Sulfosuccinic acid semi-esters of oxyalkylated polynuclear alkyl-phenols

Abstract

This invention relates to sulfosuccinic acid semi-esters of oxyalkylated polynuclear alkylphenols of the formula ##SPC1## In which R represents a group of the formula ##SPC2## (OX) represents oxyalkylene radicals, R.sub.1 represents an alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R , n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal, and their use as dispersing and wetting agents for sprayable powders or dispersable concentrates containing water-insoluble organic biocidal agents.

Description

Organic water-insoluble biocidal agents are often used in the form of so-called spray powders. These spray powders are powdery preparations of biocidal agents which are applied in the form of aqueous suspensions. In order to permit easy application, the suspensions must have a good suspension and wetting property. In addition to the active substance (biocidal agent), the spray powders in general contain carrier substances such as aluminium or magnesium silicates or synthetic silicic acids and optionally adhesives and, in addition, wetting and dispersing agents. The content of active substance in the spray powders may vary within wide limits; it amounts in most cases to about 20 to 80 percent by weight. The proportion of wetting and dispersing agents in the spray powders is in general about 0.5 to 8 percent by weight.

Typical examples of organic biocidal agents are, for example, chlorohyrocarbons such as DDT, Lindan, Chlordan, Aldrin, Dieldrin, Endrin and Toxaphen, and phosphoric acid esters such as Parathion, Methylparathion, Malathion, Trithion and Systox as well as carbamates such as Carbaryl and similar compounds.

It is already known from U.S. Pat. No. 3 236 627 that sulfosuccinic acid semi-esters of oxalkylated alkyl-phenols are suitable dispersing agents for water-insoluble biocidal agents. However, the dispersing action of these known compounds is often considered as insufficient.

The present invention provides sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols, a process for preparing them and their use as dispersing and wetting agents for water-insoluble organic biocidal agents.

The sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the present invention are compounds of the general formula I ##SPC3##

in which R represents a group of the formula ##SPC4##

--(O--X) represents oxyalkylene radicals, in particular oxyethylene and/or oxypropylene, R.sub.1 represents a saturated, straight chain or branched alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R, n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal.

The present invention furthermore provides dispersable concentrates of water-insoluble organic biocidal agents which contain sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the formula I as dispersing or wetting agents.

For preparing the sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the formula I, mono-alkyl-phenols of the formula ##SPC5##

are condensed with formaldehyde in a molar ratio of 2 : 1 to 10 : 9 according to known methods (ef. Hultzsch, "Chemie der Phenolharze", 1950, page 114) in the presence of acid catalysts to yield novolak resins, these resins are reacted with 2 to 25 moles, referred to each phenol group, of alkylene-oxide according to known methods, preferably in the presence of alkaline catalysts, whereupon novolak resin oxalkylates are obtained whose free hydroxyl groups are then totally or partially esterified, at 20.degree. to 100.degree.C, with maleic acid anhydride to yield maleic acid semi-esters which are finally reacted in aqueous phase with water-soluble salts of sulfurous acid to yield sulfosuccinic acid semi-esters.

For the formation of the novolak resins, there may be used as mono-alkyl-phenols of the formula ##SPC6##

for example hexyl-, heptyl-, octyl-, nonyl-, dodecyl- or tetradecyl-phenol or mixtures of these alkyl-phenols, the alkyl groups optionally being straight chain or branched groups. In the reaction, formaldehyde in form of an aqueous solution or of para-formaldehyde may be used. The acid catalysts may be mineral acids such as sulfuric acid, phosphoric acid or, owing to the fact that it can be easily eliminated during removal of the water by distillation, preferably hydrochloric acid. In general, the acids are used in a concentration of 0.1 to 5 percent by weight, referred to the alkyl-phenol. The condensation is effected at temperatures in the range of from about 20.degree. to 150.degree. C, preferably from 80.degree. to 130.degree. C, suitably under an atmosphere of nitrogen. The water present after the condensation is then removed by distillation to a residual content in the novolak resin of less than 0.5 percent by weight. This operation is carried out finally under reduced pressure of less than 50 Torr.

The novolaks obtained constitute more or less brittle, clear, yellow-brown coloured resins in the form of big blocks. They are mixtures of polynuclear alkyl-phenols which are linked by methylene bridges. Their composition depends above all on the ratio of alkyl-phenol to formaldehyde.

