DE1542875A1 - Emulsifier for biocidal organic thiophosphoric acid esters - Google Patents

Description

JAKBWERKE HIGH DAY. Genäorf, 2.5.1966

v'ormale Meiater Lucius & Brüning Dr.Br/HH III Gd 1393

Description for

P ate η ta η me Id u ng "Emulsifier for biocidal organic thiophosphoric acid esters"

Suitable emulsifiers for liquid concentrates of water-insoluble organic bio-eids are known to include, inter alia, iseiiungen or combinations of non-ionic Tenaidic polyalkylene glycol ethers, (thioethers, esters) of higher molecular weight fatty alcohols, (mercaptans, -c acids) or alkylphenols on the one hand and b'llb 'sliehen alkaline earth metal, preferably calcium salts of anionic alkyl aryl sulphonic acids, in particular the Doöecylbenaol- or tetra · propylene benzene sulfonaäure the other hand, the Anteilverhältnio'der mixture components can be varied within a fairly wide range and as a result, both to the special properties of the biocidal active substance and of the solvent also The concentrates are generally prepared by homogeneously mixing the biocidal active ingredient, usually pre-dissolved in an organic solvent, with the previously prepared emulsifier combination or de ren components.

US Pat. No. 2,696,453 and British Pat. No. 717,279 give numerous examples of the type described.

biocidal active ingredient 20 to 50 solvents 40 to 75 wt .- ^ Emulsifier mixture 5 to 10 wt. ~ #

A major disadvantage of these emulsifiers or "Smulgatorkombinationen is that in particular when using thiophosphorus säuree s ter-V / irkst of fen whose concentration can not be increased significantly over about 50 f" in the emulsifiable concentrates, even at high Emulgatoreinsatz.

ORIGIMAL

009823/1848

The slowing down or cessation has a further disadvantageous effect the emulsifying effect in very hard water, e.g. such from 400 to 1000 ggm. The self-emulsifiable one for normal people Water hardness of 0 to 400 ppm adjusted biooid concentrate can only be used in very hard water thereby making it possible to change the blending ratio of the emulsifier components and / or also increases the total amount of emulsifier. On the other hand, it shows, that in most cases a for very tough V'äsaer adjusted concentrate shows completely inadequate emulsification behavior in normally hard water

There is a further disadvantage of the emulsifier combinations mentioned in that, with a given active ingredient concentrate and given water hardness, you can produce differently concentrated use emulsions such as 0.1 percent, 5 percent or 25 percent emulsions in tap water of e.g. 400 ppm for each concentration range also a different reconciliation relationship in each case of the emulsifier components needed to achieve an optimal emulsifying effect.

In contrast, an emulsifier combination was found that especially for the thiophosphoric acid ester active ingredients which are known to be particularly difficult to emulsify, such as "malathion" (S- (1,2-diethoxycarbonylethyl) -0, O-dimethyldithiophosphoric acid ester), "Parathion" (0,0-diethyl-O-p-nitrophenyl-thiophosphoric acid ester) and "methyl parathion" (0,0-Dimethy1-0-p-nitrophenyl-thiophosphoric acid ester) is particularly suitable and does not have the above-mentioned disadvantages of the known emulsifier combinations.

The invention relates to a concentrate of biocidal thiophosphoric acid esters, Containing 50 to 80 percent by weight of phosphoric acid ester and 50 to 20 percent by weight of an emulsifier combination, from

a) a block polymer of propylene oxide and ethylene oxide with molecular weights from about 2000 to about 3300 and

b) an alkaline earth salt of an alkylarylsulfonic acid

in weight ratio from 50 to 90, preferably 65 to 75, 50 to 10, preferably 35 to 25.

009823/1848 ~ ~

The inventive Enralgatorkomblnation consists on the one hand of 50 to 90 _t, preferably 63 "to 75 parts by weight of a block polymer of 60 to 80, preferably 65 to 75 parts by weight of polypropylene oxide, on which 20 to 40, preferably 25 to 35 parts by weight of polyethylene oxide are attached, and on the other hand from 10 to 50, preferably 25 to 35 parts by weight of a 40% SO% solution of an alkaline earth metal, in particular the calcium glycate of an anionic acid, such as dodecylbenzene or tetrapropylene benzene sulfonic acid in an organic solvent

Preferred solvents are alkanols which are limitedly miscible with water, such as butanol or isobutanol, because tie are hardly phytotoxic on the one hand and on the other hand have sufficiently high flash points .; the tightened shipping and storage technology Make measures superfluous "

Not necessary when using the claimed emulsifier combination In most cases, the usual help of a additional organic solvent for the biocidal active ingredient. The concentrates can therefore be prepared in a simplified manner by adding the active ingredient to the previously prepared liquid Entered emulsifier blanks and stirred until homogeneous will"

Above all, however, the emulsifier combination according to the invention brings you a significant technical progress in that it allows the preparation of high concentrates with up to 80 y £ Thiophoephoreäureester enables active ingredients, wae at the same time signifies considerable economic progress.

