AU611593B2 - Granules for spreading and process for their preparation - Google Patents

Description

r 611593 COMMONWEALTH OF AUSTRALIA FORM PATENTS ACT 1952 COMPLETE SPECIFICATION FOR OFFICE USE: Class Int.Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: S..Related Art: too* Name of Applicant: RHONE-POULENC CHIMIE Address of Applicant: 25, Quai Paul Doumer, 92408, Courbevoie, France "Actual Inventor: Christian Segaud ddress for Service: SHELSTON WATERS, 55 Clarence Street, Sydney Complete Specification for the Invention entitled: "GRANULES FOR SPREADING AND PROCESS FOR THEIR PREPARATION" The following statement is a full description of this invention, including the best method of performing it known to us:- 1 i i la- GRANULES FOR SPREADING AND PROCESS FOR THEIR PREPARATION The present invention relates to granules for spreading, containing active ingredients for plant treatment and to a process for their preparation; a property of these granules is that they disintegrate and slowly release the active ingredient, and this enables soils to be treated in a uniform manner.

The granules for spreading, based on at least one 10 active ingredient for plant treatment and forming the subject of the invention, contain a binder and are characterized in that the said binder comprises a waterdispersible sulphonated polyester.

Among the active ingredients for plant treatment forming part of the composition of the granules of the invention there may be mentioned insecticides, acaricides, fungicides and their various combinations, herbi- Scides, nematocides, molluscicides, attractants, repellants and rodenticides.

As examples of insecticides there may be mentioned those belonging to the groups of: organohalogen or chlorine compounds, carbinols, organophosphorus compounds, sulphones and sulphonates, carbamates, benzoylureas, K -2- -synthetic pyrethrinoids.

The fungicides may be chosen from: -carbamates, -benzene derivatives, -phenol derivatives, -quinones, -dicarboxiinides, -amnines, amnides, -diazines, -suiphamides and sulphur derivatives, -guanidines, -heterocycilic compounds, -metal monoethyl phosphites, -organostannic compounds.

By way of chemical substances exhibiting herbi- ,0*0 cidal properties, use may be made of those to be found in the following chemical classes: phenolic compounds, carbainates, substituted ureas, diazines, triazines, amides, quaternary amnmonium compounds, benzonitriles, toluidines, triazoles and others.

I ii~ 3 The water-dispersible sulphonated polyesters which may form the binder are known products. They can be prepared by cocondensation of an organic diacid (such as a saturated or unsaturated aliphatic diacid, an aromatic diacid, a diacid containing several aromatic nuclei, or an arylaliphatic diacid), one of its diesters or its anhydride, with a sulphonated organic diacid or one of its diesters with a diol, in the presence of a conventional polyesterification catalyst such as tetraisopropyl i10 orthotitanate.

As starting monomers commonly employed for the preparation of the water-dispersible sulphonated polyesters, there may be mentined, as: -organic diacids: saturated or unsaturated aliphatic diacids, aromatic diacids, such as succinic, adipic, suberic and sebacic acids, maleic, fumaric and itaconic acids, ortho-phthalic, isophthalic and terephthalic acids, anhydrides of these acids and their diesters, such as methyl, ethyl, propyl and butyl diesters. The prefer- 20 red compounds are adipic acid and ortho-phthalic, iso- 'e phthalic and terephthalic acids; -sulphonated organic diacids: sodium sulphonate diacids or their diesters such as dialkyl isophthalates and dialkyl sulphosuccinates like sodium phthalatesulphonate or sodium dimethyl sulphosuccinate; diols: aliphatic glycols such as ethylene glycol, diethylene glycol, dipropylene glycol and the higher 1: i i 4 homologues, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and cyclanic glycols such as cyclohexanediol and dicyclohexanediolpropane. The diols which are preferably chosen are ethylene glycol and diethylene glycol.

The preferred water-dispersible sulphonated polyesters are those which have a number-average molecular mass of between 10,000 and 35,000, an acid value of less than 5 mg of KOH/g, and a sulphur content of between 0.8 and 2 by weight, preferably between 1.2 and 1.8 The present invention is aimed more particularly at granules for spreading containing: from 2 to 97 of their weight, preferably from *f 5 to 95 of their weight of active ingredient for plant treatment from 0.3 to 40 of their weight, preferably from S1 to 15 of their weight, very particularly from 5 to S, 15 of their weight of water-dispersible sulphonated polyester binder from 0 to 95 of their weight, preferably from 0 to 85 of their weight of a filler from 0 to 25 of their weight, preferably from 0 to 10 of their weight of a dispersing agent with a binding property.