The oxalkylation of the novolak resins is carried out according to known methods with ethylene oxide or 1,2-propylene oxide or ethylene oxide and propylene oxide in the presence of alkaline catalysts at about 100.degree. to 210.degree. C, preferably at 140.degree. to 170.degree. C. As alkaline catalysts, there may be used above all alkali metal hydroxides such as potassium hydroxide or, preferably, sodium hydroxide, or alkali metal-alkoxides such as sodium methylate or sodium ethylate. These alkaline catalysts are preferably used in a concentration of 0.05 to 1.0 percent by weight, referred to the novolak resin. The oxalkylation may be effected without pressure or in pressure vessels and the alkylene oxide may be introduced either in gaseous or liquid form. The alkylene oxide is used in such an amount that 2 to 25 moles of alkylene oxide groups are introduced per each phenolic hydroxyl groups. It is preferred to use 3 to 15 moles of ethylene oxide per mole of starting alkyl-phenol.

The reaction of the novolak oxalkylate with maleic acid anhydride to yield the maleic acid semi-ester is carried out by mixing the components and stirring them at about 20.degree. to 100.degree.C, preferably at 40.degree. to 80.degree.C, in the presence of alkalis, preferably alkali metal hydroxides. These alkaline catalysts are used in a concentration of about 0.05 to 1.0 percent by weight, referred to the novolak oxalkylates. Since maleic acid anhydride tends to sublimation, it is advantageous to carry out the reaction in pressure vessels under a pressure of about 0.2 to 1.0 atmosphere gauge of nitrogen or air and to ensure thorough mixing, because at the beginning the molten maleic acid anhydride can not easily be mixed with the novolak oxalkylates. The maleic acid anhydride may be used in such an amount that all novolak oxalkylate hydroxyl terminal groups or a part thereof, at least however one terminal hydroxyl group of the novolak oxalkylate, are reacted.

Transformation of these maleic acid semi-ester compounds into the corresponding sulfo-succinic acid semi-esters is effected in an aqueous medium by reaction with water-soluble sulfites or hydrogen sulfites. The sulfites or hydrogen sulfites, preferably alkali metal or alkaline earth metal sulfites -bisulfites or -pyrosulfites are used in quantities of about 1.0 to 1.5 mole, preferably 1.05 to 1.1 mole, calculated as sulfurous acid per maleic acid semi-ester group. For this reaction, the di-alkali metal sulfites are particularly suitable, since they lead to the formation of dialkali metal salts of the sulfosuccinic acid semi-esters.

The quantity of water added during the reaction may amount to 50 to 85 percent by weight, referred to the total solution or mixture. It depends on the solubility of the sulfosuccinic acid semi-ester salts and on the viscosity of the solutions. The reaction temperatures are kept at about 20.degree. to 100.degree. C, preferably at 40.degree. to 80.degree. C.

For their use as dispersing and wetting agents, the sulfosuccinic acid semi-ester salts of the present invention may be applied optionally without purification directly in the form of their solutions. If desired the aqueous solutions of the sulfosuccinic acid semi-ester salts may also be dehydrated according to known methods, for example by spray-drying. This spray drying may also be carried out in the presence of other components, for example pyrogenic silicic acid. The salts of the sulfosuccinic acid semi-esters of oxalkylated novolak resins are sticky to solid substances; they are excellent wetting and dispersing agents with moderate foam formation and are therefore particularly suitable for biocidal spray powders. For this purpose the amount of wetting and dispersing agents may be in the range of 0.5 to 8 percent by weight.

The following Examples describe the preparation of the sulfo-succinic acid semi-esters of the formula I, the preparation of mono-nuclear comparative substances and comparative tests of these substances as dispersing agents in spray powders on the basis of water-insoluble organic biocidal agents.

A. Preparation of the Sulfosuccinic Acid Semi-Esters of Oxalkylated Novolak Resins

a. Preparation of the Novolak Resins

z+ 1 Moles of alkyl-phenol and z moles of formaldehyde were mixed at room temperature and, after addition of 0.55 percent by weight of concentrated hydrochloric acid (d 1.18), referred to the alkyl-phenol, stirred for 4 hours at 95.degree.-106.degree. C under reflux. Then, the water is removed by distillation, while working finally under a reduced pressure of about 20 to 2 Torr.

