DK145445B - LOW-VISCUS CONCENTRATES OF ANION-ACTIVE BIOCID EMULGATORS IN ORGANIC OH-GROUP-FREE NON-POLAR SOLVENTS - Google Patents

Description

® (12) PUBLICATION <n) 145445 B

(19) DENMARK

*

DIRECTORATE OF

PATENT AND TRADEMARKET SYSTEM

(21) Application No 389/76 (51) lnt (3.9 A 01 N 25/30 (22) Submission date 30 · Jan 1976 // B 01 F 17 / ½ (24) Running day 30 Jan 1976 (41) Available Aug. 1, 1976 (44) Submitted Nov. 22, 1982 (86) International Application No. - (86) International Filing Day - - (85) Continuation Day - (62) Standing Application No. - a

(30) Priority Jan 31 1975 * 2504136 * DE

(71) Applicant H0ECHST AKTIENGESELLSCHAFT, 6230 Frankfurt / Main 80, BE. > (72) Inventor Zoltan Damo, DE: Manfred Schmidt, DE: Wilhelm Sten? * Ger, DE.

(74) The engineering firm Budde, Schou & Co.

(54) Low viscous concentrates of anion = active biocide emulsifiers 1 organic OH-free, non-polar solvents.

Biocides are used to eradicate insects and weeds in agriculture. The biocides can be compounds of different chemical structure. Known biocides are, for example: chlorinated hydrocarbons, e.g. the commercial product DDT (dichlorodiphenyltriphloroethane), lindane (hexachlorocyclohexane), aldrin (hexachlorohexahydro-dimethane-naphthalene), dieldrin or endrin (hexachloro-epoxy-octahydroxide)

ISLAND

-j- -dimethano-naphthalene), heptachlor (heptachlorodomethylene-tetrahydro-indene) and toxaphene (chlorinated camphene). Significant and indispensable biocides are also certain organic phosphoric and thiophosphoric esters, e.g. the trading products £ methylparathione (p-nitrophenyl-dimethyl-thiophosphoric ester), ^ ethylparathion (p-nitrophenyl-diethyl-thiophosphoric ester) and

Malathione (0,0-dimethyl-S- (X, 2-dicarbethoxyethyl) -dithiophosphate), diazinone (0,0-diethyl-O- [2-isopropyl-6-methyl-pyrimidinyl- (5)]) thiophosphoric acid ester and phosdrin (0,0-dimethyl-O- (1-carbomethoxy-1-propen-2-yl) -phosphoric ester) as well as other known water-insoluble biocides.

For the preparation of spray liquids of these water-insoluble biocides, they are used in the form of their emulsion concentrates which, in addition to the active substances, further contain organic solvents and emulsifiers. Suitable and widely used emulsifiers are, above all, mixtures of alkaline earth metal salts of alkylbenzenesulfonic acids or long chain chloro paraffin sulfonic acids and nonionic surfactants, e.g. adhesive compounds of ethylene oxide and / or propylene oxide with high molecular weight alcohols, thioalcohols, alkylphenols or carboxylic acids having approx. 8-24 carbon atoms and approx. 4-60 oxyalkylene groups. Such emulsion concentrates are described e.g. in United States Patent No. 2,696,453, British Patent No. 717,279 and German Patent No. 2,118,619.

The emulsion concentrates are prepared by manufacturers of plant protection products, preferably by mixing the biocides or their solutions in organic solvents with the most frequently liquid non-ionic emulsifiers, the alkaline earth metal sulphonates serving as anionic emulsifiers in the form of their high-percentage organic solvents and organic solutions, solvents and other additives. The ratio of the single components may hereby differ depending on the biocidal agent to be emulsified, because in practice any biocide to produce an optimum effective emulsion needs a different composition than the emulsifier mixture.

Consequently, it has been found appropriate that the single emulsifier co-pencils be offered commercially separately and first blended by the manufacturers into the finished biocide emulsion concentrates.

