AU610388B2

AU610388B2 - Surface-active compositions

Info

Publication number: AU610388B2
Application number: AU33954/89A
Authority: AU
Inventors: Yvette Girardeau; Georges Ruffo; Christian Segaud
Original assignee: Rhone Poulenc Chimie SA
Current assignee: Rhodia Chimie SAS
Priority date: 1988-05-04
Filing date: 1989-05-02
Publication date: 1991-05-16
Anticipated expiration: 2009-05-02
Also published as: EP0341126A1; FR2630926B1; CA1334274C; JPH0214729A; AU3395489A; BR8902076A; JPH0577449B2; FR2630926A1

Description

Application(s) made in a Convention country in respect of the invention, the SUtject ot mne Application.

EECARE atCOURBEVOIE ,France 27th day of JUKE 19 89 Made feiKe ~ance FABRE (Signature of Declarant) 0 Personal Signature ofDeclarant (no seal, witness or legalisaton) 4

I

TU~ NANAIQ~ICTh1FR C~F PATENTS.

T _FrMIIWNROFPTNS 1~ COMMONWEALTH OF AUSTRALIA FORM PATENTS ACT 1952 CO0M P LET E SPEC IF I CA TI ON S P E C I F I Q A T 1 0 N FOR OFFICE USE: Class nt .Class Application Number: Lodged.1: Complete Specification Lodged: Accepted: Published: Priority: Related Art: This document contains the amjendments made undr., Section 49 and is correct ior printing N1ame of AppljCcant: RHONE-POULENC CHIMIE I Address of Applicant: 25, QUAI PAUL

FRANCE

DOUMER, 92408, COURBEVOIE, Actual Inventors: YVETTE GIRARDEAU, GEORGES RUFFO and CHRISTIAN SEGAUD Address for Service: SHELSTON WATERS, 55 Clarence Street, Sydney Complete Specification for the Invention entitled; "SURFACE-ACTIVE COMPOSITION61" The following statement is a full description of this invention, including the best mothod of performing it known to me/us:- 1- 4.

la SURFACE-ACTIVE COMPOSITIONS The present invention relates to a surface-active composition based on phosphoric esters of polyoxyalkylenated poly-(l-phenyl-ethyl)-phenols, its preparation process and'.its use in obtaining fluid aqueous dispersion of solid or liquid active substances called "flowables", which are then diluted during use, wettable powders or granules, which ire then brought into an aqueous dispersion state.

It is known to use phosphoric monoesters and diesters of polyoxyethylenated poly-(l-phenyl-ethyl)-phenols in acid or neutralized form for the preparation of flowables (British patent 2 115 284 and German patent 3 302 648).

The Applicant has found a new surface-active composition making it possible to reduce the viscosity of "flowables" with an identical active substance concentration.

The present invention therefore specifically relates to surface-active compositions based on phosphoric esters of polyoxyalkylenated poly-(l-phenyl-ethyl)-phenols, characterized V, in that they are constituted by a mixture of phosphoric mono.esters and diesters of polyoxyalkylenated poly(li-pheny-ethyl)phenols and polyoxyalkylenated p.ly,-(lt-phenyl-ethyl)-phenols of formulas I to III: o (I) lo/ *,1 I 0

CH

2 -0\ P 0 fox+ o -Cli 2 1 CkI 2

-Y

(II)

U

io qf r 0 CH 2

CH

2

OH

2 2 (111) in which: 44 4 o I C 6041 4t

I

m is equal to 2 or 3; &OX n represents, a statistical succession of oxyethylenated and oxypropylenated units; n being such that the total number of oxyalkylenated units of the radical OXn 0 CH 2 2

CH

2 is 14 to 35, with a ratio of the number of oxyethylenated units to the number of oxypropylenated units between 40:60 and 70:30 and preferably 40:60 and 60i4O, sai( esters of formulas I and II being in acid"or neutralized form.

