution has formed.

b) 49.03 by weight .'20 99 9 2 9 :25 e@* of water is subsequently added dropwise to the solution of the active substance in the emulsifiers.

The mixture is subsequently stirred for a further 3 hours at 25 30 0 C. An emulsion wit: a particle size of 50 0.41 Am forms.

Example 4 Based on the finished formulation, a) 43.00 by weight of a compound of the formula I, 1.42 by weight of calcium dodecylbenzene- 1.92 by weight sulfonate (Phenylsulfonat-Ca, Hoechst AG), of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510) and of C 12

-C,

4 -coconut fatty acohol 3.03 by weight C _LI_ 10 with 2.5 EO (Arlypon® F by Henkel) are stirred for 2 hours at 40 0 C until a solution has formed.

b) 50.63 by weight of water is subsequently added dropwise to the organic solution.

The mixture is subsequently stirred for a further 3 hours at 25 30 0 C. An emulsion with a particle size of 50 0.37 Am forms.

.00.

0o.

*.i C .C C* Example Based on the finished a) 20.6 by weight 2.2 by weight co.

CC C 5.8 by weight 3.0 by weight b) 68.4 by weight formulation, of a compound of the formula of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG), of polypropylene glycol 3000 40 by weight of ethylene oxide (Hoe S 1816-1), of C, 1

-C

14 -coconut fatty alcohol with 2.5 E, (Arlypon® F by Henkel) and of water.

00 C. S

CS

C

5 The preparation is as described in Example 1. An emulsion with a particle size of 50 0.36 Am forms.

Example 6 Based on the finished formulation, a) 20.4 by weight of a compound of the formula

I,

2.2 by weight of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, 11 Hoechst AG), 5.7 by weight by weight b) 68.7 by weight of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510), of C 12

-C

4 -coconut fatty alcohol with 2.5 EO (Arlypon® F by Henkel) and of water.

0000 00.

:00.: 0* 0 *0 i a 0.*@a *00 The preparation is as described in Example 2. An emulsion with a particle size of 50 0.34 pm forms.

0 as 0 :20 9500 dl a *s S 0* S CL .:25 Example 7 Based on the finished a) 21.3 by weight 2.2 by weight 5.8 by weight by weight b) 67.7 by weight formulation, of a compound of the formula

I,

of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG), of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510), of C 12

-C

1 4 -coconut fatty alcohol with 2.5 EO (Arlypon® F by Henkel) and of water.

The preparation is as described in Example 1. An emulsion with a particle size of 50 0.36 pm forms.

The viscosity of the aqueous emulsions of Examples 6 and 7 is 19 23-mPa s at a low shearing stress of 16.8 sec-" and at 15 18.mPa s at a high shearing stress of 144 sec 1 12 Example 8 Based on the finished a) 7.3 by weight 1.3 by weight by weight formulation, of a compound of the formula I, of calcium dodecylbenzenesulfonate (Phenylsulfonat-Ca, Hoechst AG), of n-butanol propylene oxide/ ethylene oxide block alkoxylate (Hoe S 3510), of C.

2

-C

14 -coconut fatty alcohol with 2.5 EO (Arlypon® F by Henkel) and 1.8 by weight 0*6@

S

,b sc. S

C.

*r C er

CC'S

o C C CC C, C b) 86.1 by weight of water.

The preparation is as described in Example 1. A 15 transparent microemulsion forms.

The concentrated aqueous emulsions of Preparation Examples 1-8 are homogeneous after storage for three months at 200C, 400C and 50 0 C, after storage for 14 days at 54°C and after storage for 14 days at 0°C, no phase 20 separation or precipitation of solids is observed.

When diluted to the use concentration, the concentrated aqueous emulsions of Examples 1 to 8 meet the international test standards before and after storage; i.e.

after a standing time of 6 hours, no creamy or oily 25 substances separate out from an emulsion diluted to 5 with water at 30 0 C and a hardness of 342 ppm (CIPAC standard water D (CIPAC Handbook, Vol. 1, p. 878, Collaborative International Pesticides Analytical Council Ltd. (1970), see also Specifications for Pesticides used in public Health, World Health Organization, Geneva (1973)).