In order to assure the emulsion concentrates of plant protection products good manageability of the starting products as well as the greatest possible freedom in the selection of prescriptions of their mixtures, the alkaline earth metal sulphonates serving as anionic emulsifiers are preferably offered as highly concentrated as possible pourable solutions in organic solvents. all in isobuta-nol.

·; * - **.

3 145445

Now it is e.g. known from R. Weglir "Chémie der Pf láirzen-schutz- und Schådlingsbekåmpfungsmittel" Volume 1, pages 248-256: (1970) and C. Pest and KJ Schmidt, "The" Chemistry and OrganophdS-phorus Pesticides ", pages 25-42 (1973) that certain biocidal active water-insoluble phosphoric esters and their sulfur homologue as well as derivatives of these compounds, depending on their substituents, may react more or less strongly with water or alcohols and during hydrolysis and alcoholysis, respectively, thereby reducing their biocidal action. and / or the solvolysis products: e.g. upon precipitation leads to disturbances within the mixtures.

In addition, the disintegration effects of dissociated phosphorus-containing biocides have a higher hot blood toxicity than the actual active substances. Thus, e.g. D. Mello, FR Pt% a and R. Benintendi in "Biologico" 38, 136-139 (1972) on severe poisoning cases with an emulsion concentrate of the commercial product "Diazinon" which, by partial decomposition of the active substance to 'tetraethyl monothiopyrophosphate (LD 2 -q 5 mg / kg) had become 3x more toxic than a concentrate with the original harmless active substance (LD 50 300 mg / kg).'

This danger of degradation is, of course, found especially in the so-called short-term biocides, which, after a few days after the spread, must have lost their biological activity, so that "treated" objects can be brought to market. This accelerated loss of action of the biocides is preferably achieved by greater hydrolysis or solvation sensitivity or by a higher vapor pressure thereof. active substance.

Such sensitive biocides to water and alcohols are among others. also the insecticides used in practice phosphoric acid and thiophosphoric acid esters, such as 1-phenyl-3- (0,0-diethylthinophds-1 'phoryl) -1,2,4-triazole (hereinafter referred to as biocyclic), 2- ( O, O-Diethylthionophosphoryl) -5-methyl-6-carbethoxy-pyrazolo [1,5-ajpyrimidine (biocide B) and 6- (0,0-dimethylphosphoryl) -7-chloro-bicyclo [3.2.0 ] -heptadiene (biocide C). - ''

The hydrolysis sensitivity of such biocides is shown e.g. in the following experiments: 1200 mg of the biocide to be tested is stored with approx. 800 mg of isobutanol for 16 hours at 80-9 ° C and then analyzed.

Here are the following results: 4 145445

Biocide A: 10% by weight loss of active ingredient, releasing corresponding amounts of 1-phenyl-3-hydroxy-1,2,4-triazole and diethylisobutylthiophosphate,

Biocide B: 35% Loss of Active Substance Releasing 2-Oxo-5-Methyl-6-Carbethoxy-1,2-Dihydro-Pyrazolo [1,5-a] Pyrimidine, Diethyl Isobutyl Thiophosphate and Other Decomposition Products .

Biocide C: 48% Loss of Active Substance Releasing 6-Iso-Butyloxy-7-Chloro-Bicyclo [3,2,0] -Heptadiene (2,6), Diethyl-Isobutyl Phosphate and Other Cleavage Products .

As mentioned above, as the solvent for the alkaline earth metal salts used as anionic emulsifiers, isobutanol is most often used. However, in terms of possible solvolysis and hydrolysis, this solvent has the disadvantage, on the one hand, of containing hydroxy groups which can cause an alcoholysis and, on the other hand, dissolving water up to 16%, the complete removal of which by azeotropic distillation is very difficult in the presence of of alkaline earth metal sulfonates.