The respective quantities of different constituents correspond to approximately 0 to 70% by weight, preferably to 60% by weight of constituent of formula III, a weight ratio of the diester of formula II to the monoester of formula I between 0 and 18 and preferably 0.3 and 15, when said esters are in acid form and 0 and 30, preferably 0.3 and when said esters are in neutralized form.

A particularly advantageous composition is formed by the constituents of formulas I to III in which m is equal to 3, n is equal to 16, the ratio of the number of oxyethylenated units to the number of oxypropylenated units is 50:50.

-3lenated poly-( -phenyl-ethyl)-phenol of formula III and in accordance with known methods.

A particularly favourable phosphatation process consists of carrying out two stages: a phosphatation stage carried out by continuously introducing phosphoric anhydride into a medium subject to turbulent stirring conditions, said medium being constituted by said polyoxyalkylenated derivative of formula III containing an adequate quantity of water to initiate the phosphatation reaction, at a temperature of approximately to 40 0 C at the start of the reaction, said temperature being maintained at equal to or below 45°C to the end of phosphoric anhydride introduction, the total phosphoric It anhydride quantity used corresponding to a molar ratio of the polyoxyalkylenated derivative to P 2 0 5 equal to 3 t 0.3; foll-,,:ed by an aging stage of the reaction mediul l obtained icarried out under turbulent stirring conditions at a 20 temperature between 40 and 600C.

The water quantity present in the polyoxyalkylenated derivative is that just necessary for initiating the phos- Sphatation reaction, the water formed during the reaction being adequate to maintain said reaction. The water quantity used is generally approximately 0.0025 to 0.05 mole per mele of polyoxyalkylenated derivative.

The temperature maintained during the phosphatation stage must be adequate to obtain a medium having a sufficiently low viscosity to undergo turbulent stirring conditions, but must not exceed 45 0 C, the temperature during the aging stage having to be kept at between 40 and 600C.

The complete phosphatation operation can be carried out at atmospheric pressure, whereby the first stage can last 1 to 6 hours and the second 30 minutes to 2 hours.

The present invention also relates to surface-active compositions obtained by neutralization of the acid functions L 4 of the basic surface-active compositions of at least one mixture of phosphoric monoester of formula I, phosphoric diester of formula II and nonionic compound of formula III.

This operation of neutralizing the acid functions can be carried out with the aid of a base in an adequate quantity to obtain a composition having a pH of at least 7 and generally approximately 7.5 to 8.

Bases which can be used are alkaline hydroxides (soda, potash, etc.) and amines (diethanol amine, triethanol amine,, morpholine, N-methylcyclohexyl amine' etc.).

As this operation is exothermic, it is carried under turbulent stirring conditions at a temperature such that that of the medium does not exceed 60 0 C. This is industrially Soo carried out at a temperature of approximately 45 0 C and generally lasts between approximately 15 and 45 minutes.

6° The polyoxyalkylenated poly-(l-phenyl-ethyl)-phenols of S. formula III used can be obtained according to known methods 9'oo by the simultaneous addition of monoethylene glycol and monopropylene glycol to a poly-(l-phenyl-ethyl)-phenol with the final addition of 1 mole of monoethylene glycol, the o respective quantities of monoethylene glycol and ionopropylene glycol being determined by the ratio of the number of oxyethylenated units to the number of oxypropylenated 444o units previously chosen. This operation generally lasts to 40 minutes at 140 to 1800C, in the presence of 0.5 to by weight, based on the end product, of an alkaline base, such o as soda as the catalyst, the monoalkaline glycol and poly-(lphenyl-ethyl)-phenol quantities being stoichiometric.

The surface-active composition according to the invention is particularly suitable for the formulation of active substances insoluble or difficultly soluble in water requiring a suspending during their application.

As stated, the starting substance or substances must be insoluble or difficultly soluble in water at ambient temperature, which is usually betWan 15 and 25 0 C. The term "difficultly soluble" is understood to mean a solubility less than 1% by weight.