b. Oxalkylation of the Novolaks and Preparation of the Maleic Acid Semi-Esters

1 Mole of the novolak resin was combined with 0.2 percent by weight of sodium hydroxide, referred to the novolak resin, and (z+1).sup.. n moles of ethylene oxide and/or propylene oxide were added at 150.degree.-160.degree. C. The oxalkylate was then reacted at 50.degree.-80.degree. C, while stirring and after addition of 0.1 percent by weight of sodium hydroxide, referred to the novolak oxethylate, with z + 1 moles or at least 1 mole of maleic acid anhydride to yield the maleic acid semi-esters (n and z having the meanings given above).

c. Preparation of the Sulfosuccinic Acid Semi-Esters

After addition of water, the maleic acid semi-esters were reacted with 1.05 to 1.1 mole of sodium sulfite per mole of the maleic acid anhyride previously used. The sodium sulfite was stirred as an aqueous solution into the solution of the maleic acid semi-ester within about 60 minutes at 40.degree. to 80.degree.C. When the batch had become clearly soluble in water, stirring was continued for 1 hour. The total quantity of water added during the reaction wa 50 to 80 percent by weight, referred to the solution of the sulfosuccinic acid semi-ester obtained after completion of the reaction.

The values for the compounds of the formula I prepared according to this method are indicated in Tables Ia and Ib.

Table Ia __________________________________________________________________________ Ex- Starting - Novolak Ethylene- Maleic acid- Maleic acid semi-ester ample oxide anhydride Na.sub.2 SO.sub.3 7H.sub.2 O No. Refrac- Acid number tion Found Calc. index n.sub.D 25 Mole R.sub.1 z Mole (z+1).sup.. n Mole Mole __________________________________________________________________________ 1 C.sub.9 H.sub.19 1 1 6 2 1.5153 137.0 122.5 2.2 2 " 1 1 12 2 1.5078 96.7 95.4 2.2 3 " 1 1 21 2 1.4987 79.2 70.8 2.2 4 " 1 1 12 1 1.5025 50.8 50.7 1.1 5 " 2 1 9 3 1.5208 126.8 122.3 3.3 6 " 2 1 12 3 1.5156 -- -- 3.3 7 " 2 1 18 3 1.5098 97.2 94.8 3.3 8 " 2 1 21 3 1.5075 99.1 88.4 3.3 9 " 2 1 18 2 1.5085 67.6 67.2 2.2 10 " 3 1 12 4 1.5222 123.0 121.5 4.4 __________________________________________________________________________

Table Ib __________________________________________________________________________ Ex- Starting - Novolak Ethylene- Maleic acid- Maleic acid semi-ester Na.sub.2 SO.sub.3 7H.sub.2 O ample oxide, or anhydrid Refrac- No. Propylene- tion Acid Number oxide index Found Calc. R.sub.1 z Mole Mole Mole n.sub.D.sup.25 (z+1).sup.. n __________________________________________________________________________ 11 C.sub.9 H.sub.19 3 1 4 1.5190 113.5 116.5 4.4 12 " 3 1 18 4 1.5168 108.8 106.4 4.4 13 " 3 1 21 4 1.5129 107.0 100.0 4.4 14 " 8 1 54 9 1.5111 102.6 94.4 9.9 15 " 2 1 60 3 1.4881 50.4 46.6 3.3 16 " 8 1 224 9 FP34.5-35.5 40.4 39.3 9.9 .degree.C 17 C.sub.12 H.sub.25 2 1 24 3 1.5050 76.6 77.5 3.3 18 C.sub.9 H.sub.19 2 1 6 PO 3 1.5056 89.1 88.9 3.3 12 EO 1) 19 " 2 1 6 PO 3 1.4992 90.5 90.5 3.3 12 EO 2) 20 C.sub.6 H.sub.13 4 1 27 EO 5 1.5134 107.4 107.1 5.5 __________________________________________________________________________ 1) At first 6 moles PO (=propylene-oxide), then 12 EO (ethylene-oxide) (" Block"-oxalkylate) 2) A mixture of 6 moles PO and 12 mol EO added (mixed oxalkylate with statistical distribution of the PO and EO groups).