Therefore, it is sought for these alkaline earth metal sulfonates to use OH-group-free solvents, especially alkylbenzenes such as toluene or xylene, as well as mixtures of higher-boiling alkylbenzenes of about 3-5 carbon atoms in the alkyl groups (commercially, for example, under the trade name Shellsol A). However, such experiments showed no satisfactory results. Namely, as a disadvantage of these solvents, it was found that the alkaline earth metal sulphonate solutions thus obtained can no longer be poured at relatively low concentrations. Thus, e.g. a 20% by weight solution of calcium tetrapropylene benzenesulfonate in xylene high viscosity and a 25% by weight solution can no longer be poured. By comparison, they succeeded in preparing over 70% by weight solutions of calcium tetrapropylene benzenesulfonate in isobutanol.

The present invention relates to low viscous concentrates of anionic biocide emulsifiers in organic non-polar, non-polar solvents, which concentrate is characterized in that they contain from ca. 25 to approx. 75 wt% anion - active emulsifiers and as viscosity reducing additives contain from approx. 0.5 to approx. 15% by weight of compounds of the general formula R 1 - (O - X) n - O - R 2 (I) 1 2 wherein R and R are alkyl groups of 1-4 carbon atoms, alkylcarbonyl groups of 2-4 carbon atoms or a carbamoyl group having 1-4 carbon atoms, X means an alkylene group having 2-4 carbon atoms, and n means 1-20.

Surprisingly, it has been found that by adding small amounts of the above-mentioned compounds of general formula (I) to solutions of anionic, emulsifying-acting sulfonates in nonpolar OH-group-free organic solvents, a very strong reduction in the viscosity of these solvents so as to produce higher concentrated pourable solutions.

In the general formula, R and R are in particular methyl, ethyl or tertiary butyl groups, the carbonyl group acetyl or butyryl or the carbamoyl group methyl or butylcarbamoyl. In particular, X means the ethylene, methylethylene, trimethylene or tetramethylene group.

In particular, X means the ethylene group.

For the purposes of the present invention as viscosity-lowering agents, compounds of the above formula have proved particularly suitable in which R and R are alkyl groups of 1-4 carbon atoms, X is ethylene and n is 1-4.

As non-polar, OH-group-free organic solvents for the preparation of the concentrates according to the invention, aromatic hydrocarbons and their mixtures with aliphatic hydrocarbons are primarily considered. Suitable solvents are e.g. benzene, toluene, xylene, polymethylated naphthalene, mixtures of aromatic hydrocarbons as present in the commercial product Shellsol A or mixtures of aromatic and aliphatic hydrocarbons as present in kerosene.

Generally, for the preparation of the solutions of anionic emulsifiers in non-polar solvents, a relatively small addition of the compounds of formula I used as viscosity-lowering agents is generally sufficient. Depending on the concentration of the emulsifiers, amounts of * 0.5 to approx. 15 weight percent, especially 1-10 weight percent, attributed to the weight of the emulsifier solution.

As anionic emulsifiers, the known emulsifiers used in the preparation of emulsion concentrates of water-insoluble organic biocides are considered.

6 1A5ååS

In particular, such anionic emulsifiers are alkaline earth metal salts, preferably calcium salts of alkylbenzenesulfonic acids or longer-chain chloro paraffin sulfonic acids, such as those e.g. is disclosed in U.S. Patent No. 2,696,453 and German Patent No. 2,118,619.

In the concentrates according to the invention, the anionic emulsifiers may be present in concentrations of approx. 25 to approx. 75% by weight Preferably the concentrations in the solutions are adjusted to 35-60% by weight.

In addition to the emulsion concentrates of anionic emulsifiers, nonionic emulsifiers are used in addition to the concentrates of anionic emulsifiers. These non-ionic emulsifiers are the already known adhesive compounds of ethylene oxide and / or propylene oxide known with fatty alcohols, fatty acids, alkylphenols or thioalcohols. However, as non-ionic emulsifiers for hydrolysis-sensitive organic biocides, the compounds described in Danish Patent Application No. 379/76 preferably come with the following formulas II and / or III.

