AU635875B2 - A silicone glycol-silicone alkane terpolymer adjuvant for herbicidal compositions - Google Patents

Description

P/00/011 28/11 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990 63 5 8705 ft...

ft...

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: A SILICONE GLYCOL-SILICONE ALKANE TERPOLYMER ADJUVANT FOR HERBICIDAL COMPOSITIONS The following statement is a full description of this invention, including the best method of performing It known to ft.

ft ft.

.ft*ftft~ 1 A SILICONE GLYCOL-SILICONE ALKANE TERPOLYMER ADJUVANT FOR HERBICIDAL COMPOSITIONS This invention relates to silicon glycol-silicone alkane terpolymer adjuvants and is divided from application No. 56972/90.

It has been found that the efficacy of a foliar-applied herbicide can be synergistically increased by the inclusion of a silicone glycol-silicone alkane terpolymer in a herbicidally effective composition, "herbicidally effective" meaning that the composition provides the desired kill control of the particular weed in question.

Moreover, this combination can provide increased rainfastness in the very same formulation without the need for an additional sticking agent.

The present invention therefore provides composition comprising a silicone glycol-silicone alkane terpolymer adjuvant having the average formula selected from the group consisting of Me Me Me3SiO(SiMe20)x(SiO)y(SiO)zSiMe3 and A G Me Me *I I Me 3 SiO(SiO)y(SiO)zSiMe3 A G 15 wherein Me denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms, G is a glycol moiety having the formula -R'(OCH 2

CH

2 )mOR, in which R' is a divalent alkylene group having 2 to 6 carbon atoms, R is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 carbon atoms and m is 12 to 32, x is 0.01 to 3, y is 0.1 to 1.25 and z is 20 0.75 to 1.9, with the proviso that when the weight fraction of -OCH 2

CH

2 groups of said terpolymer (II) is less than 0.7 said alkyl radical A contains from 6 to 12 carbon atoms and when the weight fraction of -OCH 2

CH

2 groups of terpolymer (II) is more than 0.8 said alkyl radical A contains from 8 to 24 carbon atoms.

Preferably the terpolymer has the average structure Me Me MesSiO(SiO)(SiO)zSiMes A CHCH2CH2(OCH2CH2)OC(O)Mp in which Me denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms, m is 12 to 32, y is 0.1 to 1.25 and z is 0.75 to 1.9, with the proviso that when the weight fraction of -OCH 2

CH

2 groups is less than 0.7 said alkyl radical A contains from 6 to 12 carbon atoms and when the weight fraction of -OCH 2

CH

2 groups is more than 0.8 said alkyl radical Acontains from 8 to 24 carbon atoms. Preferably the silicone glycol-silicone alkane terpolymer adjuvant has the average formula Me Me I I Me 3 SiO(SiO)0.6 4 (SiO)1.36 SiMe 3 LC2CH2H2(OCH(O 2CH2)24OC(0)CH3

(CH

2 11

CH

3 wherein Me denotes a methyl radical.

The compositions of the present invention are useful in the preparation of herbicidal compositions for inhibiting the growth of narrowleaf annual and perennial weeds, particularly Barnyardgrass, Rhizone Johnsongrass and Rhizome Quackgrass.

The herbicidal composition isa homogeneous mixture comprising a foliarapplied herbicide and (II) the silicone glycol-silicone alkane terpolymer adjuvant.

15 the foliar-applied herbicide used with compositions of the present invention is selected from those herbicides well known in the art to be effective when applied after the emergen,:e of a plant.

Herbicides which are useful in this invention include triazines, ureas, S carbamates, acetamides, uracils, acetic acid or phenol derivatives, triazoles, benzoic acids, nitriles, biphenyl ethers and the like such as: Heterocyclic nitrogen/sulfur derivatives including 2-chloro-4-ethylamino- 6-isopropylamino-s-triazine, 2-chloro-4, 6-bis(isopropylamino)-s-triazine; 2chloro-4,6-bis(ethylamine)-s-triazine; 3-isopropyl- H-2,1,3-benzothiadiazin-4- (3H)-one 2,2-dioxide, 3-amino-1,2,4-triazole; 5-bromo-3-isopropyl-6methyluracil; 2-(4-isopropyl-4-methyl-5-oxo-2-imdazolin-2-yl-)3-quinolinecarboxylic acid; isopropylamine salt of 2-(4-methyl-5-oxo-2-imidazolin-2-yl)- Snicotinic acid, methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m- 3 toluate; and methyl 2-(4-isopropyl-4-m ethyl-6-oxo-2-i midazoli n-2-yi) -p-tol uate; and further including acidslesterslalcohols such as (2,2-dichloropropionic acid; 2methyl-4-chloropheno xyacetic acid, 2,4-dichloro-phenoxyacetic ai, methyl-2-[4- (2,4-dichloro-phenoxy)phenoxy]propionate, 3-amino-2,5-dichlorobenzoic acid, 2methoxy-3,6-dichlorobenzoic acid, 2,3,6-trichlorophenyl-acetic acid, N-inaptpthylphthalamic acid, sodium 5-[2-chloro-4-(trifluoromethyl)phenoxyl-2-nitrobenzoate, 4,6-dinit~o-o-sec-butylphenol, butyl 2-f-I(trifluromethyl)-2-pyridinyl)oxy]-phenoxy]propanoate; and cyclohexanediones such as sethoxydium and garlon and ethers such as 2,4-dichlorophenyl-4-nitrophenyl ether, 2-chloro-trifuluorop-tolyl- 1 0 3-ethoxy-4-nitrodiphenyl ether, 5-(2-ch loro-4-trif lu orom ethylph enoxy)- N- methylsulfonyl 2-nitrobenzamide, 1 '-(carboethoxy) ethyl 5-[2-chloro-4-(trifluorom ethyl) ph enoxyl-2-nitrobenzoate and other diphenylethers and other miscellaneous herbicides such as 2,6-dichlorobenzonitrile, monosodium acid methanearsonate, disodium methanearsonate, 2-2(-chlorophenyl)methyl-4-dimethyl-3-isoxazolidinone.