B. Preparation of Sulfosuccinic Acid Semi-Esters of Oxyethylated Mono-Nuclear Mono-Alkyl-Phenols (Comparative Substances V and W)

n Moles of ethylene oxide were added, at 140.degree.-160.degree. C, to 1 mole of alkyl-phenol in the presence of 0.2 percent by weight of sodium hydroxide, referred to the alkyl-phenol. The oxethylate was then reacted at 50.degree.-80.degree. C, while stirring thoroughly, with 1 mole of maleic acid anhydride. 1.05 mole to 1.1 mole of sodium sulfite in the form of an aqueous solution were stirred within about 60 minutes into the aqueous solution of the maleic acid semi-ester obtained. When the batch had become clearly soluble in water, the whole was further stirred for 1 hour at the indicated temperature. The total quantity of water present in the solution obtained was found to be 50 to 85 percent by weight.

The dates of the compounds obtained are indicated in Table II.

TABLE II __________________________________________________________________________ (comparative product): Pro- Start- Moles Ethy- Maleic Maleic acid semi-ester Na.sub.2 SO.sub.3 7H.sub.2 O duk- ing lene- acid Refraction Acid number ts phenol oxide an- index hydrid found calc. Mole Mole n.sub.D.sup.25 Mole (n) __________________________________________________________________________ V Mono- 1 6.0 1.0 1.4980 102.2 95.6 1.1 nonyl- W phenol 1 9.7 1.0 1.4932 78.5 75.2 1.1 __________________________________________________________________________

In the tests regarding application, the dispersing and wetting properties and the foaming behaviour of the sulfosuccinic acid semi-esters of the invention and of the comparative substances V and W in the use of wetting and dispersing agents in biocidal spray powders were tested comparatively. In these tests, the determination of the suspension property was effected according to the cylinder method described by Fischer (cf. Handbuch der landwirtschaftlichen Versuchs- und Untersuchungsmethodik (Methodenbuch), Volume VII "Die Untersuchungen von Pflanzenschutzmitteln" by W. Fischer (1941), page 53 and page 12).

The determination of the wetting power was carried out as follows: a glass beaker having a capacity of 500 ml (8 cm diameter) was filled with tap water of 20.degree. C and a hardness of 12.degree.dH (German hardness) and 1 gram of the spray powder to be tested was strewn on the surface. The time which is required for wetting the powder is measured and indicated in seconds as wetting time.

The test for the foaming property was carried out according to J. Ross and G. D. Miles (cf. Oil and Soap 18 (1941), 99) with a concentration of 4 grams of the spray powder to be tested per liter of water at a quantity measured in of 500 ml. The height of the foam in cm was measured at the beginning and after a period of time of 5 minutes.

The following spray powder formulations were used for the comparative tests with the wetting and dispersing agents to be tested:

A.

50 % by weight of Lindan

37 % by weight of siliceous chalk

10 % by weight of silicic acid

3 % by weight of wetting and dispersing agent.

B.

50 % by weight of commercial DDT

37 % by weight of siliceous chalk

10 % by weight of silicic acid

3 % by weight of wetting and dispersing agent.

C.

30 % by weight of Endosulfan

64 % by weight of siliceous chalk

3 % by weight of silicic acid

3 % by weight of wetting and dispersing agent.

D.

20 % by weight of Dieldrin

77 % by weight of siliceous chalk

3 % by weight of wetting and dispersing agent.

The results of these comparative tests are compiled in Tables III to VI.

A comparison of the results indicated in Tables III and VI with those of Table VII shows above all the superior outstanding dispersing power (suspending power) and often also a better wetting power of the sulfosuccinic acid semi-esters of exalkylated novolaks of the present invention (Examples 1 to 19) over that of the sulfosuccinic acid semi-esters of mono-nuclear mono-alkylphenols (comparative substances V and W).

Further tests with the wetting and dispersing agents according to Example 2 of Table Ia show that these novel dispersing and wetting agents are also excellently suitable for formulations with those active substances which are difficult to wet. The results of these tests are contained in Table VIII.

Table III __________________________________________________________________________ Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated binuclear novolaks (Example Nos. 1 - 4) in spray powder formulations. Spray Suspension property in % Wetting power in secs. R + M - Foam (immediately/after 5 mins.) powder Wetting and dispersing agents Example current nos. of Table 1a) formu- lations __________________________________________________________________________ 1 2 3 4 1 2 3 4 1 2 3 4 __________________________________________________________________________ A 91 90 91 90 10 15 10 17 4.5/3.5 10.0/9.5 9.0/8.5 -- B 78 83 77 78 15 25 10 20 2.0/0.1 4.0/3.5 4.0/3.5 -- C 85 85 83 75 10 15 10 15 2.5/2.0 5.0/4.5 8.0/7.5 -- D 83 89 88 81 10 15 10 15 3.5/3.0 8.0/7.0 10.0/9.5 -- __________________________________________________________________________