I 1 Active substances which can be formulated according to the invention are pigments and extenders, dyes, optical brighteners or bluing agents and various additives in numerous industries, such as plastics materials, paints, textiles, concrete, cosmetics, pharmacy, etc.

A preferred sphere of application for the invention is is phytopharmacie and more specifically the formulation of active substances such as insecticides, acaridtdes 'fungicides and their various combinatiois, herbicides, nematicides, molluscicides, attractants, repellents and rodenticides.

Examples of insecticides suitable for the invention are those belonging to the groups: organo-halogens or chlorines; carbinols; organiphosphorus compounds; S0 sulphones and sulphonates; o carbamates; benzoyl ureas; synthetic pyrethrinoids.

20 Fungicides which can be used in the invention can be Schosen from: carbamates; SL, benzene derivatives; phenol derivatives; quinones; dicarboxymides; amines and amides; diaz'nes; sulphamides and sulphur derivatives; guanidines; heterocyclic compounds; S metallic monoethyl phosphites; organostannic compounds.

Chemical substances having herbicidal properties are those belonging to the following chemical groups: phenol compounds; -6carbamates; substituted ureas; diazines; triazines; quaternary ammoniums; benzonitriles; toluidines; triazoles, etc.

A particularly interesting application of the surfaceactive composition according to the invention is in the formulation of at least one solid active substance in the form of fluid aqueous dispersions called "flowables". The active substance chosen has a melting point higher than t and preferably higher than 100 0 C and must not be sensitive to hydrolysis.

In aqueous media, said dispersions contain: at least one solid active substance, the surface-active composition according to the invention and optionally one or more other conventional anionic or nonionic surfactants for this type of application at least one gelling preventing agent optionally a wetting agent optionally a thickening agent and various adjuvants.

The surface-active composition according to the invention has a wetting power, so that the presence of a wetting agent is not indispensable. However, i? the presence of such an agent is desired, it can be chosen from among the following: alkali metal soaps, such as C 8

-C

24 saturated or unsaturated fatty acid potassium or sodium salts, sodium Nlauryl sarcosinate and sodium N-acyI sarcosinate; alkaline sulphonates, such as alkyl sulphonates of the sodium diethylhexyl sulphosuccinate type, alkylbenzene sulphonates such as ninyl or dodecyl benzene sulphonates of sodium, diethanolamlne, triethanolamine or N-methylcyclohexyl amine, alkaline alkylnaphthalene sulphonates and alkaline 7 N-alkyl laurates; sulphates and sulphated products, such as alkaline alkyl sulphates of the sodium lauryl sulphate type, polyoxyethylinated and sulphated fatty alcohols and polyoxyethylenated and sulphated alkyl phenols.

The gelling preventing age'ts prevent the possible formation of crystals during the storage of the dispersions, it being possible to use conventional gelling preventing agents such as ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, urea, etc.

Thickeners are preferably used with a view to maintaining the active substance in suspension and for preventing o any sedimentation during storage. It is possible to use o organic thickening agents, which are hydrosoluble or able 0 4 4 to swell in water, such as polysaccharides of the xanthane gum type, alginates, carboxylated or hydroxylated methyl r* celluloses, synthetic macromolecules such as polyacrylates, polymaleates, polyvinyl pyrrolidones, polyethylene glycols, polyvinyl alcohols. It is also possible to use inorganic thickeners, such as bentonites, silicas, etc, il The auxiliary additives which can be used are antifoaming agents polysiloxanes), protective agents with respect to oxidation, UV rays or pH variations, dyes, bactericides, adjuvants for modifying the adhesion of the treatment mixture to the plants, etc.

4 Tie weight proportions of the different constituents of the dispersions are generally as follows: 10 to 89% water 10 to 65% active substance or substances 0.2 to 20% surface-active composition according to the invention 0.8 to 20% of gelling preventing agent 0 to 10% witting agent 0 to 5% thickener.