1 5 One preferred foliar-applied herbicide is N-phosphonomethylglycine (glyphosate) or an agriculturally acceptable salt thereof. The isopropylamine salt of this compound i marketed under the trade name ROUNDUP (Monsanto Agricultural Products Co., St. Louis, MO) and is particularly preferred.

Other preferred herbicides may be selected from sulfonylurea herbicides, such as those marketed by Du Pont (Wilmington, DE) under the trade names ACCENT, HARMONY, CLASSIC, PINNACLE, EXPRESS, GLEAN, ALLY and FINESS. A particularly preferred herbicide of this class is 3-[4,6-bis(difluoromethoxy)-pyrimidin-2-y]-1- (2-methoxy-carbonyl-phenylsulfonyl)-urea (common name: Primisulfuron).

This material is marketed under the trade name BEACON (Ciba-Geigy Agricultural Division, Greensboro, NC).

The silicone glycol-silicone alkane terpolymer (11) of the present invention has the average structure selectcc_ from the group consisting of Me Me *I I Me Me I I Me 3 SiO(SO)y(SiO)ZSiMe3 wherein Me hereinafter denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms and G is a glycol moiety having the formula

-R'(OCH

2

CH

2 )MOR, in which R' is a divalent alkylene group having 2 to 6 carbon atoms, R is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and w acyl group having 2 to 4 carbon atoms. In the above formulas, m is 12 to 32, x is 0.01 to 3, y is 0.1 to 1.25 and z is 0.75 to 1.9.

In addition to the above stated restrictions, it has been found that component (II) of the present invention must further be limited such that the number of carbon atoms of alkyl radical A is 6 to 12 when the calculated hydrophilic-lipophilic balance 1 0 (HLB) of the terpolymer is less than 14 and the number of carbon atoms of A is 8 to 24 when the calculated HLB is greater than 16. The calculated HLB value is defined herein as the weight percent of ethylene oxide units -OCH 2 C-H- units) in the terpolymer divided by 5. Thus, in order to be within the scope of the present invention, the number of carbon atoms of alkyl radical A is 6 to 12 when the weight fraction of ethylene oxide units is less than 0.7 and the number of carbon atoms of A is 8 to 24 when the weight fraction of ethylene oxide units is greater than 0.8.

A particularly preferred component (II) of the present invention has the average formula Me Me I I MeSiSiOiO)o.

64 (SiO) .a 6 SiMea

CH

2 CH 2

(OCHH

2 24 0C(O)CH 3 (CH2) 1

CH

3 20 The silicone glycol-silicone alkane terpolymers described above may be prepared by methods well known in the art. Briefly, for example, the corresponding allylterminated glycol and alpha-alkene are coupled to an SiH-functional siloxane having the average structure Me Me3SiO(SiMe 2 O)SiO)y.,SiMe 3 or

H

Me Me 3 SiO(SiO)y.SiMe 3

H

Coupling is accomplished in the presence of a platinum catalyst at temperatures in the range of about 20°C. to about 150°C., the reaction preferably being carried out at about 105°C. using an effective amount of a solvent such as toluene or isopropanol. The skilled artisan will recognize that, in such hydrosilylation reactions, a fraction of the allylterminated glycol and the alpha-alkene is not converted and will remain as an impurity in the final product terpolymer. The herbicidal compositions may contain such impurities.

In addition to the aforementioned components, the compositions of the present invention may also be used with other herbicide adjuvants commonly employed in the art.

The phytotoxicant compositions, preferably contain (in addition to the herbicide active and silicone) an inert adjuvant or conditioning agent and one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface active agent into the compositions of this invention greatly enhances their efficacy. By the term surface active agent, it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein, Anionic, cationic and nonionic agents cay be employed with equal facility.

