CA2015797A1

CA2015797A1 - Concentrated liquid compositions based on n-phosphonomethylglycine

Info

Publication number: CA2015797A1
Application number: CA002015797A
Authority: CA
Inventors: Mohammad Dookhith; Hubert Linares
Original assignee: Rhone Poulenc Agrochimie SA
Current assignee: Bayer CropScience SA
Priority date: 1989-05-02
Filing date: 1990-05-01
Publication date: 1990-11-02
Also published as: DK107890A; AU5450290A; IT9020184A0; GB2230955A; IT1240693B; HU902645D0; PT93938A; IT9020184A1; SE9001558D0; LU87728A1; ATA100290A; DK107890D0; SE9001446D0; NL9001009A; SE9001558L; GR900100309A; HUT54273A; GR1000368B; DE4013930A1; GB9009827D0

Abstract

Company called: RHONE POULENC AGROCHIMIE
ABSTRACT
CONCENTRATED LIQUID COMPOSITIONS BASED ON
N-PHOSPHONOMETHYLGLYCINE
Concentrated compositions containing N-phosphonomethylglycine and/or one of its derivatives in the form of liquid compositions consisting of liquid suspensions in an organic solvent medium, containing:
a) N-phosphonomethylglycine and/or one of its derivatives having an inherent solubility in water of more than 5 g/l, this N-phosphonomethylglycine and/or its derivative being present in the compositions in a proportion of at least 100 g/l glyphosate equivalent, at least part of this N-phosphonomethylglycine or its derivatives being in a form insoluble in the medium under consideration, b) a surfactant having an activator character and having the formula in which R is a straight-chain or branched alkyl or alkenyl hydrocarbon chain (8 to 22 carbon atoms), A represents an alkylene group, n + n' is between 2 and 40 and preferably between 20 and 25.
R1 is H or acyl.

Description

The pre~ent invention relate~ to new concentrated formulations based on N-phosphonomethylglycine or compounds containing an N-phosphonomethylglycyl group.
N-Phosphonomethylglycine (sometimes called S glyphosate), and the analogous compounds, their herbicidal properties and the formulations containing them are dei~cribed in particular in US Patent 3,799,758. Although numerous water-soluble or water-insoluble derivatives of glyphosate are known, in fact 10 it is very generally preferred to use the water-soluble ~ -derivatives and it is for this reason that it is the salts of N-phosphonomethylglycine which have been generally developed or marketed, especially the isopropylammonium salt.
More riecently (European Patent Application No. 290416) it has been sought to develop concentrates ba~sed on N-phosphonomethylglycine salts, which can contain N-phosphonomethylglycine in acid form but in all circumstances contain this N-phosphonomethylgycine and/or its derivatives in so1uble or solubilized forms, these concentrates being solutions characterized by the presence of an activator which i8 an alkoxylated amine of a particular type. This alkoxylated amine must have at moist 12 alkoxy groups per molecule and it must have a surfactant character and it must promote the herbicidal activity of N-phosphonomethylglycine derivatives. It can be used in a smaller amount than the known surfactants in the known formulations of . . - .
. ,. . ~ ~ .

. .

201~7~7 N-phoRphonomethylglycine, at least with regard to the production of concentrates intended for application in the open air, in the form of dilute spraying mixtures, at a rate of 100 to 600 l/ha.
Formulations have also been proposed (US Patent 4528023~ which contain the tetraaluminium salt of N-phosphonomethylglycine, which is virtually insoluble in water, as well as a surfactant of a special type. One of the consequences of this insolubility of the active substance is that when the concentrate is diluted in water to obtain the final spraying mixture for spraying, this spraying mixture i8 not in the form of a perfect solution, which is pre~udicial to the application and to obtaining a ~atisfactory efficacy.
However, those skilled in the art have not attempted to apply the formulations of this patent to active substances of higher solubility because experience shows that the production of concentrated suspensions from partially soluble active substances encounters very great difficulties due to a tendency of the concentrated suspensions to ~olidify. One of the explanations for these difficulties and this olidification is that there is a pronounced tendency for growth of the crystals in the continuou~ (aqueous) phase of the suspensions, thi~ growth being able to develop extremely until solidification occurs.
One aim of the present invention is to provide compositions based on N-pho~phonomethylglycine or its .. , . , ~ . : :