CC CC d* 4 a Ce C

CC

6

Claims (12)

1. A concentrated, aqueous emulsion comprising at least one compound of the formula I ACH R2 R3 B CH 3 z (I) in which A and B independently of one another are CH, CR 4 of N, X is CH 2 O or S, Y is CH or N, Z is H or F, R 1 and R 4 independently of one another are H, halogen, (Cl-C3)-alkyl, (C1-C 3 )-haloalkyl, (Ci-C 3 )-alkoxy, (Ci-C 3 )-haloalkoxy, (CI-C4)- alkylthio, (C1-C 4 )-haloalkylthio or Ri and R 4 together are -CH 2 -O-CH 2 R2 is H, (C 1 -C 3 )-alkyl, ethynyl, vinyl, halogen or cyano, R 3 is H, halogen, (C1-C 4 )-alkyl or (C 1 -C 3 )-alkoxy and M is C or Si, and (C 1

2-C1 4 )-fatty alcohol ethoxylates with a narrow distribution of hcmologs and a low degree of ethoxylation, in combination with an anionic emulsifier and a non-ionic propylene oxide ethylene oxide block alkoxylate. 2. A concentrated, aqueous emulsion as claimed in claim 1, wherein, in formula I, wherein, in formula I, A and B a;e CH or N, X is CH 2 R 1 is (Ci-C3)- alkoxy, R 2 is H, R 3 is H or F and M is Si. 14

3. A concentrated, aqueous emulsion as claimed in claim 1 or 2, wherein, in formula I, M is Si, R 1 is ethoxy, A and B are CH, X is CH 2 R 2 is H, Y is CH, Z is F and R 3 is H.

4. A concentrated, aqueous emulsion as claimed in any one of claims 1 to 3, which, after dilution, comprises 0.1 70% by weight of a compound of the formula I, 0.5 7.0% by weight of anionic emulsifier, 1 10% by weight of C 12 -C 14 -fatty alcohol with a low degree of ethoxylation and 0.5 10% by weight of block alkoxylate.

A concentrated, aqueous emulsion as claimed in any one of claims 1 to 4, which, after dilution, comprises 0.1 45% by weight of a compound of the formula I, 1.0 4.0% by weight of anionic emulsifier, 2 5% by weight of C 12 -C 14 -fatty alcohol with a low degree of ethoxylation and 1.0 6.5% by weight of block alkoxylate.

6. A concentrated, aqueous emulsion as claimed in any one of claims 1 to which comprises an alkali metal salt or alkaline earth metal salt of dodecylbenzenesulfonic acid as anionic emulsifier and, as non-ionic emulsifier, C12-C1 4 -coconut fatty alcohol with 2.5 mol of ethylene oxide with a narrow distribution of homologs and/or propylene oxide/ethylene oxide block oxalkylate.

7. A concentrated, aqueous emulsion as claimed in any one of claims 1 to 6, comprising a block alkoxylate composed of 2% by weight of n-butanol, 44% by weight of propylene oxide and 54% by weight of ethylene oxide.

8. A concentrated, aqueous emulsion as claimed in any one of claims 1 to 6, which comprises between 4 and 15% by weight of the mixture of two non-ionic and one anionic emulsifier.

9. A concentrated, aqueous emulsion as claimed in claim 8, which comprises between 5 and 12% by weight of the mixture of two non-ionic and one anionic emulsifier.

A method of controlling noxious insects or acarids, which comprises applying an effective amount of concentrated, aqueous, optionally diluted emulsion as claimed in any one of claims 1 to 9 to these noxious insects or acarids or to the plants, areas, substrates or seed infested with them.

11. The use of a concentrated, aqueous, optionally diluted emulsion as claimed in any one of claims 1 to 9 for controlling noxious insects or acarids.

12. A process for the preparation of aqueous emulsions as claimed in any one of claims 1 to 9, which comprises stirring the active substances of the formula I and the above-described emulsifiers until a solution has formed and subsequently adding water, or stirring water and subsequently adding the aforesaid solution. DATED this 25th day of July, 1996 HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA a *i AU4755093.WPC[DOC. 007]KJS:EK HOE 92/F 305 Abstract of the disclosure Novel concentrated aqueous emulsions of neophanes and azaneophanes Concentrated, aqueous emulsions of compounds of the formula I R2 C H 3 y 3 A. H 3 (I in which A and B independently of one another are CH, CR 4 or N, X is CH 2 0 or S, Y is CH or N, Z is H or F, R, and R 4 independently of one another are H, halogen, (CI-C 3 )-alkyl, (C,-C 3 -halo- alkyl, (CI-C 3 -alkoxy, (CI-C 3 -halo- alkoxy, (Ci-C 4 -alkylthio, (C-C 4 haloalkylthio or R, and R 4 together are -CH 2 -O-CH 2 R, is H, (C 1 -C 3 )-alkyl, ethynyl, vinyl, halogen or cyano, R 3 is H, halogen, (C 1 -C 4 )-alkyl or (C 1 -C 3 -alkoxy and M is C or Si, which comprise (C 12 -C 14 )-fatty alcohols with a narrow distribution of homologs and a low degree of ethoxy- lation, in combination with an anionic emulsifier and a non-ionic propylene oxide ethylene oxide block alkoxylate, I have a good shelf life, good p0urability and environmentally- and user-friendly properties. p. 0S 0@ 6 00 0. 0S0* 0 04.. S. 5 0 0 0. 0