Table IVa __________________________________________________________________________ Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated trinuclear novolaks (Example Nos. 5 - 9) in spray powder formulations. Spray SuspensIon property in % Wetting power in secs. R + M - foam (immediately/after 5 mins.) powder formu- wetting and dispersing agents Example current nos. of Table Ia. lations __________________________________________________________________________ 5 6 7 8 9 5 6 7 8 9 5 6 7 8 9 __________________________________________________________________________ A 95 92 91 90 86 20 20 25 20 35 3.0/2.0 3.0/2.0 4.0/3.0 4.5/4.0 4.5/4.0 B 71 79 77 75 76 20 20 20 15 45 1.5/0.5 2.0/1.0 2.5/1.5 2.5/1.0 2.5/0.5 C 83 86 83 84 78 15 15 15 15 20 2.5/1.5 2.5/1.5 2.5/1.5 4.5/2.5 4.5/2.5 D 88 90 90 87 86 15 15 10 10 25 4.0/2.0 4.5/2.5 4.5/2.5 4.5/2.5 4.5/2.5 __________________________________________________________________________

Table IVb __________________________________________________________________________ Wetting and dispersing power of sulfosuccinic acid semi-esters of oxalkylated trinuclear novolaks (Example Nos. 15, 17 - 19) in spray powder formulations. Spray Suspension property in % Wetting power in secs. R + M - foam (immediately/after 5 mins.) powder formula- Wetting and dispersing agents Example current nos. of Table Ib. tions __________________________________________________________________________ 15 17 18 19 15 17 18 19 15 17 18 19 __________________________________________________________________________ A 65 71 90 89 10 60 17 23 2.5/1.0 3.5/2.0 3.5/3.0 3.5/3.0 B 58 80 82 78 15 50 20 35 2.0/0.5 2.0/0.5 1.5/0.5 1.0/1.0 C 66 86 80 80 10 25 12 12 2.5/1.0 2.5/1.0 2.0/1.0 2.0/1.0 D 75 90 84 83 15 30 15 15 3.0/1.0 2.0/1.0 2.0/1.0 3.0/2.0 __________________________________________________________________________

Table V __________________________________________________________________________ Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated Novolak with 4 nuclei (Example Nos. 10 - 13) in spray powder formulations. Spray Suspension property in % Wetting power in secs. R + M - foam (immediately after 5 mins.) powder formula- tions Wetting and dispersing agents Example current nos. to Table Ia and Ib. __________________________________________________________________________ 10 11 12 13 10 11 12 13 10 11 12 13 __________________________________________________________________________ A 88 86 88 88 20 20 20 20 3.5/1.5 3.5/2.0 3.5/2.0 4.5/3.5 B 68 71 71 71 20 20 25 25 2.5/1.0 2.5/1.0 2.5/1.0 3.0/2.0 C 82 81 81 80 15 15 15 15 1.5/0.0 3.0/1.0 3.0/1.0 3.5/2.0 D 90 91 91 90 15 20 15 15 2.0/0.5 2.0/0.5 2.5/1.0 3.0/2.0 __________________________________________________________________________

Table VI __________________________________________________________________________ Wetting and dispersing power of sulfosuccinic acid semi-esters of oxethylated novolaks with 9 nuclei (Examples 14 and 16) in spray powder formulations. Spray Suspension property in % Wetting power in secs. R + M - foam (immediately/after 5 mins) powder formu- Wetting and dispersing agents Example current nos. of Table Ib. lations __________________________________________________________________________ 14 16 14 16 14 16 __________________________________________________________________________ A 87 93 60 55 -- 4.5/4.0 B 70 79 55 95 -- 2.0/0.5 C 80 85 40 65 -- 2.0/0.5 D 86 88 45 70 -- 2.5/1.0 __________________________________________________________________________

Table VII __________________________________________________________________________ Wetting and dispersing behaviour of the comparative substances V and W (according to Table II) in spray powder formulations. Spray Suspension property in % Wetting power in secs. R + M - foam powder in cm formula- Comparative substances according to Table II. (immediately/after tions 5 mins.) __________________________________________________________________________ V W V W V W __________________________________________________________________________ A 50 22 20 20 19.5/15.0 15.0/11.0 B 31 35 20 20 8.5/7.0 7.5/6.5 C 22 15 15 20 14.0/13.0 13.5/11.5 D 35 28 20 20 15.0/11.5 14.0/12.0 __________________________________________________________________________