The fillers are inert compounds which can be used: either as a carrier for the active ingredient and the various constituents if they are liquid 5 or as a dilution agent for the active ingredient.

i These are ground natural substances such as kaolin, attapulgite, bentonite, chalk, talc, or synthetic products such as precipitated or pyrogenic silica, calcium carbonate, and the like.

Among the dispersants with a binding property there may be mentioned naphthalenesulphonates, condensed sodium methylnaphthalenesulphonates, condensed 4,4dihydroxydiphenyl sulphones, and sodium or potassium 99o *0 salts of maleic anhydride-diisobutylene copolymers, optionally mixed with an ethoxylated distyrylphenol.

Besides these main constituents there may be present: -nonionic, anionic or cationic surface-active agents; there may be mentioned: as nonionic surface-active agents: ethoxylated fatty alcohols, ethoxylated alkylphenols, esters of fatty acids and of glycerol, esters of fatty acids and of polyethylene glycol, esters of sorbitan and of optionally 20 ethoxylated fatty acids, ethoxylated oils and fats, Soptionally ethoxylated fatty acid mono- and diethanolamides, oxyethylene/oxypropylene block copolymers, saccharoglycerides, etc, as example of anionic surface-active agents: alkali metal or ammonium salts of fatty acids or of aminocarboxylic acids (N-acylsarcosinates), sulphonates and sulphonated derivatives such as alkylbenzene-

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l 6 sulphonates, naphthalenesulphonates, lignosulphonates, alkanesulphonates, sulphonated olefins, dialkyl sulphosuccinates, amidosulphonates (N-acyl-N-alkyltaurates), 2sulphoethyl esters of fatty acids (acyl isethionates), etc; sulphates and sulphated derivatives such as optionally ethoxylated sulphated fatty alcohols, sulphated ethoxylated alkylphenols, sulphated fatty acids, sulphated fatty acid esters, sulphated alkanolamides, sulphated natural oils and fats, etc, and phosphoric ::10 esters of ethoxylated alkylphenols or of ethoxylated 9 fatty alcohols, etc, as example of cationic surface-active agents: amine oxides, ethoxylated alkylamines, etc, -other binders such as polyvinyl alcohol, polyacrylate salts, xanthan gum, antistatic agents which may be inorganic salts 4 such as lithium chloride or organic phosphates such as Sphosphates of fatty alcohols or fatty acids, especially the potassium salt of tridecylphosphoric acid, protective agents enabling the active ingredient to be stabilized against oxidation, UV rays and pH variations (buffer mixture) and various other additives such as colorants, adjuvants, repellants and attractants.

The granules for spreading forming the subject of the invention are obtained by agglomeration of the active ingredient with the binder and the other constituents 7which may be present.

The agglomeration operation may be carried out according to the conventional granulation processes, for example in a fluidized bed, by spraying if the melting temperature of the active ingredient permits, by extrusion, by granulation on a rotary tray, etc.

If the active ingredient is in the liquid state, it is quite possible to absorb it onto a pulverulent carrier, to have a solid formulation.

Precipitated silicas of high absorption capacity, used in sufficient quantity to obtain a dry powder, or I else calcium silicates, are preferably chosen.

Various methods of preparing granules, illustrating the various granulation methods are given below, no limiting character being implied.

The preparation of the granules in a fluidized 6 bed consists in making a premix of the solid active ingredient (ground or absorbed on a carrier) with whole or some of the quantity of binder and of any other constituents used, and then spraying onto this premix water optionally containing the fraction of binder which is not premixed.

The material is kept in a fluidized state by means of a rising stream of warm air from 20 to 806C.

When the granules have been formed, they can be dried with the aid of a stream of warm air at a temperature below the melting or decomposition temperature of

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I

8 the active ingredient.

The size of the granules obtained may vary within quite wide limits between 0. 1 and 2 mm.

The spray-granulation method consists in spraying into a stream of hot air at between 140 and 240°C a concentrated slurry (50 to 70 of solid content) containing water, the active ingredient, the binder and the other constituents which may be present.

The size of the granules obtained generally 'tO varies between 100 and 500 pm.