R1 (-0-X) n ~ Y (II) ch2-oco- (ch2) 7-ch = ch-ch2-ch- (ch2) 5-ch3

(0CH2CH2) X-Y

CH-COC (CH2) 7-CH = CH-CH2-CH- (CH2) 5 "CH3 (OCH2CH2) yY (III) CH2-OCO- (CH2) 7-CH = CH-CH2-CH- (CH2) 5 "CH3

(0ch2ch2) z-Y

In these formulas, R represents an alkyl or alkenyl group of 8-20 carbon atoms or an alkylphenyl group of 4-12 carbon atoms in the alkyl group, X means ethylene or ethylene and propylene groups, preferably ethylene groups, Y means halogen, especially chlorine or bromine. or the group OR, wherein R is a lower alkyl group, a phenyl, tolyl or benzyl group, or an alkylcarbonyl group of 1-18 carbon atoms, an acetoacetyl group or an N-alkyl or phenylcarbamyl group, n, x, y and z mean 6-60, whereby the sum of x, y and z, which can assume equal or different values, is 18-180.

7 U5U5

Water-insoluble organic biocides for which emulsification due to their sensitivity to hydrolysis or solvate concentrates according to the invention of anionic emulsifiers in hydroxyl-group-free solvents and non-ionic emulsifiers of general formulas (II) and (III) may be used for all such within the group of phosphoric or thiophosphoric esters or their derivatives.

As such hydrolysis- or solvolysis-sensitive biocides, e.g. The following products are mentioned: Tetraethyl pyrophosphate (TEPP), [2-chloro-2- (diethylcarbamoyl) -1-methylvinyl] dimethyl phosphate (Phosphamidone), dimethyl phosphate of 3-hydroxy-N, N-dimethyl-cis-crotonamide (Dicrotophos ), dimethyl phosphate of 3-hydroxy-N-methyl-cis-crotonamide (Monoerotophos), dimethyl-2,2,2-trichloro-1-butyryl oxethane phosphonate (Butonate), dimethyl-3-hydrocogluta-conate dimethyl phosphate ( Brorayl), dimethyl-2,2-dichlorovinyl-phosphate (DDVP), dimethyl-1,2,2-dibromo-2,2-dichloroethyl phosphate (Bi-bromo), dimethyl- (2,2,2-trichloro) -1-hydroxyethyl) phosphonate (Dip-terex), 2-chloro-1- (2,4,5-trichlorophenyl) -vinyl-dimethyl-phosphate (Gardona) ethyl 3-methyl-4- (methyl-thio) -phenyl- (1-methyl-ethyl) -phosphoric acid amide (Nemacur), 0,0-diethyl 1-O- (2-isopropyl-6-methyl-5-pyrimidinyl) phosphorothioate (Diazinone), 1- phenyl-3- (0,0-di-ethyl-thionophosphoryl) -1,2,4-triazole (Hostathion), 0,0-diethyl-O- (3-oxo-2-phenyl-dihydro-pyridazine-6 -yl) phosphorothionate (Gnak), 0,0-diethyl-5-phenyl-3-isoxazolyl-phos Phththioate (Isoxathione) 2-Carbomethoxy-1-methylvinyl-dimethyl-phosphate (Phosdrin), 0,0-Diethyl-0-2-quinoxalinyl-phosphorothioate (Bayrusil), 0,0-Diethyl-O- (α-cyano -benzylidene-amino) -monothiophosphate (Phoxy), 0.0-dimethyl-S- (N-methyl-N-formylcarbamoylmethyl) -phosphorodithioate (Formothion), N- (mercaptomethyl) -phthalimide-S- (0.0 -dimethylphosphorus dithioate) (Imidan), 6- (0,0-dimethylphosphoryl) -7-chloro-bicyclo- (3,2,0) -heptadiene (2,6) (Hostaquick), 6-chloro-4-thio -chromanyl-diethyl-thiophosphate, 2- (0,0-diethyl-thionophosphoryl) -5-methyl-6-carbethoxy-pyrazolo [1,5-a] -pyrimidine (Pyiazophos) and diethyl-dithiobis- ( thionoformate) (Herbisan 5).