These aqueous dispersions can be obtained in known manner, e.g. by dissolving tile surface-active composition in 8 the gelling preventing agent and water and then dispersing under vigorous stirring the active substance in the solution, grinding until a particle size of approximately 1 to microns is obtained and then degassing.

The thus obtained dispersions have a very good storage stability, a high active substance content, a low viscosity and a good stability when diluted in Water at the use dose and throughout the application period.

A second application of the surface-active composition according to the invention is in the formulation of at least one active substance in microgranule form.

If the active substance is in the liquid state, it can be absorbed on a pulverulant support, such as calcium silicates, precipitated silicas with a high absorbing power RHONE-POULENC ZEOSIL 39 A) and brought into a quantity adequate for obtaining a dry powder.

The microgranules produced according to the invention comprise: at least one active substance o* 20 the surface-active composition according to the invention and optionally one or more other conventional surface-active agent or agents for this particular application type S a binder optionally a wetting agent optionally a filler optionally a disintegrating agent optionally auxiliary products.

The weight proportions of the different constituents are generally as follows: 10 to 95% active substance or substances S 3 to 10% of surface-active composition according to the invention 2 to 10% of binder 0 to 75% of filler or fillers 0 to 5% of wetting agent or agents 0 to 5% of disintegrating agent or agents.

I i r. r A* -i I, 9 The following binders can be used: tne copolymers obtained from an unsaturated carboxylic acid and and a-olefin compound and/oo a vinyl compound, such as maleic anhydride diisobutylene copolymers sold by RIONE-POULENC or GERONAZZO under the trade names SOPROPON T 36, SOPROPON T 36 K or GEROPON TA 72; carboxylic copolymers, such as the polyacrylic acids sold by RHONE-POULENC under the name DISPERSANT DG or DA; polynaphthalene sulphonates, polyalkyl naphthalene sulphonates sold by RHONE-POULENC under the trade name SUPRAGIL NS 90 or MNS 90 or by GERONAZZO under the name GEROPON RM 210.

Among the surfactants which can be present alongside the surface-active composition according to the invention, reference can be made to polyoxyethylenated and/or polyoxy- S propylenated derivatives of aliphatic alcohols, as well as optionally polyoxyethylenated fatty amides.

The wetting agents which can optionally be used are as referred b hereinbefore.

;20 Among the fillers which can be used, reference can be l made to crushed or ground natural inert compounds, such as kaolin, attapulgite, bentonite, chalk, talc, etc. or via synthetic products, such as precipitation or combustion silica, calcium carbonate, etc.

The function of the disintegrating agents is to assist ,the release of the active substance and can be constituted by bentonite, corn starch or highly soluble mineral salts, such as sodium bicarbonate, sodium chloride, etc.

The auxiliary products are in particular: antifoaming agents, such as polysiloxanes agglomeration preventing agents such as precipitated silica antistatic agents such as lithium chloride, as well as tridecylphosphoric acid potassium salt oxidation, UV or pH-variation protecting agents various additives, such as dyes or adjuvants for modifying the adhesion of the treatment mixture to the plants.

1 10 The said granules can be prepared according to i,,own granulation or agglomeration methods, e.g. in a fluidized bed, by atomization if the melting temperature of the active substance permits it, on a turntable, by extrusion, etc.

The size of the granules obtained can vary between 100 and 500 microns or between 0.1 and 2 mm, as a function of the granulation methods used.

The thus obtained granules are highly dispersable in water, have a good resistance to handling without dust formation, a high active substance content, a good physicochemical stability and good fluence.

Another application of the surface-active composition o according to the invention is in its use for the formulation of the aforementioned active substances as wettable powders.

The wettable powders according to the invention are S generally constituted by at least one a(,ctve substance, at Sleast the surface-active composition according to the S Invention, optionally a filler and optionally auxiliary products.