-- 20~5797 derivatives having an active substance concentration clearly higher than that of sLmilar compositions known in the prior art.
Another aLm of the present invention i8 to provide compositlons based on N-phosphonomethylglycine or its derivatives which are also able to contain ad~uvants, such as inorganic ammonium salts, in concentrations clearly higher than those of similar compositions known in the prior art.
Another aim of the present invention is to provide concentrates based on N-phosphonomethylglycine or its derivatives which give rise to dilute spraying mixtures having a good herbicidal activity.
Another aim of the present invention is to provide ~ 15 concentrated compositions which are based on N-;~ phosphonomethylglycine or its derivatives and also contain one or more surfactants having an activator action, that is to ~ay having an action promoting the ~ - :, ~ biological activity of the active substance, and in : ~ :
20 ~ particular its herbicidal activity.
Another aim of the pre6ent invention i~ to provide ~-concentrated composition-~which are based on N-phosphonomethylglycine or its derivatives and have -~
favourable properties, 6uch as a good and rapid dispersibility in water.
:
Another aim of the present invention i~ to provide concentrated compositions which are based on N-phosphonomethylglycine or its derivatives and have 201~797 favourable properties, such as a good fluidity at low temperature.
Another aim of the present invention is to provide concentrated compositions which are based on N-S phosphonomethylglycine or its derivatives and havefavourable properties, such as a low tendency to produce foam, which enables lower quantities of anti-foam to be used.
Yet another aim of the present invention is to provide concentrated compositions, or formulations, (also termed concentrates) based on N-phosphono-methylglycine and especially simple N-pho~phono-methylglycine which is sparingly soluble in water.
Another aim of the present invention is to provide compositions based on N-phosphonomethylglycine having the abovementioned advantages, these compositions also containing one or more other herbicides.
It has now been found that these aims can be achieved, in whole or in part, by virtue of the compo-itions according to the invention. Wher- there is no specific indication, the percentsges in the text which follows are percentages in weight/volume.
Moreover, glyphosate equivalent is used to designate the corresponding amount of product as if all of the N-phosphonomethylglycine derivative were in the form of ordinary N-phosphonomethylglycine.
These compositions are liquid compositions consisting of (concentrated) suspensions in an organic, , . ... ~ . .. ~ ..

:;. ~ ~ -,, .: , ''`: ~ ' ' 20~5797 or possibly aqueous-organic, ~olvent medium, containing:
a) N-phosphonomethylglycine and/or one of its derivative~ having an inherent solubility in water of more than 5 g/l, preferably more than 9 g/l, this N-phosphonomethylglycine and/or its derivative being present in the compositions in a proportion of at least 100 g~l glyphosate equivalent, at least part of this N-phosphonomethylglycine or its derivatives being in a form insoluble in the medium under consideration (the ~insolubility results in particular from the fact that the amount of N-phosphonomethylglycine and/or of its :
derivative exceeds the solubility limit in the medium), b) a surfactant having an activator charactsr and 15 having the formula ~;~