Preferred wetting agents are alkyl benezene and alkyl naphthalene sulfonates, 20 sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, :"polyoxyethylene derivatives of alkyl phenols (particularly isooctylphenol and nonylphenol), polyoxyethylene derivatives of fatty acid esters of hexito anyhydrides (sorbitan) and silicone glycols. Preferred dispersants are methycellulose, polyvinylalcohol, sodium lignin sulfonates, polymeric alky naphthalene sulphonates, 6 sodium naphthalene sulfonate, polymethylene bisnaphpthalene-sulfonates and sodium Nmethyl-N-long chain acid laurates.

Suitable surfactants (adjuvants) are disclosed in U.S. Patent 3,799,758 and 4,405,531. Examples of other adjuvants include crop oil concentrate, ORTHO X-77 spreader, drift control agents, such as LO-DRIFT, defoaming agents, such as D-FOAMER, compatibility agents, such as E-Z MIX and other adjuvants well known in the herbicide art.

In order to prepare the compositions of the present invention, from about 0.1 to about 10 parts by weight of the silicone glycol-silicone alkane terpolymer (II) is thoroughly mixed with each part by weight of herbicide Preferably, from 0.5 to 4 parts by weight of (II) are employed for each part of the pesticide For a given herbicide, the skilled artisan will readily arrive at a herbicidal composition having the optimum ratio of the ingredients by routine experimentation.

The above herbicidal composition may then be dispersed in water and sprayed onto plants according to the method of the present invention, described infra.

Alternatively, the silicone glycol-silicone alkane terpolymer adjuvant (II) may be added directly to a water solution or dispersion of herbicide Th-t compounds of the present invention also may be therefore used, in a method for i ihibiting the growth of narrow-leaf weeds, particularly the species S 20 Echinochloa crus-galli, hereinafter referred to by its common name of "Barnyardgrass", Agropyron r mDens, hereinafter referred to by its common name of "Quackgrass" and Sorghum halepense, hereinafter referred to by Its common name "Johnsongrass". This method comprises contacting at least part of the weed with the above described herbicidal composition. This composition, usually in water dispersion 25 form, is applied to the foliage of the weed by any of the methods common!y practiced in the art, preferably by spraying. The composition may be either apackage mix or a tank o. mix. The amount of the dispersion and the herbicide contained therein, to be applied to the weed may be varied to a great extent, the optima being determined by such factors as .o soil conditions, weather conditions and the type of crops or other plants growing alongside the weed. Generally, however, the effective application rate is about 0.5 to pounds per acre of herbicide formulation. The skilled artisan is directed to United States Patent Numbers 3,799, 758 and 4,405,531 for further suggestions as to appropriate application rates for N-phosphonomethylglycine based herbicides.

When the compositions are used according to the above described method, there is observed a statistically significant improvement in the efficacy and/or rainfastness of the herbicidal compositions relative to compositions employing prior art silicone glycol adjuvants or only the unmodified herbicide. There is provided a distinct advantage by the instant compositions in that they permit the use of lower herbicide levels to attain a similar degree of injury to a weed, this advantage often being maximized when there is a reasonable likelihood of precipitation after applying the herbicide. Such a reduction in herbicide levels generally results in reduced injury to adjacent cash crops and is considered highly desirable.

The following examples are presented to further illustrate the compositions of this invention, but are not to be construed as limiting the invention, which is 1 0 delineated in the appended claims. All parts and percentages in the examples are on a weight basis unless indicated to the contrary.

Examples 1-10 A silicone glycol-silicone alkane terpolymer adjuvant of the present invention was prepared as follows: A three neck 1 liter flask, equipped with nitrogen 1 5 inlet/thermometer, claisen head with addition funnel/condenser and mechanical air driven stirrer was charged with 50.37 g (0.17 mole) of an SiH-functional siloxane having the average formula Me Me3SiO(SiO) 2 .ooSiMe3 S2. H 24.2 g (0.14 mole) of alpha-dodecene, 398.2 g (0.32 mole) of an allyl-functional glycol having the formula CH 2

=CHCH

2

(OCH

2

CH

2 24 0C(O)CH 3 and 0.2 g of sodium acetate.

Dissolved air was removed from the mixture under vacuum, the flask was purged with nitrogen gas and the contents heated to 140°C. The stirred mixture was then catalyzed with 10 ppm of chloroplatinic acid (as a 1% solution in isopropyl alcohol). The .exothermic reaction brought the temperature of the mixture to 1550C. The mixture was held at a temperature of 15000. for 2 hours, after which all of the initial SiH functionality had reacted, as determined by IR analysis The mixture was cooled to 500C.

and 0.5 wt% Nucap 200, 0.5 wt% Celite 545 (filtration aids) and 150 g of isopropanol were added. This mixture was stirred for one hour, pressure filtered and the isopropanol solvent vacuum stripped off to provide 423.5 g (90% yield) of a final product having the 3 0 calculated average formula 8 Me Me Me3SiO(SiO) 0 64 (SIO)1.