The active substance defined hereinbefore is in solid A. or liquid form. The solid active substance generally undergoes crushing or grinding in order to bring it to the desired 0 0* grain size, which is such that 95% by weight of the particles have an apparent diameter below 20 4m and the mean diameter is between 2 and 10 tim. The mean diameter is defined as that at which 50% by weight of the particles have a diameter higher or lower than the mean diameter.

Account must be taken of the melting point with regards to the choice of the grinding process. Compressed air grinding Is preferable in the case of active substances with a low melting point 150 0 This melting point also has an influence on the possible active suLtance concentration, which can increase with the melting point. If the active substance Is in the liquid state, it is possible to absorb it on the pulverulent support in order to have a solid presentation.

Preference is given to precipitated silicas with a high /2 into a quantity adequate for obtaining a dry powder, or calcium silicates.

The fill-rs are inert compounds which can either serve as a suoport for the active substance and the surfaceactive composition according to the invention, if they are liquid, or as an active substance diluting agerut. They are ground natural products, such as kaolin, attapulgite, bentonite, chalk, talc, or synthetic products, such as precipitation or combustion silica, calcium carbonate, etc.

Account must be taken of the following characteristics when choosing the fillers: fineness: this characteristic has a very great 1nfluence on the content in suspension and the fluence; •r pH: it is important that the pH o the filler is S, matched to the active substance, whose stability is often o dependent on this factor; free water content: generally it is desirable for this content to be as low as possible, the deterioration of the active substances generally being assisted by the Spresent'e of water; agglomeration-preventing property: this is particularly important for wettable powders in high concentration or obtained from active substancei with a low melting point; price: the importance of this factor obviously increases as the formulation is less concentrated in active Ssubstances.

The auxiliary products which can be used are antifoamlng Sagents, aggloneration preventing agents, antistatic agents, protecting agents and the various additives referred to hereinbefore.

In the case of particularly hydrophobic active substances, it is advisable to add a wetting agent of the type referred to hereinbefore.

The various aforementioned constituents can be used in wettable powders in the following proportions: It in which: m is equal to 2 or 3; /3 12 10 to 90% active substance or substances 0.5 to 20% surface-active composition according to the invention 9.5 to 75% filler or fillers 0 to 5% wetting agent or agents 0 to 5% au;iliary product or products.

The production process for the said wettin.g powders -differs as a function of whether the active substance is solid or liquid. When the active substance is solid it is mixed with the other constituents, such as the surface-active composition according to the invC.ltion and the wetting agent will be absorbed beforehand on an obsorbing filler if in S, liquid form.

.It is possible to add to the mixture a diluting filler and possibly auxiliary products. The various constituents can be added simultaneously or successively, the order not being critical.

The mixing time is a function of the apparatus used and will easily be determined by the Expert in such a way that a homogeneous mixture is obtained.

o The mixing operation can be carried out in a known 0 powder mixer, e.g. free fall mixers of the drum type, helical screw horizontal or vertical mixers and planetary mixers.

When the active substance is liquid, its atomization takes place on an absorbing filler. It may be of interest to slightly heat the active substance if its viscosity is (igh at ambient temperature. This is followed by the IJdition of the surface-active composition and the wetting agent simultaneously with the active substance. It is also possible to add a dilution filler and optionally auxiliary products. Mixing is continued until it is homogeneous. i The wettable powders obtained using the composition according to the invention have an excellent storage stability.

The following examples are given in an informative and non-limitative manner: 13 EXAMPLE 1 Preparation of the Surface-Active CompositionsAccording to the Invention in Acid Form 3 molar parts of polyoxyalkylenated derivative of formula III are introduced into a reactor equipped with a turbulent helical stirring system, a cooling system and a heating system. The temperature is raised to 370C and then 1 molar part of P 2 0 5 is introduced accompanied by continuous turbulent stirring and at a constant flow rate. As the reaction is exothermic, the temperature of the medium is maintained at 43 t I1C by cooling up to the end of P 2 0 introduction, which lasts approximately 75 minutes.

At the end of P205 addition, the reaction is allowed to continue at the same temperature for 3v minutes (aging stage), whilst continuing stirring.