Another method of granulation consists in agglomerating the active ingredient on a rotary tray.

The solid materials (active ingredient, all or some of the binder and the other constituents which may be present) are charged onto the rotary tray and the mixture of the said materials is homogenized by rotating S. the tray.

0V To agglomerate the active ingredient, a water spray is applied, optionally additionally containing a proportion of binder and of surface-active agent in S" liquid form.

The granules thus obtained must be dried in a second stage to a water content of 0.3 to 1 depending on the active ingredient.

The drying operation is carried out at a temperature below the melting or decomposition temperature of the active ingredient. It may be performed in air or L p.

9 under reduced pressure.

The granules are more or less spherical in shape and their size varies between 100 and 500 Am.

The extrusion granulation method takes place as follows: In a first stage, a powder/powder mixing is carried out of the active ingredient, ground or on a carrier, of the binder in solid form and of the other constituents which may be present in solid form.

.10 The mixture obtained is moistened by addition of 10 to 30 by weight of water. The addition of water may be performed by spraying.

The mixing of the constituents is carried out in a powder mixer of known type.

The paste obtained is then extruded, generally in an equipment operating at low pressure.

S" After extrusion, the granules must be dried.

Their dimensions are of the order of 1 to 4 mm in o9 length and 0.5 to 2 mm in diameter.

The granules for spreading forming the subject J of the invention have the advantage of disintegrating and of slowly releasing the active ingredient.

This property allows them to be employed for treating soils in order to combat parasites, for crop protection, etc.

The following examples are given by way of guidance and cannot be considered as a limit of the scope I t -1 i i 10 and of the spirit of the invention.

The granules for spreading were prepared in the following general manner: The following are mixed: the active ingredient(s) optionally, the carrier consisting of Rh6ne- Poulenc silica Zeosil 39 AB the binder based on water-dispersible sulphonate polyester Argirec B24 kaolin marketed by Blancs Min6raux de Paris .9 optionally a dispersing agent in a Moritz-type rapid mixer marketed by Moritz.

Moistening is carried out by spraying with water.

The moist paste obtained is then extruded in an Alexander Werk AGM/R extruder fitted with rolls, marketed by Alexander Werk.

Granules 1 mm in diameter and 2.5 mm in length are thus obtained.

These are then dried in an oven at 50"C for 1 hour and are then screened at 200 microns in order to Sremove dust.

Disintegration control The control of granule disintegration is carried out using an apparatus consisting of a glass column with a working height of 25 cm and an inner diameter of 15 mm provided with a glass sinter at its base and fitted: I C 11 with a stopcock in its lower part with a pump connected to a distilled water reservoir, in its upper part; the output of this pump is set at 11 ml/minute.

A collecting receiver is situated under the column.

The following are introduced into the column: 2 g of glass beads with a diameter of between and 0.75 mm 0 "010 in successive layers, 0.2 g of granules to be tested and 8 g of glass beads them 2 g of glass beads.

The column is filled with distilled water, slowly at first and then quickly up to a height of 15 cm above the packing.

The pump is started up and the lower stopcock is opened so as to keep the height of water in the column constant. This percolation is maintained at a rate of 11 ml/minute, the collector receiver being changed every 20 10 minutes.

The percolator is stopped when the last fraction collected is perfectly clear, corresponding to the disintegration of the granules.

The larger the number of fractions collected which are not clear, the slower the granule disintegration.

i, 12 Example 1 Granules are prepared according to the method described above, from: 7.5 g of diazinon adsorbed on 5 g of Zeolex 39 6.5 g of dry Gerol PS 30 (water-dispersible sulphonated polyester marketed by Rh6ne-Poulenc) 80 g of kaolin 15 g of water.

The result of the disintegratio test is shown in 10 Table I.

Exiaple 2 The operation described in Example 1 is repeated, the 6.5 g of Gerol PS 30 being replaced with 6.5 g of dry Gerol PS 20, another sulphonated polyester marketed by Rh6ne-Poulenc.

The result of the disintegration test is siown in Table I.

Examples 3 and 4 The operation described in 7xainple 1 is repeated, the 6.5 g of Gerol PS 30 being replaced with: S- 6.5 g of Geropon HB, sodium polyacrylate with a mass in the region of 5000, marketed by Rh6ne-Poulenc (Example 3) 6.5 g of Geropon DG, potassium polymethacrylate with a mass in the region of 3000, marketed by Rh6ne- 1 Poulenc (Example 4).