36 SiMe 3 L CHCH2CH(OCHCH)24OC(O)CHa

(CH

2 1

CH

3 wherein Me hereinafter denotes a methyl radical. This product is designated as FLUID A in Table 1.

A similar procedure was employed to prepare other silicone glycol-silicone alkane terpolymers (FLUIDS B-G) and comparative silicone glycols (FLUIDS also shown in Table 1. These fluids had the average formula Me Me Me3SiO(SiMe 2 0)x(SiO)y(SiO)zSiMe3 A G wherein A is a normal alkyl radical having n carbon atoms, G is an acetoxy terminated glycol moiety having the formula -CH 2 CHi

C

H2(OCH 2

CH

2 )mOC(O)CH3 the values of m, n, x, S 1 0 y and z for the various terpolymers being given In Table 1, below.

TABLE 1 FLUID a Y 7 A 12 24 0 0.64 1.36 B 12 24 8.5 1.00 4.50 C 12 24 2.00 1.50 2.50 D 12 4 8.50 0.50 5.00 E 12 4 2.00 0.50 3.50 12 4 0 0.25 1.75 G 12 12 19.00 2.00 9.00 H 12 12 0 0.84 1.36 1 8 12 0 0.73 1.27 J 7 0 0 1.00 K* 4 0 0 1.00 L-77** glycol terminated with -OH instead of -OC=O

CH

3 SILWET L-77 (Union Carbide Corp.. D-nbury, CT) 1 5 Comparative silicone glycol adjuvants used in the following evaluations of herbicidal activity included: FLUID J, described in Table 1.

FLUID K, also described in Table 1.

SILWET L-77 (Union Carbide Corp., Danbury, CT) is described as a silicone glycol surfactant for use in agriculture.

Test Protocol The following weed species were used as indicator weeds: Common Name Scientific Name Rhizome Quakgrass AQropyron repens Rhizome Johnsongrass Sorghum halepense Barnyardgrass Echinochloa crus-alli Velvetleaf (a broadleaf) Abutilon theophrasti The narrowleaf and broadleaf test weeds were seeded separately into plastic pots 4 inches in diameter and 3 inches deep with drainage holes on the bottom. The pots 1 0 contained Dupo silt loam soil obtained from the St. Charles Research Farm of Monsanto Company located in St, Charles, Missouri. Prior to use, the soil was steam sterilized at a temperature of 180 0 F. The soil used was mixed with a slow release 14-14-14 fertilizer.

Barnyard grass and velvetleaf were started from seeds while rhizome 1 5 johnsongrass and rhizome quackgrass plants were grown from rhizome pieces. In all cases, sufficient seeds or stock propagules were planted to produce several seedlings in each pot. Approximately 7 to 10 days after seeding, the velvetleaf seedlings we.a thinned out leaving 2 to 3 healthy seedlings per pot.

After the pots were seeded, the pots were moved into the greenhouse or a growth chamber and placed on trays with each tray holding 40 to 60 pots. The trays wire lined with absorbent mats for subirrigation. The greenhouse temperature was maintained at 86 0 F. during the day and 70 0 F. during the night while the growth chamber was maintained at 15 0 C. day temperature and 9°C. night temperature. Photoperiod in the greenhouse was maintained at 14 to 16 hours daylength using supplemental lighting and 25 10 hours in the growth chamber. The seeded pots were watered via subirrigation as required.

Depending on the weed species used in a given test, the chemical treatments were applied within 14 to 60 days after planting. At that time, the narrowleaf weeds were approximately 4 to 16 inches tall while the broadleaf weeds were 1 to 4 inches tall.

3 0 Chemical treatments were applied post-emergence with the foliage of the weeds as the locus of application using a tract sprayer equipped with a single 8001E spray nozzle. The sprayer was previously calibrated to deliver a spray volume equivalent to about 20 gallons per acre of spray solution at a spraying pressure of about 30 psi.

The chemical compositions illustrative of compositions of this iventicn used in the tests were formulated as tank mixtures the same day of application. The formulations comprised Roundup® (an agriculturally acceptable salt of N-phosphonomethylglycine, namely the isopropylamine salt and inert adjuvant as a surfactant) a silicone copolymer and water.

Rates of application based on N-phosphonomethyglycine ranged from about 1/8 to about 3 pounds glyphosate acid equivalent per acre. The ingredient ratios employed in the formulations were glyphosate to silicone of about 1:0.1 to 1:10. Rainfall treatment was applied one hour after spraying of the compositions using a rain tower calibrated to deliver approximately 1/4 inch of simulated rainfall within a period of about minutes.

1 0 After application of rainfall, the treated plants were placeJ on carts and moved into the greenhouse. After the plants had sufficiently dried out, the pots were returned to the greenhouse (growth chamber) irays and arranged in a randomized complete block experimental design. Each treatment contained 3 replications. Control plants and appropriate standaid treatments were provided in each test. A duplicate set of plants 1 5 which received the same treatment and which were treated in a similar manner as the rainfall treated plants were also provided for comparison under no rain condition.