S, The. thus obtained product is potentiometrically analyzed. It is possible to measure the diester content and i the monoester content, the remainder mainly being constituted by the derivative of formula III.

20 EXAMPLE 2 Preparation of the Surface-Active Compositions According to the Invention Neutralized by TrieF'oano Amine or Potash The product obtained in example r is neutralized by triethanol amine or 38% potash until a pH of the medium of approximately 8 is obtained. During this operation, cooling is regulated so that the temperature does not exceed In the tables, the ester levels are expressed in acid form, i.e. prior tc, neutralization.

EXAMPLE 3 Preparation of a "Flowable" parts of the surface-active composition according "1 i i 14 to the invention are dissolved in 70 parts of monoethylene glycol, followed by the addition of 0.3 parts of antifoaming agent 416/R manufactured by RHONE-POULENC and 393 parts of water. 400 parts of active substance are added slowly and accompanied by stirring. Stirring is continued for approximately 3 minutes to obtain a homogeneous mixture.

This gives a predispersion, which is then ground in a "Mini Motor Mill" marketed by EIGER ENGINEERING LTD. The grinding chamber is filled with 59 g of diameter 1 mm glass.

balls, the speed being 4000 rpm. Grinding is continued for approximately 4 minutes, in order to obtain particles with a diameter between 2 and 6 microns.

The mixture obtained is left to stand for 3 to 4 hours (in order to eliminate bubbles and foam present).

The "flowable" obtained is checked by measuring the consistency with a FORD section no. 4 (cf 4) rheological control and measurement of the BINGHAM VB plastic viscosity SP using the RHEOMAT 30 of CONTRAVES ("Initiation h la Rh6ologie" Technique et Documentation Lavoisier pages 55 and 56).

t 20 EXAMPLES 4 TO 9 r Using the operating procedure of example 3, a flowable containing as the active substance atrazine (chloroethylamino- :44 butylamino-s-triazine), as the surface-active composition, a composition prepared according to the operating procedure of example 2 from polyoxyalkylenated tri-(l-phenyl-ethyl)-phenol and whereof the oxyethylene unit (OE) oxypropylene unit (OP) quantities and the OE/OP proportion are given in table I is prepared. The properties of the flowable obtained appear in table I.

EXAMPLE The operation described in example 4 is repeated replacing atrazine by diuron (dichlorophenyldimethyl urea). The properties of the flowable obtained appear in table I.

I

15 EXAMPLE 11 The operation described in example 4 is repeated by replacing the atrazine by carbaryl (naphthyl N-methylcarbamate) and using a surface-active composition in acid form (i.e.

prepared according to the operating procedure of example 1) and not neutralized. The properties of the flowable obtained appear in table I.

EXAMPLES 12 TO 14 The operation described in examples 4 to 6 are repeated by replacing the surface-active composition by a composition prepared according to the operating procedure of example 2 from polyoxyalkylenated tri-(phenyl-ethyl)-phenol of formula:

CH

3 3 -CHZ CH OH The properties of the flowable obtained appear in table II.

SEXAMPLE The operation described in example 4 is repeated, whilst replacing the surface-active composition by the same quantity of SOPROPHOR FL (marketed by RHONE-POU.LENC) constituted by a mixture based on phosphoric monoesters and diesters of polyoxyethylenated tri-(l-phenyl-ethyl)-phenol containing 16 OE, in neutralized form. The properties of the flowable obtained appear in table II.

EXAMPLE 16 The operation described in example 11 is repeated, whilst replacing the surface-active composition by the same quantity 3, n i s eq ualI to 16, the rat io of the number of oxyethylIen ated units to the number of oxypropylenated units is 50:50.

_I 1 -16 Of SOPROPHOR 3 D 33 (markeLed by RHONE-POULENC) constituted by a mixture based on phosphoric monoesters and diesters of polyoxyethylenated tri 1-phenyl -ethyl) )-phenol containing 16 OE, in acid form.