~ ( AO ) n Rl ~:
; R - N ~ . ::
(A)n~ R1 : in which ~;~ 20 R is a straight-chain or branched alkyl or alkenyl hydrocarbon chain havlng from 8 to 22 carbon atoms, A represents an alkylene group, preferably ethylene or propylene, n and n' are integers such that n + n' i~ between 2 and 40, preferably between 16 and 30 and still more preferentially between 20 and 25, and Rl is a hydrogen atom or an acyl radical such as formyl, acetyl, propionyl (that is to say CH3-CH2-CO) or '.~,' ~ ' ' .~ ' :
'~"' ''' ',, '' -~ 6 201~797 benzoyL.
The term "derivative" of N-phosphonomethylglycine is intended to include compounds comprising the group -C0-CH2-N-CH2-P=0, preferably a salt, ester or amide. These terms are to be understood in a broad sense, for example so as to include sulfonamides.
Of course, it is possible to replace this single activator surfactant by a mixture of surfactants in which, on average, R, n and n' correspond to the definitions given above.
The herbicidal active substance used in the invention is thus N-phosphonomethylglycine and/or one of its derivatives having an inher-ent solubility in water of more thàn 5 g/l and preferably more than 9 g!l. Derivatives which may be used are the very numerous derivatives of N-phosphonomethylglycine known per se, in particular the salts, taken on their own or as mixtures. The following may be mentioned amongst the most appropriate derivatives: the sodium, potassium or inorganic :
or organic ammonium salts, in particular the isopropylammonium salts, and the sulphonium salts; N-methyl-N-(methylsulphonyl)-N, N'-(phosphonomethyl)-glycylamine; the aluminium salt is not included in ~` ~ the invention. Of course, the use of these products must respect the percentage and solubility conditions indicated elsewhere.
Advantageously, the present invention relates to concentrated com-positions~of the type described above and also having one and/or the other of the following characteristics:
a) the N-phosphonomethylglycine or its derivative is in an amount ln excess of the solubility limit in the medium under consideration, preferably of between 120 .

Sp: ! ~ ' 2~

and 250 g/l and still more preferentially between 160 and 220 g/l; the proportion of undissolved N-phosphono-methylglycine derivative is greater than 30 % and preferably greater than 75 %.
b) N-Phosphonomethylglycine, or its derivative, which i~ insoluble, is in the form of solid particles having a diameter of less than 30 microns and preferably of I ;
between 1 and 20 microns.
c) The concentrated composition contains an ammonium -~:
0 (NH~t) salt such as the nitrate, the phosphate, the sulphamate, the thiocyanate or preferably the sulphate, in a proportion of 100 to 500 g/l, preferably 200 to 350 g/l. . :
d) The concentrated compositions are intended to be 15 diluted by the agriculturalist~ in containers ~ : :
: - . .
containing water so as to be able to spread these dilute spraying mixtures at a rate of 100 to 600 l/ha, the active material ~tself being applied at a rate of 0.125 to 1.5 kg/ha.
e) The weight ratio alvDhosate equivalent ~: surfactant ~activator) ~: 18 between 0.5 and 6 and preferably between 0.6 and 2.
This relatively large amount of surfactant relates to this surfactant having a biological activator/herbicide ;~ 25 character, it being understood that the compositions - according to the invention can also contain, as will be specified below, all types of other components and ln particular of surface-active agents (or surfactants) of i ` 8 2015797 very diverse natures having a wetting or dispersing or emulsifying character; these ~urfactants are then used in dosages very much lower than the dosage of activator.
f) The solvent is an organic solvent, preferably miscible with water, which can contain up to gO ~i of water, preferably less than 30 %, the said solvent being such that N-phosphonomethylglycine is sparingly soluble therein, that is to say soluble to the extent of less than 80 g/l and preferably of less than 40 g/l.
The concentrated suEipensions according to the invention are prepared in a manner such as to obtain a stable fluid product which does not ~iettle (fine grinding).
~ 15They usually contain from 10 to 75 % of active : substances (herbicides), from O.S to 40 % of surfactant(s) having an activator character, from 10 to 50 % of an ammonium salt (ad~uvant), from 0.1 to 10 %
:of ordinary surfactant(s), that i~ to say having a dispersing and/or wetting and/or emulsifying character, and from 0 to 30 % of appropriate additives, such as anti-foams, corrosion inhibitors, protective colloids, thickeners, sequestering agents, thixotropic or pseudoplastic agents, stabilizers, penetrating agents , 25: and~adhesive~, and, as carrier, an organic liquid in :which the active substance is sparingly soluble or insoluble. Some organic solid substances or inorganlc salts can be dissolved or in suspension in the carrier ~....