Observations on the effects of the treatments were taken within 7 to 10 days for early burndown effects and again within 21 to 28 days after treatment for longer term effects. A rating scale of 0% to 100% was used in estimating the degree of weed control 2 0 with 0% having no observable effect and 100% as complete kill of the weed. The degree of burn, chlorosis,, necrosis, stature reduction and other observable effects of the treatments on plant species present in the test were taken into consideration in making the ratings. Ten examples follow which illustrate compositions and method of use of this invention.

Example 1 ***Response to barnyardgrass (BYGR) and velvetleaf (VELE) to tank mixtures containing Roundup® and silicones with or without 1/4 inch of simulated rainfall final rating.

*o o° Aveige, Inhibition (25 DAT)* Aver o.(2

DAT.

Treatment Rain (Inches) BYGR

VELE

Roundup® 0.25% Roundup® 1% Roundup® Roundup® 0.25% Roundup® 1% Roundup® 0.25% Roundup® 1% Roundup® 0.25% Roundup® 1% Roundup® 0.25% Roundup® 1% Roundup® 0.25% Roundup® 1% Untreated Control Notes: Roundup® was applied FLUID A 0 1/4 FI.UID A 0 1/4 0 1/4 L-77 0 1/4 L-77 0 1/4 FLUID J 0 1/4 FLUID J 0 1/4 FLUID H 0 1/4 FLUID H 0 1/4 FLUID I 0 1/4 FLUID I 0 '1/4 FLUID B 0 1/4 FLUID B 0 1/4 100 30 100 87 100 28 63 10 77 5 50 12 2 7 100 23 100 33 97 20 100 10 100 35 100 15 0 100 a 37 def 100 a 60 bcd 100 a 73 abc 100 a 100 a 100 a 100 a 100 a 100 a 100 a 100 a 100 a 20 fgh 99 a 17 fgh 100 a 3 gh 10 a 33 d-g 99 a 53 cde 100 a 28 e-h 0 h 4e 0 r r at 3/8 Ib ae/A (ae acid equivalent of glyphosate).

r ~.r Additive concentrations shown are based on percent of total spray volume.

All treatments were applied at a spray gallonage equivalent to 20 gallons/A of spray solution.

L77 Silwet L-77, Union Carbide silicone Surfactant.

Rainfall treatment equivalent to 1/4 inch of rain was applied approximately one hour after herbicidal treatment fo, a period of 15 minutes.

Values shown are averages of three replications per treatment.

Means followed by different letters within weed species are significantly different from one another at the 0.05 probability level using Duncan's Multiple Range Test.

*DAT Days after treatment Example 2 Effects of silicones as Roundup®D additives on rhizome quac1kgrass.

Average Inhibitaion (28 dat)

QUAOKGRASS

Treatment Rin 0. 25" ain Roundup® 0. 25% FLUID A 9 6 ab 6 0 fgh Roundup® 1 FLUID A 100 a 82 a-e Roundup®D 9 5ab 40 1 Roundup® 0.25 L-77 81 a-e 5C hi Roundup® 1 L-77 85 a-e 70 d-g Roundup® 0.25% FLUID J 9 ab 55 ghi Roundup® 1 FLUID J 83 a-e 75 c-f *.:Roundup®D 0.25% FLUIDO0 91 abc 5 8 f-i Roundup® 1 FLUIDOC 100 a 6 6 e-h *Roundup®D 0.25% FLUID G 98 ab 79 b-e Roundup®D 1 FLUID G 98 ab 7 1d-g **Roundup@®+ 0.25% FLUID B 100 a 57 f -i Roundup®g 1 FLUID B 99 ab 6 0 fgli Values shown are averages of three replications per treatment.

Example 3 Response of barnyardgrass to tank mixtures containing Roundup® and silicone in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment.

Data show average percent growth inhibition 25 days after treatment. Roundup® was applied at 3/8 Ib ae/A; silicones at 0.25% The spray gallonage was equivalent to gallons per acre of spray solution.

Trea, .,ent Roundup® FLUID A Roundup® Roundup® FLUID D Roundup® FLUID E Roundup® FLUID F Roundup® FLUID C Roundup® FLUID B Average 0 Rain 100 a 95 a 20 ef 40 d 40 d 100 a 100 a Inhibition (25 DAT) 0.25" Rain 30 de 12 fgh 0 h 0 oh 2 gh 3 gh 5 fgh

P

P..

P

P.

P. 4 Example 4 Response of barnyardgrass to tank mixtures containing Roundup® and silicone in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 24 days after treatment.