The emulsion concentrates of organic water-insoluble biocides generally have a content of approx. 3 to 35 weight percent, preferably 3 to 15 weight percent of the emulsifiers, especially of a mixture of the nonionic and anionic emulsifiers. Hereby, the ratio of non-ionic to anionic emulsifiers can be varied within wide limits. Usually this ratio is approx. 4: 1 to 1: 2, preferably 3: 1 to 1: 1 parts by weight. In addition, the emulsion concentrates of the biocides may also contain additional proportions and the total up to 50% by weight of organic solvents.

Such suitable organic solvents for the hydrolysis-sensitive biocides are, above all, hydrocarbons such as benzene, toluene, xylene or kerosene, and preferably the content of the emulsion concentrates of such solutions is 10-30% by weight. The proportion of the biocidal active substances in the emulsion concentrates can be varied depending on the active substance and the nature of the application within wide limits. The active substance content of the concentrates is usually approx. 30-90% by weight, preferably 40-60% by weight.

According to the invention, e.g. by the addition of 1% by weight of diethylene glycol dimethyl ether, a pourable 40% by weight solution of calcium tetrapropylene benzenesulfonate in xylene is obtained, while using an 8% by weight of this ether, a pourable 70% by weight solution corresponding to the concentration of hydroxyl is obtained. group-containing solutions.

In the following Tables I and II, for solutions of anionic emulsifiers in various non-polar organic solvents, at different mixing conditions with and without the addition of viscosity reducing agents, the viscosities measured with a ball drop viscometer according to Hoppier are indicated.

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Table I

Calcium tetrapropylene benzene sulfonate solutions Weight ratio of Ca-salt solution

Solution- Viscosity-lowering agent and viscosity- Viscosity

medium lowering agent at 25 ° C in cP

Toluene - 25: 75: 0 90. & 43 "Ethylene glycol dimethyl ether 25: 70: 5 2" "35: 60: 5 8" "45: 50: 5 101" "55: 40: 5 3.031

Xylene "25: 75: 0> Ί06" "35: 60: 5 15

Shellsol A "25: 75: 0> 106" "35: 60: 5 35

Xylene Ethylene glycol diethyl ether 35: 60: 5 72 "Diethylene glycol dimethyl ether 35: 60: 5 6" "45: 50: 5 89" Triethylene glycol dimethyl ether 35: 60: 5 15 "" 45: 50: 5 747 "Tetraethylene glycol dimethyl ether 35: 60: 5 14 "" 45: 60: 5 2,050 "Diethylene glycol dibutyl ether 35: 60: 5 8" Methyl tetraglycol t-butyl ether "6" Methyl glycol acetate "1,110" Butyl glycol acetate "2,773" Glycol diacetate " 4,086 "Methyldiglycol acetate" 174 "Ethylglycol methylurethane" 58 "Methyldiglycol methylurethane" 11 "(1,3) -propanediol diacetate" 3.997 "(1,4) -butanediol diacetate" 3.247 "(1,4) - butanediol dimethylurethane 5,005 10 145445

Table XX

Solutions of calcium chloro paraffin sulfonate (chain length chlorination degree 1.4) Weight ratio of Ca salt; solution solution- Viscosity-lowering agent and viscosity- Viscosity

average mean lowering agent at 25 C in cP

Toluene - 25: 75: 0> 106 "Ethylene glycol dimethyl ether 35: 60: 5 7" 45: 50: 5 72 "55: 40: 5 14.436

Xylene - 25: 75: 0> 10 ^ "Diethylene glycol dimethyl ether 35: 60: 5 7" "45: 50: 5 47" "55: 40: 5 51,640" Tetraethylene glycol dimethyl ether 35: 60: 5 17 "" 45: 50: 5 3.320