The number of thiophoreic acid ester active ingredients that can be successfully emulsified according to the method according to the invention can be increased as soon as certain proportions of about 35 to 65, preferably 45 to 55 percent by weight - of the anion-active component have been exchanged ./eröai* Gegon? n Slectre »neutral salt, formed from equivalent quantities of a? mixed mono- / dipho-phosphoric acid esters of an alkyl p'iv: i; l-; ^. ^ glycol ethers with Γ " ^: > ia 18, vorzueweice 8 to 12 KoK" - ■ "-,; nff at-jn ^ r in the alkyl ^ atte and 4 bi * ~ 20 * νοΓ, -α ·. £ £ .- ?? {* ΐ8 ^Γ ' ύ.ίπ "';J'V: ^ λ · ~ ■ ■ oxide groups \, n der Ätherk.,,; Te si: kj ^ ^i; . its unC: - \. ^ r '·,' - '.:.' :, ": - ::

009823/18 '* 8 - ---- «

BATHROOM CPJGINAL

Alkyl or alkylene monoamine polyglycol ethers on the other hand, containing 12 to 22, preferably 16 to 18 carbon atoms in the alkyl or alkylene chain and 15 to 30, preferably 17 to 23 ethylene oxide groups in the ether chain.

The high concentrates with up to 75 or 80 $> thiophosphoric acid ester active ingredients prepared with the claimed enailer combinations consisting of two or three components provide very finely dispersed emulsions when diluted to the usual application concentrations of about 0.1 to 5 i> Beyond the requirements of the World's Health Organization (WHO), it is also extremely resistant in hard water up to 1000 ppm. If the active ingredient content is reduced to .50 to 60 #, transparent, colloidal dilutions are obtained.

The following examples illustrate the use of the Emulsifier combination for the preparation of self-emulsifier- ' the biocidal thiophosphoric acid ester concentrates shown.

Form the concentrates made from emulsifier and active ingredient clear ^ solutions, even after standing for a long time with different Temperatures show no deposits and spontaneously of emulsify yourself. By simply stirring the concentrate into water from 0 to 1000 ppm, in the concentration range of 0.01 to 25> finely dispersed, bluish opalescent, very stable Emulsions.

Examples ι (All quantities are (Jewiohteteile)

1) are mixed with stirring, 70 to 75 i <> Äthylparathion

with 25 to 30 ⁰ A emulsifier consisting of

70 parts of a block polymer of about 30 moles of propylene oxide and about 20 moles of ethylene oxide.

30 parts of an approximately 45 percent solution of the calcium salt tetrapropylenebenzenesulfonic acid,

2.) are mixed under stirring 70 to 80 i »Malathion

with 30 to 20 $> emulsifier according to example

-5-. I.

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-3i) Mix with your $ 50> ethylene parathion

with 50 I » emulsifier according to Example 1,

- ^l The one obtained by diluting this concentrate with water

5% emulsion is opaque, translucent and also cloudy after standing for a long time only slightly after

4.) are mixed with stirring, 70 to 75 i "Methyl parathion

with $ 30 to $ 25> emulsifier consisting of

Share a block polymer of about 30 moles of propylene oxide and about 20 moles of ethylene oxide

Divide about a 55 percent solution of the

Calcium salts of tetrapropylenebenzenesulfonic acid

Share an electron neutral salt formed from

equivalent amounts of a mono- / diph.bosphoric acid ester of a nonylphenyl polyglycol ^x ether with 8 ethylene oxide groups in the

Ether chain and an oleylaminoxäthylate with 20 moles of ethylene oxide.

5.) Mix 70 to 80 # ethyl parathio with stirring;

with 30 to 20 $ emulsifier according to example 4 #

6.) Mix 75 to 80 $ malathion with stirring

with 25 to 20 $> emulsifier according to the example

7.) Mix 50 to 60> έ methyl parathion with stirring

with 50 to 40 ^c ß> emulsifier according to the example

Those obtained by diluting this concentrate with water 1 to 5 percent spray emulsions are opaque, translucent and only slightly cloudy even after long periods of standing after"

SAD 009823/1848

Claims (7)

Patent claims ι · 1.) Concentrate of biocidal thiophosphoric acid ester ^ containing 50 to 80 percent by weight of thiophosphoric acid ester and 50 to 20 percent by weight of an emulsifier combination, from a) a block polymer of propylene oxide and ethylene oxide with molecular weights from about 2000 to about JI300 and b) an alkaline earth salt of an alkylarylsulfonic acid in a weight ratio of 50 to 90, preferably 65 to 75 * to 50 to 10, preferably 35 to 25. 2.) Concentrate according to claim 1, characterized in that the emulsifier component a) from 60 to 80, preferably 65 to 75 parts by weight of propylene oxide and 40 to 20, preferably 35 to 25 parts by weight of ethylene oxide. 3.) concentrate according to claim 1 or 2, characterized in that the emulsifier component b) consists of a calcium alkylarylsulfonate, preferably calcium dodecylbenzene or tetrapropylenebenzene sulfonate. 4.) concentrate according to claim 3, characterized in that the calcium alkylarylsulfonate in the form of a 40 to 60 percent Solution is present in an organic solvent. 5.) concentrate according to claim 1 to 4, characterized in that the emulsifier component b) is limited in one Water-miscible alkanol, in particular butanol or isobutanol, is dissolved. 6.) concentrate according to claim 1 to 5, characterized in that that up to 50 percent by weight of the solution of the alkaline earth / salaes of the alkylarylsulfonic acid according to claim 4 by a Electroneutral salt are replaced. 7.) concentrate according to claim 6, characterized in that the electron neutral salt is formed on the one hand from one -7- 009823/1848 Monophoephoric acid ester of an alkylphenyl polyglycol ether with 6 to 18, preferably 8 to 12, atoms in the alkyl chain and 4 to 20, preferably 7 to CpH.O groups in the ether chain * possibly in the Mixture with the entepreohenden siphosphoric acid ester - and on the other hand the equivalent amount of a basic one Alkylamine polyglycol ethers with 12 to 22, preferably 16 to 18-0 atoms in the alkyl chain and 15 to 30, preferably 17 to 23 CgH ^ O groups in the ether chain. 0 0 9'8 2 3/1 84 8