Average Inhibition (24 DAT) Treatment Roundup® FLUID A Roundup® Roundup® 1% FLUID J Rain LiacGhe 0 1/4 0 1/4 0 1/4 3/8 lb ae/A 100 a 27 g-m 100 a 18 i-m 20 h-m 23 g-m 1/2 lb ae/A 100 a 63 b-f 100 a 23 g-m 33 f-l 50 c-h 0 Note: Silicone concentrations are expressed as of total spray volume based on a spray gallonage equivalent to 20 gallons/A.

Means followed by different letters are significantly different from one another at the probability level based on Duncan's Multiple Range Test.

Example Response of rhizome johnsongrass to tank mixtures containing Roundup@ and silicone in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 23 days after treatment.

Average Inhibition (23 DAT) Rain (inches) Treatment 3/8 lb ae/A 1/2 Ib ae/A Roundup@ 1% FLUID A Roundup@ Roundup® 1% L-77 Roundup@ 1% FLUID J 99 76 53 91 89 99 100 100 87 8 99 100 100 100 oeoe Note: Silicone concentrations are expressed as of gallonage equivalent to 20 gallons/A.

the total spray volume based on a spray *4h Means followed by different letters are significantly different from one another at the probability level based oni Duncan's Multiple Range Test.

ooeoo Response of rhizome johnsongrass to tank mixtures containing Roundup® and silicone in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment, Data show average percent growth inhibition 28 days after treatment. Roundup® was applied at 3/8 Ib ae/A. The spray gallonage was equivalent to 20 gallons per acre of spray solution.

Average Inhibition (28 DAT) Silicone Additive FLUID A FLUID J Silicone Conc.

0.25" Rain e 0.0625 0.125 0.25 1 0.0625 0.125 0.25 1 3 0.125 0.25 1 0.0625 0.125 0.25 1 FLUID K0.0625

S

SS

FLUID E Note: Silicone concentrations are expressed as of the total spray volume based on a spray gallonage equivalent to 20 gallons/A.

16 Example 7 Response of rhizome johnsongrass to tank mixtures containing Roundup® and silicone in the absence or presenc of 1/4 inch simulated rainfall applied one hour after treatment. Roundup® was applied at 1/2 Ib ae/A and silicones at 0.5% The spray gallonage was equivalent to 20 gallons per acre of spray solution.

Average Inhibition (22 DAT) Silicone Additive 0 Rain 0.25" Rain FLUID A 90 a-d 73 a-g NCNE 95 ab 27 ijk FLUID J 52 f-i 68 c-h FLUID E 13 kI 5 kl FLUID F 18 kI 7 kl FLUID B 92 a-d 60 e-h *e e Example 8 Effect of Roundup@ rate and silicone content on rhizome quackgrass without rain and 28 days after treatment. Roundup@ rates of 1/4 and 3/8 Ib ae/A were based on Nphosphonomethylglycine content.

too to to Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup@ Roundup® Roundup@ Roundup@ Roundup® Roundup@ Roundup@ Roundup@ Roundup@ 0.0625% 0.125% 0.25% 0.50% +1% FLUID A of 71 gh 83 a-f Average Inhibition (28 DAT) 1/4 Ib ae/A 3/8 lb ae/A 77 a-h 88 a-e 93 ab 91 abc 89 a-e 91 abc 88 a-e 89 a-e 90 a-d 91 abc 0.0625% 0.125% 0.25% 0.50% 1% 0.0625% 0.125% 0.25% 0.50% 1% 0.0625% 0.125% 0.25% 0.50% 1% FLUID B d-h a-e a-f abc ab h e-h b-g a-f b-g FLUID C FLUID J It 18 Example 9 Response of rhizome quackgrass to tank mixtures containing Roundup® and silicone in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 28 days after treatment.

Roundup® was applied at 1/2 Ib ae/A.

Treatment Roundup® Rouindup® Roundup® Roundup® 0.10% FLUID A 0.25% FLUID A 1.00% FLUID A Average 0 Rain 100 a 98 ab 99 ab Inhibition (28 DAT) 0L25" Rain 95 abc 87 cd S4 abc 70 e 99 ab S.

S

*5 o *5 Roundup® Roundup® Roundup® 0.10% L-77 0.25% L-77 1.00% L-77 100 98 100 Roundup® 0.10% FLUID I Roundup® 0.25% FLUID I Roundup® 1.00% FLUID I Note: Silicone concentrations are expressed as of gallonage equivalent to 20 gallons/A.

the total spray volume based on a spray Means followed by different letters are significantly different from one another at the probability level based on Duncan's Multiple Range Test.

S S 55555 Example Response of rhizome quackgrass to tank mixtures containing Roundup@ and silicone without rainfall treatment. Data show average percent growth inhibition 28 days after treatment.