I i i i ill 13 The results of the disintegration test are shown in Table I.

Example Granules are prepared according to the method described above from: 7.5 g of diazinon adsorbed on 5 g of Zeolex 39 7.5 g of butocarboxim dissolved in 1.3 g of xylene and adsorbed onto 5.9 g of Zeolex 39 10 g of Gerol PS 62.8 g of kaolin 19 g of water.

The result of the disintegration test is shown in Table II.

Example 6 The operation of Example 5 is repeated, the 10 g of Gerol PS 30 being replaced with 10 g of Rhodoviol 30/70, polyvinyl alcohol marketed by Rh6ne-Poulenc.

The result of the disintegration test is shown in Sable II.

,0 Example 7 Granules are prepared according to the method described above from: 80 g of preground lindane 5 g of Gerol PS 3 g of Supragil MNS 90, condensed sodium methylnaphthalenesulphonate marketed by Rhone-Poulenc 12 g of kaolin 14 21 g of water.

The result of the disintegration test is shown in Table II.

0 11 ,see, 015 ,0 60000 The abbreviations shown the following meaning: VC very cloudy VSC C cloudy VLC MC modemately WC cloudy SC slightly cloudy in Tables I and II have very slightly cloudy very little cloudiness water-clear TABLE I FRACTION EXAMPLE 1 12 3 4 APPEARANCE O~F THE FRACTION 1 C MC VC VC 2 C MC C C 3 MC MC WC MC 4 SC MC SC SC MC SC 6 SC MC IWC 7 SC VSC 8 SC VLC 9 VSC VLC VSC i VLC 11 VSC WC 12 IsC 13 WC 15 TABLE II

EXAMPLE

FRACTION 5 67 APPEARANCE OF THE FRACTION 1C cC 2 C C C 3 MC SC mc 4 SC VSC SC SC WC SC ~*I7 SC VSC 8SC WC ate*

VSC

11 VSc ,0.0 12 I WC

Claims (10)

1. Granules for spreading based on at least one active -ingredient for plant treatment and containing a binder, characterized in that the said binder comprises a water-dispersible sulphonated polyester.

2. Granules according to Claim characterized in that the water-dispersible polyester is obtained by co-condensation of: 1) an organic diacid or one of its diesters or its anhydride and, 2) a sulphonated organic diacid or one of its diesters with a diol, in the presence of a polyesterification catalyst.

3. Granules according to Claim characterized in that Sthe organic diacid is a saturated or unsaturated aliphatic diacid, a diacid containing a number of aromatic nuclei or an arylaliphatic diacid.

4. Granules according to Claim 2 or 3, characterized in that the diester of sulphonated organic diacid is a sodium dialkyl isophthalate sulphonate or a sodium dialkyl sulphosuccinate.

5. Granules according to any one of Claims 2 to 4, characterized in that the diol is an aliphatic glycol or a cyclanic glycol.

6. Granules according to any one of the preceding *claims, characterized in that the water-dispersible sulphonated polyester has a number-average molecular mass of between 10,000 and 35,000 an acid value of less than 5 mg of KOH/g and a sulphur content of between 0.8 and N'z i ~1 17 2 by weight.

7. Granules for spreading, characterized in that they contain from 2 to 97 of their weight of active in- gredient for plant treatment from 0.3 to 40 of their weight of water-disper- sible sulphonated polyester binder from 0 to 95 of their weight of a filler from 0 to 25 of its weight of a dispersing agent with binding property.

8. Granules according to the preceding claim, characterized in that they contain: from 5 to 95 of their weight of active in- gredient for plant treatment from 1 to 15 of their weight of water-disper- sible sulphonated polyester binder S- from 0 to 85 of their weight of a filler I from 0 to 10 of its weight of a dispersing agent with binding property.

9. Process for the preparation of granules for spreading forming the subject of any one of -he preceding claims, by agglomeration of the active ingredient with the water-dispersible sulphonated polyester and the optional other constituents. -18 Granules in accordance with claim 1 subgtantially as herein described with 'reference to the examples.

11. Process in accordance with claim 9 substantially as herein before dehscribed with reference to the examples. DATED this 22nd Day of September, 1989 RHONE-POULENC CHIMIE Attorney: IAN ERNST Fellow Institute of Patent Attorneys of Ausirali. of SHELSTON WATERS .0