EXAMPLE 17 The operation described in example 4 is repeated, whilst replacing the surface-active composition by a composition prepared acrigto the operating procedure of example 2 from a polyoxyalkylenated nonyl phenol of formula: OX-1 C2 C2 4C The properties of the flowable obtained appear in table II.

Ap p.

9 4 A Pp 4 A At A p p ts 4* 54 tat 4 0 TABLEI (A CD .Example 4 56 7 8 9 10 0 active substance ATR ATR ATR ATR ATR ATR Dfti .OE +OP 16 25 34 16 16 16 16 0

(D

OE OP 50/50 50/50 50,/50 40/60 60/40 30/70 50/50 *C+0 by weight diester 51.8 92.6 21.9 68.2 59.3 14.3 51.8 by weight monoester 20.3 5.3 28.1 6 8 16.3 33.9 20.3

O

0 MD .cF 4 zn s 15 15 15 16 16 *14 (nU VB l.n mPa s 13.5 14.6 12.2 16,7 14.9 18 h 0

C:

(D -S ATR rheans "atrazirse" DIUl means "Diuron" CR means "abrl not for grinding

C

=3 t)C+ 0< a. a* a *0 a 000 @00 as. a 0 a 0 0 0 a 0 00 -*a 000 0 0 3* TABLE II -11aple 12 13 14 15 16 17 active substance CAR ATR ATR ATR ATR CAR ATR OE OP 16 16 25 34 16 OE OP 50/50 50/50 50/50 50/50 50/50 by weight diester 51.8 67.2 66.2 77.8 62.4 by weight monoester 20.3 17.1 19.1 14.4 12.9 :c F in s 17 21 58 18 22 14 :V in mPa s 22 28.6 56.9 20 28 18.5 ATR means "atrazine" DIU means "Diuron" CAR means "carbaryl" not for grinding I

Claims

1. Surface-active compositions based on phosphoric esters of polyoxyalkylenated poly-(l-phenyl-ethyl)- phenols, said compositions comprising a mixture of phosphoric monoesters and diesters of polyoxyalkylenated po ly- (1-phenyl -ethyl) -phenol s and polyoxyalkylenated poly- (1-phenyl-ethyl)-phenols of formulas I to III: 414 4 44 14 4 ft I 444~ 14 14 44 4 4 I I 1 *4 4* 44 4 I I I 4 4 444114 I *44 44 I 4 4 0- cH 2 CH. 2 o\ joX, o- CH 2 l P 0 joX+ n 0 o- CH- 2 C n- 0 CH 2 IO C O (I) (II) (III) in which: 0 to 5% thickener. These aqueous dispersions can be obtained in known manner, e.g. by dissolving the surface-active composition in I i 20 m is equal to 2 or 3; -OX- represents a statistical succession of oxyethylenated and oxypropylenated units; n is such that the total number of oxyalkylenated units in the rdidical 4OX nO CH 2 CH 2 is 14 to with the ratio of the number of oxyethylenated units to the number of oxypropylenated units being between 40:60 and 70:30, said esters of formulae I and II being in acid or neutralized form.

2. Surface-active compositions according to claim 1, wherein the ratio of the number of oxyethylenated units to the number of oxypropylenated units is from 40:60 to 60:40.

3. Surface-active compositions according to any one of the preceding claims comprising from: 0 to 70% by weight of the constituent of formula III, and monoester and diester in a weight ratio of diester of 1 *formula II to monoester of formula I of from 0 to 18, when said esters are in acid form and from 0 to 10, when said esters are in neutralized form.