Average Inhibition (28 DAT)

**OD

'*I

*I *r o o* *o Treatment Roundup@ Roundup® Roundup@ Roundup® Roundup® Roundup@ Roundup® Roundup@ Roundup@ Roundup® Roundup@ Roundup® Roundup® Roundupci Roundup@ Roundup® Roundup@ Roundup@ Roundup® Roundup® Roundup® 1/4 1k1. ilsZ 0.0625% 0.125% 0.25% 0.5% 1% FLUID A ,l If iI to 59 hij 73 d-j 0.0625% 0.125% 0.25% 0.5% 1% 0.0625% 0.125% 0.25% 0.5% 1% FLUID B It FLUID C FLUID J FLUID J i8 1 b .a/A e-k abc a-d a-d a-d c-j b-i a-f a-h a-e d-j d-j h-k e-k d-j 0.0625% 0.125% 0.25% 0.5% 1% e-k g-k k jk e-k Roundup® 0.125% Roundup surfactant Roundup® 0.5% surfactant 64 f-k 73 d-j 75 c-j 80 a-f S S 555S5 Note: Additive concentrations are expressed as of the total spray volume based on a spray gallonage equivalent to 20 gallons/A.

Means followed by different letters are significantly different from one another at the probability Ivel based on Duncan's Multiple Range Test.

Examples 11-42 The adjuvant terpolymers shown in Table 2 andhaving the average structure Me Me Me3SiO(SMe20)x(SiO)y(zSO)zSiMe 3 I I A CH 2

CH

2

CH

2

-(OCH

2

CH

2 )mOC(O)Me wherein A is a normal alkyl radical having 6 to 24 carbon atoms, were prepared according to the above described methods. These terpolymer adjuvants were mixed at a level with BEACON herbicide (Ciba-Geigy Agricultural Division) and applied to plants as described infra.

Test ProtocIo Individually potted Johnsongrass plants were grown from seeds under standard greenhouse conditions in BACCTO professional potting soil mix. Temperature was controlled at 75 0 F. Irradiation consisted of normal sunlight supplemented by highpressure sodium vapor lamps to provide an added 1,200 gE/m 2 -s at bench level (pIE microeinstein), wherein the day/night cycle was set at 18 hours and 6 hours, respectively.

Fourteen days after planting, when the plants'were at the three-leaf stage, they were sprayed with water dispersions of the herbicide compositions so as to broadcast herbicide BEACON) at a rate of 0.5 grams (active ingredient) per acre (0.5 g ai/A) along with the adjuvant above described terpolymer) at a rate of 1 pint/A. Spraying was accomplished by means of a link-belt sprayer fitted with a TEEJET 8001 E nozzle which delivered the equivalent of 25 gallons/acre of the herbicide dispersion. The BEACON application rate employed was previously found to induce approximately injury to the Jonsongrass after 14 days when a commercial adjuvant, ORTHO X-77 spreader (Chevron Chemical Co., San Francisco, CA), was mixed with the BEACON and broadcast at the above rates.

In addition, the rainfastness of the herbicide compositions was evaluated by spraying half the plants with water in order to simulate rainfall. This procedure consisted of spraying plants from above (9-10 inches above plant tops) using a TEEJET nozzle which delivered 0.4 gallons of water per minute. This nozzle was also mounted on a chain drive and reciprocally moved over four plants at a time, each such traverse taking about 9-10 seconds. The water spray was started 30 minutes after application of the 21 herbicide compositions and was continued for approximately 7 minutes, at which point the equivalent of one inch of "rain" had fallen on each plant.

Plant injury was visually determined using a double-blind experimental mode wherein four replicates were run for each herbicide composition. Phytotoxicity was ranked from zero, corresponding to no observable effect, to 100%, corresponding to total destruction of the plant. These results were averaged and the values reported using the above mentioned Duncan's multiple range test to distinguish statistical differences at the confidence level.

The above described herbicide dispersions were used to spray plants and the degree of injury, both with and without rain simulation, was observed 14 days after spraying with the herbicide dispersions. These results, along with the Duncan statistical annotations, are presented in Table 2. For additional comparison, results from spraying with BEACON ORTHO X-77, BEACON alone without adjuvant) and from controls which were not sprayed with herbicide, are also reported in Table 2.