TABLE VIII ______________________________________ Wetting and dispersing behaviour of the product according to Example 2 of Table Ia in formulations with active substances which are difficult to wet. Spray powder formulations Suspension Wetting property power in % in seconds ______________________________________ 50% Folpet 47% siliceous chalk + silicic acid 88 10 3% wetting and dispersing agent according to Example 2 65% Ziram 32% siliceous chalk + silicic acid 92 15 3% wetting and dispersing agent according to Example 2 50% Atrazin 47% siliceous chalk + silicic acid 85 10 3% wetting and dispersing agent according to Example 2 25% Simazin 72% siliceous chalk + silicic acid 81 5 3% wetting and dispersing agent according to Example 2 50% Captan 47% siliceous chalk + silicia acid 89 10 3% wetting and dispersing agent according to Example 2. 50% Zineb 47% siliceous chalk + silicic acid 90 10 3% wetting and dispersing agent according to Example 2. ______________________________________

A comparison of the values indicated in Tables III to VI to those given in Table VII shows that the sulfosuccinic acid semi-esters of oxalkylated novolaks of the invention, prepared from mono-alkyl-phenols and formaldehyde (Examples 1 to 19) have above all an outstanding dispersing power (suspending property) and partly also a better wetting power over the sulfo-succinic semi-esters of mono-nuclear mono-alkyl-phenols (comparative substances V and W).

Since in biocidal spray powders a strong foam formation of the dispersing and wetting agents is a considerable disadvantage in the use of these spray powders, the advantageous low tendency to foam formation of the compounds of the invention should be particularly pointed out.

The utilization of the sulfosuccinic acid semi-esters of the formula I as dispersing and wetting agents in the preparation of spray powders on the basis of water-insoluble organic biocidal agents is a preferred application of this sulfosuccinic acid semi-ester. In addition thereto, these compounds are excellently suitable as dispersing and emulsifying agents also for other purposes, for example for preparing emulsion concentrates of water-insoluble organic biocidal agents. The amount of wetting and dispersing agents may be in the range of 1 to 30% by weight of the emulsion concentrate. In this case, the sulfosuccinic acid semi-esters may be used alone or with other, preferably non-ionogenic emulsifiers, for example the reaction products of ethylene-oxide with lipophilic compounds. The following examples of emulsifiable concentrates of organic biocidal agents are intended to illustrate this use of the sulfosuccinic acid semi-esters of the present invention.

EXAMPLE 21

20% of pentachloronitrobenzene

20% of the dispersing agent of Example 7 in Table Ia

60% of cyclohexanone

35% of Endosulfan

15% of the dispersing agent of Example 7 in Table Ia

5% of a reaction product of 1 mole of triisobutylphenol and 18 moles of ethylene-oxide

2% of epichlorhydrin

43% of xylene

When stirred into water, both emulsion concentrates give spray liquors which are ready for use.

Claims

We claim:

1. Sulfosuccinic acid semi-esters of oxalkylated polynuclear alkyl-phenols of the general formula I ##SPC7##

in which R represents a group of the formula

--(O--X) represents oxyethylene, oxypropylene and mixture thereof, R.sub.1 represents a saturated straight chain or branched alkyl group having 6 to 14 carbon atoms, Y represents hydrogen or has the same meaning as that given for R, n represents a number from 2 to 25, z represents a number from 1 to 9 and Me stands for hydrogen or an alkali metal.

2. The polynuclear compound of claim 1 having the formula ##SPC8##

wherein R is selected from the group consisting of ##SPC9##

Z is equal to 1 and (Z+1).sup.. n is equal to 21.

3. The polynuclear compound of claim 1 having the formula ##SPC10##

wherein R is selected from the group consisting of ##SPC11##

Z is equal to 2 and (Z+1).sup.. n is equal to 18.

4. The polynuclear compound of claim 1 having the formula ##SPC12##

wherein R is selected from the group consisting of ##SPC13##

Z is equal to 8 and (Z+1).sup.. n is equal to 224.

5. The polynuclear compound of claim 1 having the formula ##SPC14##

wherein R is selected from the group consisting of ##SPC15##

Z is equal to 2 and (Z+1).sup.. n is equal to 24.