4. Surface-active compositions according to any one of the preceding claims wherein m is equal to 3, n is equal to 16 and the ratio of the number of oxyethylenated units to the number of oxypropylenated units is 50:50, Process for the preparation of surface-active compositions by phosphatation of at least one polyoxy- alkylenated poly-(l-phenyl-ethyl)-phenol of formula L S n I~k, 0 to 75% of filler or fillers 0 to 5% of wetting agent or agents 0 to 5% of disintegrating agent or agents. 2\ -fl CH 0- CH 0H (III) in which; m is equal to 2 or 3; (OX) represents a statistical succession of oxy- ethylenated and oxypropylenated units; n is such that the total number of oxyalkylenated units of the radi'cal (OX0n CH 2 C- i 2 s 14 to with a ratio of the number of oxyethylenated units to the number of oxypropylenated units between 40:60 and 70;30.

6. Process according to claim 5, characterized in that the ratio of the number of oxyethylenated units to the number of oxypropylenated units is between 40:60 and 60:40'. "X 7. Process according to claims 5 or 6, characterized in that m is equal to 3, n is equal to 16 and the ratio of the number of oxyethylenated units to the number of oxy- propylenated units is 50:50. 1t,, 8, Process according to any one of the claims 5 to 7, characterized in that the phosphatation operation is I carried out in two stages: a phosphatation stage carried out by cantinuously introducing phosphoric anhydride into a medium subject to turbulent stirring conditions, said medium being consti- tuted by said polyoxyalkylenated derivative of formula III containing an adequate quantity of water to initiate the phosphatation reaction, at a temperature of approximately 35 to 40C at the start of the reaction, said temperature being maintained at equal to or below 45 0 C to the end of phosphoric anhydride introduction, the total phosphoric anhydride quantity used corresponding to a molar ratio of the polyoxyalkylenated derivative to P 05 equal to 3 t 0.3; followed by an aging stage of the reaction medium I trioecyipnospnoric acia potassium salt oxidation, UV or pH-variation protecting agents various additives, such as dyes or adjuvants for modi- fying the adhesion of the treatment mixture to the plants. 22 obtained carried out under turbulent stirring conditions at a temperature between 40 and 60 0 C.

9. Use of the surface-active compositions according to claims I to 4 in the formulation of water-insoluoDle phytosanitary active substances. Use aciord!ng to claim 9 in the formulation of water-insoluble phytosanitary active substances in the form of fluid aqueous dispersions.

11. Fluid aqueous dispersions of water-insoluble phytosanitary substances constituted by 10 to 89% by weight water 10 to 605% by weight active substance or substances S 0.2 to 20% by weight of surface-active composition according to one of the claims I to 4 0.8 to 20% by weight of gelling preventing agent 0 to 10% by weight wetting agent 0 to 5% by weight thickener.

12. Use according to claim 9 in the formulation of phytosanitary active substances in granule form. ysa13. Granules constituted by: to 95% by weight of phytosanitary active substance or substances 3 to 10% by weight of surface-acti've composition according to one of the claims 1 to 4 2 to 10% by weight binder 0 to 75% by weight filler or fillers 0 to 5% by weight wetting agent or agents to 5% by weight disintegrating agent or agents.

14. Use according to claim 9 in the formulation of phytosanitary active substances in the form of wettable powders. Wettable powders constituted by: 10 to 90% by weight of phytosanitary active substance or substances S f 3 o 1% b weiht f srfae-aci'v copostio i, i ii substance is in the liquid state, it is possioie Lo aubus U L on the pulverulent support in order to have a solid presentation. Preference is given to precipitated silicas with a high 23 0.5 to 20% by weight of the surface-active composition according to one of the claims 1 to 4 9.5 to 75% by weight of filler or fillers 0 to 5% by weight of wetting agent or agents 0 to 5% by weight of auxiliary product or products.

16. A surface-active composition in accordance with claim 1 substantially as herein described with reference to the examples.

17. A process in accordance with claim 5 substantially as herein described with reference to the examples.

18. Fluid aqueous dispersions in accordance with claim 11 substantially as herein described with reference to the examples. DATED this ist day of MAY, 1989 RHONE-POULENCE CHIMIE Attorney: W\ILLAM S, LLOYD FTellow mnstitute of Patent Attornys of Australia of SHELSTQN WATERS k'4 i