,, 2~1S797 to assi~t in preventing sedimentation, or as antigels.
More generally, the compounds used in the invention can be combined with all solid or llquid additives corresponding to customary formulation techniques.
S In addition to N-phosphonomethylglycine and/or its ~-derivatives, the compositions used in the invention can contain other known active substance~ having herbicidal properties or plant growth-regulating properties.
The following may be mentioned as herbicidal substances which can be mixed with the glyphosate derivatives in the compositions according to the invention: acifluorfen, aclonifen, bifenox, diflufenican, asulam, the triazine~ (in particular simazine and atrazine), diuron and oxadiazon, herbicides of the hormone or phenoxy types, in particular 2,4-D, 2,4-DB, NCPP, hydroxybenzonitriles (in particular bromoxynil and ioxynil), imidazolinones (in particular imazaquin and imazapur), and sulphonylureas (in particular chlorsulphuron and metsulphuron). The above names are standardized names for designation of herbicides.
These herbicides are mo~t frequently used in a proportion of from 1 to 400 parts by weight per 100 parts of glyphosate or glyphosate equivalent. By -~ 25 using the term glyphosate equivalent, the calculation :of the parts i~ thus reduced to as if all of the glypho~ate derivatives were in the form of N-phosphonomeehylglycine.
, . . -:

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'\'` :' ~

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2~1~7~7 , 10 More precisely, when herbicidal active substances other than glyphosate are used and mixed with glyphosate, the following proportions are generally used for the weight ratio wr:
S glyphosate or glyphosate equivalent (wr is equal to other herbic~de glyphosate + acifluorfen: 4 s wr s 9 glyphosate + diuron or oxadiazon: 2 s wr s 4 glyphosate + aclonifen: 1 s wr s 10 glyphosate + bifenox: 1 s wr s 1 15 glyphosate + diflufenican: 2 s wr s 20 glyphosate + asulam: 1 s wr s 1 glyphosate + phenoxy: 2 s wr s 4 glyphosate + hydroxybenzonitrile: 1 s wr s 10 glyphosate + triazine: 1 s wr s 1 glyphosate + imidazolinone: 1 s wr s 4 glyphosate + sulphonylurea: 100 s wr s 100 : 25 . 6 In accordance with what hs~ ~lready been stated, the concentrated suspen~ions according to the invention :

. , , . . ~ ., , ., . ~ . - , 11 20157~7 contain an organic solvent (or sometime~ termed carrier). This solvent is a natural or synthetic organic or inorganic substance with whlch the active substance or substances are combined to facilitate S their application to the plant or to the 80il . Thi 8 solvent is therefore generally inert and acceptable in agriculture, in particular on the treated plant. In the present invention, the solvent can therefore be an organic liquid such as, for example, esters, in particular methyl glycol acetate; ketones, in particular cyclohexanone and isophorone, petroleum fractions; aromatic hydrocarbons, in particular the xylenes, or paraffin hydrocarbons; aliphatic or aromatic chlorinated hydrocarbons, in particular the chlorobenzenes, glycols, liquid oligoglycols or polyglycols, that is to say of low molecular weight, or vegetable oils, which may be esterified.
In accordance with what has already been stated, the concentrated composLtions according to the invention can contain one or more surfactants in addielon to the surfactant having an activator character defined furtber above. The surfactant used can be an emulsifying agent, dispersing agent or wetting agent of the ionic or nonionic type or a mixture of such surfactants. Examples which may be mentioned are ~aits of polyacrylic acid~, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensation products . - , . - .~

20i~7~

of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), the salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates), the phosphoric esters of alcohols or of polycondensation products of ethylene oxide with phenols, esters of fatty acids and polyols, and the derivatives of the above compounds containing .
sulphate, sulphonate and phosphate functions.
10The following examples, given as non-limiting examples, illustrate the invention, in particular the concentrated suspensions according to the invention and their use, and show how this invention can be implemented.