ease• e *eo *oe eeoc *ooe TABLE 2 S S

S

S

S. S .5 4*

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Siiicone-GIyvcol-Silicone Alkane Terpolvmer Percent Injury to Plant No. of carbons in No Rain With Rain Example x _y AlkyI Radical A z m HLB 11 0 0.10 24 1.90 12 14.41 99a 45 c 12 0 0.10 12 1.90 12 14.57 96a 23d-i 13 0 1.14 8 0.86 24 13.49 96a 23d-i 14 0 0.40 12 1.60 12 13.52 95a 33cde 0 1.00 8 1.00 32 15.28 94a 13g-j 16 0 0.10 8 1.90 12 14.62 94a 17 0 1.25 12 0.75 32 13.43 94a 13g-j 18 0 0.53 12 1.47 32 16.50 91 a 13g-j 19 0 0.10 12 1.90 24 16.75 90a 13g-j 0 0.14 24 1.86 24 16.51 90a 21 0 0.64 12 1.35 24 15.24 90a 15 t-j 22 0 0.64 12 1.36 24 15.25 89a 23 0 0.14 24 1.86 24 16.51 88a 24 0 0.65 12 1.35 24 15.22 88a 10 hij 0 0.51 6 1.49 12 13.51 88 a 18e-i 26 0 1.20 6 0.80 24 13.43 88 a 10 hij 27 0 0.53 12 1.47 32 16.50 86a 28 0 0.70 24 1.30 32 15.24 85a 29 0 1.14 8 0.86 24 13.49 85a 23d-i 30 0 0.25 8 1.75 24 16.50 84 a 23 d-i 31 0 0.30 6 1.70 24 16.45 70b 32 0 1.05 6 0.95 32 15.28 70 b 10 hij 33 0 0.10 6 1.90 12 14.65 70b 38cd Comparative Examples 34 2 1.50 12 2.50 24 14.89 38 cd 15 fj 35 0 1.55 8 0.45 50 13.56 38 d 25 d-h 36 0 1.65 8 0.35 10015.25 35 cd 25 d-h 37 0 0.82 24 1.18 24 13.52 30 def 28d-g 36 0 1.40 24 0.60 10015.45 28 d-g 28 d-g 39 0 0.65 6 1.35 32 16.51 25 d-h 18e-i 0 1.40 12 0.60 97 16.50 25d-h 41 0 1.30 24 0.70 50 13.50 25d-h 23d-i 42 0 1.70 12 0.30 10013.92 18e-i BEACON ORTHO X-77 63 b 13g-j BEACON alone (No Adjuvant) 8 ij 0 j CONTROL (No Herbicide) 0j Oj

S

Claims (3)

1. A silicone glycol-silicone alkane terpolymer adjuvant having the average formula selected from the group consisting of Me Me I I Me3SIO(SiMe20)x(SiO)y(SiO)zSiMeS and A G Me Me Me3SiO(SiO)y(S!Co)SiMe3 A G wherein Me denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms, G is a glycol moiety having the formula -R'(OCH

2 CH 2 )m OR, in which R' is a divalent alkylene group having 2 to 6 carbon atoms, R is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 carbon atoms and m is 12 to 32, x is 0.01 to 3, y is 0.1 to 1.25 and z is 0.75 to 1.9, with the proviso that when the weight fraction of -OCH 2 CH 2 groups of said terpolymer (II) is less than 0.7 said alkyl radical A contains from 6 to 12 carbon atoms and when the weight fraction of -OCH 2 CH 2 groims of terpolymer (II) is more than 0.8 said alkyl radical A contains from 8 to 24 carbon atoms. The adjuvant according to claim 1 wherein said terpolymer has the average structure Me Me Me3S0O(SiO)y(SiO)zSiMe 3 I A LCH 2 CHCH2(OCHCH2)mOC(O)Me in wh.h Me denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms, m is 12 to 32, y is 0.1 to 1.25 and z is 0.75 to 1.9, with the proviso that when the weight fraction of -OCH 2 CH 2 groups is less than 0.7 said alkyl radical A contains from 6 to 12 carbon atoms and when the weight fraction o' -OCHCHI 2 groups is more than 0.8 said alkyl radical A contains from 8 to 24 carbon atoms. c' A" o UR 24

3. The adjuvant according to claim 1 or 2 wherein said silicone glycol-silicone alkane terpolymer adjuvant has the average formula Me Me Me 3 SiOC(8i0) 064 (SiO) 1 .36 SiMe 3 L LCH 2 CH 2 CH 2 (OCH 2 CH 2 2 4 00(O)0H 3 -(OH 2 1 1 OH 3 wherein Me denotes a methyl radical. DATED this 24th day ofNovember, 1992. DOW CORNING CORPORATION WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BUR WOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA 0 S 0* S *S S S S S S cK~ ABSTRACT A composition is disclosed comprising a silicone glycol.silicone alkane terpolymer adjuvant having the average formula selected from the group consisting of Me Me Me 3 SiO(SiMe 2 0)x(S)(SiO)SiO)zSiMe3 and A G Me Me Me3SiO(SiO)y(SiO)zSiMe3 IA A G wherein Me denotes a methyl radical, A is a linear or branched alkyl radical having 6 to 24 carbon atoms, G is a glycol moiety having the formula -R'(OCH 2 CHI)m OR, in which R' is a divalent alkylene group having 2 to 6 carbon atoms, R is selected from the group S: consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 carbon atoms and m is 12 to 32, x is 0.01 to 3, y is 0.1 to 1.25 and z is 0.75 to 1.9, with the proviso that when the weight fraction of -OCH 2 CHa- groups of said I terpolymer (II) is less than 0.7 said alkyl radical A contains from 6 to 12 carbon atoms and when the weight fraction of -OCHaCH 2 groups of terpolymer (II) is more than 0.8 said alkyl radical A contains from 8 to 24 carbon atoms. S *eeo* eee*