N-Phosphonomethylglycine (acid) 200 g/l Ammonium sulphate (ad~uvant) 200 g/l Surfactant (activator) defined below:200 g/l :~: Dispersing agents/wetting agents:
polycondensation products of ethylene : oxide with tris(phenylethyl)phenol pho~phate 20 g/l ~ ;
; ammonium dodecylbenzenesulphonate10 g/l -Organopolysiloxane oil (anti-foam) 2 g/l - ~-25 Bentonite (thixotropic agent) 2 g/l Poly~inyl alcohol (protective colloid) 8 g/l -~
Solvents~
propylene glycol 300 g/l . ';. ,', ~' 201~7~97 water 250 g/l The surfactant used in this example was a product of formula C~Hl,-N-(CH2-CH2-O)lo~C~CH3 ( CH2-CH2-O ) lo-CO-CH3 This mixture is ground in a ball mill 80 as to obtain a concentrated microsuspension in which 73 % of the N-phosphonomethylglycine is in 6u6pension in the form of particles having a size of between 5 and 20 microns. One fraction of this concentrated suspension is treated by centrifuging; after analysis of the liquid phase, 27 g/l of N-phosphonomethylglycine are found in this liquid phase. ;~
This concentrated composition retains its physicochemical properties a) after standing for one month at 50-C, and also b) after standing for one month divided into eight ~ periods of equal duration, four at 35-C and four at ; ~ 20 -10-C, alternately.
~` A concentrated composition such as prepared in the present example iB then diluted in water using one litre of concentrat- per 100 litres of water. A dilute and homogeneous spraying mixture is thuis obtained, virtually inistantaneously, which is sprayed at a rate of 250 l/ha on the following weedss Portulaca oleraceae, Centauria cyanus, Sinapis arvensis, Panicum trichoides and Abutilon theophrasti. Using a dosage of active substance of 500 g/ha, the above weeds are ~; , .
... ~ . . . ~

.~..... . ~

201~7~7 destroyed at respec~ive degrees of destruction of 95 %, 100 ~, 9~ ~, 100 % and 100 %.

N-Phosphonomethylglycine (acid) 200 g/l 5 Ammonium sulphate (ad~uvant) 200 g/l Surfactant (activator) used in Example 1: 200 g/l Dispersing agents/wetting agentss polycondensation products of ethylene oxide with tris(phenylethyl)phenol phosphate 20 g/l ammonium dodecylbenzene~ulphonate10 g/l Organopolysiloxane oil (anti-foam) 2 q/l Polyvinyl alcohol (protective colloid)8 g/l Bentonite (thixotropic agent) 2 g/l Solvent:
:~ polyethylene glycol (molecular weight = 400) 552 g/l This mixture i8 ground as in Example 1 and ha~ the same stabillty characteristics as the concentrated .:
~composition of Example 1.

N-Phosphonom~thylglycine (acid) 125 g/l ~, ; ,Oxadiazon 125 g/l Surfactant used in Example ls 125 g/l : 25 (NH~)2SO~ 125 g/l ~.. ~.. ..
:~ Di3persing agents/wetting agents~
polycondensation products of ethylene - oxide with tris(phenylethyl)phenol . .. ~..~.
-201~7~7 phosphate 20 g/l ammonium dodecylbenzenesulphonate 10 g/l polycondensation products of ethylene oxide with dodecanol (20 EO) 50-g~l 5 Organopolysiloxane oil 2 g/l Bentonite (thixotropic agent) 2 g/l Poly~inyl alcohol (protective colloid) 8 g/l Solvent:
polyethylene glycol (NW = 400) 410 g/l This mixture is ground as in Example 1 and has the same stability characteristics as the concentrated composition of Example 1.

N-Phosphonomethylglycine (acid) 12S g/l 15 Aclonifen 250 g~l Surfactant used in Example 1: 125 g/l (NH~j2so~ 125 g/l Dispersing agents/wetting agents:
polycondensation products of ethylene oxide with tris(phenylethyl)phenol ~ phosphate 30 g/l `
`~ ~ Propylene glycol 270 g/l .H2O 175 g/l This mixture i8 ground a~ in Example 1 and has the ~: 25 same stability characteristics a6 the concentrated ~: composition of Example 1.
EXAMPLE S
N-Phosphonomethylglycine (acid)200 g/l - . . . .

, 201~7~7 Chlorsulphuron 2 g/lSurfactant used in Example 1: 200 g/l(NHffff)2SOf~ 200 g/1Dispersing agents/wetting agents:
polycondensation products of ethylene oxide with tris(phenylethyl)phenol phosphate 14 g/l A 4:1 ethylene oxide/dodecanol condensation product 14 g/l A 6:1 ethylene oxide/decanol condensation product 40 g/l Attapulgite (thixotropic agent) 8 g/lSolvents in an amount sufficient for l l:
aromatic hydrocarbons, petroleum distilla-15 tion fraction containing C9 to Cl~ compounds. :
This mixture is ground as in Examplef l and has the ~ same stability~characteristics as the concentrated . :
: composition of Example 1. ~ ~:
-~ This concentrated composition i8 diluted so as to ~: .
~ . ~
~:~ 20 spread 750 g/ha of active substance and 300 l/ha of dilut- spraying mixtur- over land infestffsfd with weeds. .
The following degrees of destruction are obfsferved on .
fthe treated weedss 99.7 % (ffftfffentauria cyanus), 97.5 %
~chrysanthemum), 80 % (Galium aparine), 85 % (Sinapis ~:: 25 alba), 92.5 % (Sinapis arvensis), 92.5 % (Stellaria media), 93.5 % (Agrotis tenuis), 96.5 % (Alopecu NS ..
myosuroides)~ 98.5 % (Avena fatua), 97.6 % (Lolium --~
multiflorum), 97.6 % (Phalaris canariensis) and 82.5 %

~;~

201~7~7 ( Poa annua ) .

; ~ ~

.

.

. :; ., , ::

. ~

,.,: ~ . . ~
.. .. -- - : - -

Claims

1. The concentrated composition containing N-phosphonomethylglycine and/or one of its derivatives, which is a liquid composition consisting of a suspension in an organic, or possibly aqueous-organic, solvent medium, containing:
a) N-phosphonomethylglycine and/or one of its derivatives having an inherent solubility in water of more than 5 g/l, preferably more than 9 g/l, this N-phosphonomethylglycine and/or its derivative being present in the composition in a proportion of at least 100 g/l glyphosate equivalent, at least part of this N-phosphonomethylglycine or its derivatives being in a form insoluble in the medium under consideration, b) a surfactant having an activator character and having the formula in which R is a straight-chain or branched alkyl or alkenyl hydrocarbon chain having from 8 to 22 carbon atoms, A represents an alkylene group, preferably ethylene or propylene, n and n' are integers such that n + n' is between

2 and 40, R1 is a hydrogen atom or an acyl radical such as formyl, acetyl, propionyl (that is to say CH3-CH2-CO) or benzoyl.
2. The composition according to claim 1, wherein A is an ethylene or propylene group and/or n + n' is between 16 and 30 and preferably between 20 and 25.

3. The composition according to one of claims 1 or 2, wherein the N-phosphonomethylglycine derivative is chosen from the group consisting of the sodium, potassium or inorganic or organic ammonium salts, in particular the isopropylammonium salts, and the sulphonium salts, taken individually or as a mixture.

4. The composition according to one of claims 1 to 3, wherein N-phosphonomethylglycine or its derivative is in an amount in excess of the solubility limit in the medium under consideration, preferably of between 120 and 250 g/l.

5. The composition according to claim 4, wherein N-phosphonomethylglycine or its derivative is in an amount of between 90 and 220 g/l.

6. The composition according to one of claims 4 or 5, wherein the proportion of undissolved N-phosphono-methylglycine derivative is greater than 30 % and preferably greater than 75 %.

7. The composition according to one of claims 1 to 6, wherein N-phosphonomethylglycine, or its derivative, which is insoluble, is in the form of solid particles having a diameter of less than 30 microns and preferably of between 1 and 30 microns.

8. The composition according to one of claims 1 to 7, which contains an adjuvant such as an ammonium salt, this salt being able to be, in particular, a nitrate or a phosphate or a sulphamate or a thiocyanate or a sulphate.

9. The composition according to claim 8, which contains an adjuvant in a proportion of 50 to 500 g/l and preferably 100 to 350 g/l.

10. The composition according to one of claims 1 to 9, which is intended to be diluted with water 80 as to be spread at a rate of 100 to 600 l/ha, the active substance itself being applied at a rate of 0.125 to 1.5 kg/ha.