Use of aqueous drift-reducing compositions

Abstract

The invention relates to the use of compositions which contain A) one or more copolymers, said copolymers containing one or more structural units resulting from a) 19.9 to 75.9 wt.-% of glycerin, b) 0.1 to 30 wt.-% of at least one dicarboxylic acid, and c) 24 to 80 wt.-% of at least one monocarboxylic acid according to formula (I): R.sup.1—COOH, wherein R.sup.1 is (C.sub.5-C.sub.29) alkyl; (C.sub.7-C.sub.29) alkenyl; phenyl or naphthyl, and B) water for reducing drift during the application of a spray emulsion that contains one or more pesticides.

Claims

1. A method for reducing drift on application of a spray liquor comprising at least one pesticide, comprising the step of including at least one drift reducing composition comprising A) at least one copolymer, wherein the copolymer is a copolymer of a) 19.9 to 75.9 wt. % of glycerol b) 0.1 to 30 wt. % of at least one dicarboxylic acid selected from the group consisting of oxalic acid, a dicarboxylic acid according to formula (II)
HOOC—R.sup.2—COOH  (II) and a dicarboxylic acid according to formula (III) ##STR00002## and mixtures thereof, wherein R.sup.2 is a (C.sub.1-C.sub.40) alkylene bridge or a (C.sub.2-C.sub.20) alkylene bridge or a mono or dihydroxy-substituted (C.sub.2-C.sub.20)-alkylene bridge and R represents H, a (C.sub.1-C.sub.20)-alkyl, (C.sub.2-C.sub.20)-alkenyl, phenyl, naphthyl, benzyl, halogen, —NO.sub.2, (C.sub.1-C.sub.6)-alkoxy, —CHO, or —CO((C.sub.1-C.sub.6)-alkyl), and (c) 24 to 80 wt. % of at least one monocarboxylic acid according to formula (I)
R.sup.1—COOH  (I) wherein R.sup.1—COOH is a fatty acid having 8 to 24 carbon atoms, wherein the wt % are based on the total weight of the monomers a), b), and c) and B) water in the spray liquor comprising at least one pesticide.

2. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the composition comprises water in an amount of greater than 1.0 wt. % and less than 99 wt. %, based on the total weight of the composition.

3. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the at least one dicarboxylic acid b) is phthalic acid and the at least one monocarboxylic acid c) is a coconut fatty acid.

4. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein in the drift reducing composition the content of the at least one copolymer of component A) is 1 to 90 wt. %, and the content of component B) is 10 to 99 wt. % based on the total weight of the drift reducing composition.

5. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the drift reducing composition further comprises at least one auxiliary substance or at least one additive or mixtures thereof (component C).

6. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 5, wherein the content of the at least one copolymer of component A) is 1 to 89.9 wt. %, the content of component B) is 2 to 98.9 wt. %, and the content of component C) is 0.1 to 70 wt. %, in each case based on the total weight of the drift reducing composition.

7. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the at least one pesticide is selected from the group consisting of water-soluble pesticides.

8. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 7, wherein the spray liquor comprises at least two water-soluble pesticides.

9. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 8, wherein the at least two water-soluble pesticides are selected from the group consisting of the water-soluble acids and salts thereof.

10. A method for reducing drift on application of a spray liquor comprising at least two pesticides comprising the step of including at least one drift reducing composition comprising A) at least one copolymer, wherein the copolymer is a copolymer of a) 19.9 to 75.9 wt. % of glycerol b) 0.1 to 30 wt. % of at least one dicarboxylic acid selected from the group consisting of oxalic acid, a dicarboxylic acid according to formula (II)
HOOC—R.sup.2—COOH  (II) and a dicarboxylic acid according to formula (III) ##STR00003## and mixtures thereof, wherein R.sup.2 is a (C.sub.1-C.sub.40) alkylene bridge or a (C.sub.2-C.sub.20) alkylene bridge or a mono or dihydroxy-substituted (C.sub.2-C.sub.20)-alkylene bridge and R represents H, a (C.sub.1-C.sub.20)-alkyl, (C.sub.2-C.sub.20)-alkenyl, phenyl, naphthyl, benzyl, halogen, —NO.sub.2, (C.sub.1-C.sub.6)-alkoxy, —CHO, or —CO((C.sub.1-C.sub.6)-alkyl), and (c) 24 to 80 wt. % of at least one monocarboxylic acid according to formula (I)
R.sup.1—COOH  (I) wherein R.sup.1—COOH is a fatty acid having 8 to 24 carbon atoms, wherein the wt % are based on the total weight of the monomers a), b), and c) and B) water in the spray liquor comprising at least two pesticides, wherein the at least two pesticides are a combination of water-soluble acids and/or salts, and wherein the combination is selected from the group consisting of a) glyophosphate and 2,4-D, b) glyophosphate and dicamba, c) glyophosphate and fomesafen, d) glyophosphate and glufosinate, e) 2,4-D and dicamba, f) glufosinate and 2,4-D, and g) glufosinate and dicamba.

11. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the spray liquor includes at least one safener.

12. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the total amount of the at least one copolymer of component A) in the drift reducing composition is from 10 to 50 g/l, based on the total volume of the spray liquor.

13. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 5, wherein the content of the at least one copolymer of component A) is 0.1 to 40 wt. %, the content of the at least one pesticide, is 0.1 to 75 wt. %, and the content of the at least one auxiliary substance or additive is 0.1 to 30 wt. %, in each case based on the total weight of the composition.

14. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the spray liquor comprises 0.01 to 10 wt. % of the at least one pesticide, and 0.001 to 3 wt. % of the at least one polymer of component A), in each case based on the total weight of the spray liquor.

15. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein R.sup.1—COOH is a fatty acid having 12 to 22 carbon atoms.

16. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the at least one dicarboxylic acid b) is phthalic acid.

17. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the at least one dicarboxylic acid b) is phthalic acid, itaconic acid, tartaric acid, succinic acid, malic acid and/or adipic acid.

18. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the at least one monocarboxylic acid c) is a coconut fatty acid.

19. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the copolymer A) is a copolymer of 34.0 to 62.0 wt. % of glycerol, 0.2 to 21.0 wt. % of the at least one dicarboxylic acid, and 24.0 to 54.0 wt. % of the at least one monocarboxylic acid.

20. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 17, wherein the at least one dicarboxylic acid is phthalic acid and the at least one monocarboxylic acid is coconut fatty acid.

21. The method for reducing drift on application of a spray liquor comprising at least one pesticide as claimed in claim 1, wherein the spray liquor comprises 0.01 to 10 wt. % of the at least one pesticide, and 0.001 to 3 wt. % of the at least one polymer of component A), in each case based on the total weight of the spray liquor.

Description

EXAMPLES

(1) The invention is illustrated in the following with the aid of examples which, however, are in no way to be regarded as a limitation.

(2) The percentage data stated in the following are percentage by weight (wt. %) unless explicitly stated otherwise.

(3) The commercial products employed are: Genamin® 267 amine ethoxylate from Clariant Synergen® GA C.sub.8/C.sub.10 alkyl-N-methylglucamide from Clariant Sterling Blue dicamba DGA herbicide formulation (480 g/l a.e.) from Winfield DGA diglycolamine [2-(2-aminoethoxy)ethanol] Glyphosate IPA salt isopropylammonium salt of glyphosate

(4) “a.e.” denotes “acid equivalent”

Preparation Examples

A) General Instructions for the Preparation of Copolymers 1 to 7

(5) The copolymers are prepared in two steps, wherein in the first step glycerol is subjected to a condensation reaction to give the corresponding polyglycerol, which is then reacted with monocarboxylic acid and dicarboxylic acid to give the copolymer.

(6) Preparation of polyglycerol (n=9.7): 2,000 g of glycerol and 6.0 g of NaOH (50 wt. % strength in water) were heated to 270° C. in a stirred apparatus with a nitrogen inlet and water removal unit, while stirring. After a reaction time of 9 hours and a discharge of 444 g of water, a sample was taken and the OH number was determined. The OH number determined was 891 mg of KOH/g. This corresponds to an average degree of condensation n of 9.7 glycerol units.

(7) Preparation of polyglycerol (n=5.0): 2,000 g of glycerol and 6.0 g of NaOH (50 wt. % strength in water) were heated to 270° C. in a stirred apparatus with a nitrogen inlet and water removal unit, while stirring. After a reaction time of 4 hours and a discharge of 226 g of water, a sample was taken and the OH number was determined. The OH number determined was 1,009 mg of KOH/g. This corresponds to an average degree of condensation n of 5.0 glycerol units.

(8) The method described in DIN 53240 is used to determine the OH number.

(9) Condensation of polyglycerol with mono- and dicarboxylic acid to give the copolymer: The polyglycerol was introduced into a stirred container with a line for passing N.sub.2 through and a water removal unit and coconut fatty acid (Cana) and phthalic acid were added. The reaction mixture was then heated to 220° C., while stirring, until the copolymer has an acid number of <1.00 mg KOH/g (three to nine hours)

(10) The method described in DIN EN ISO 2114 is used to determine the acid number.

(11) The absolute amounts employed for the monomers for the preparation of copolymers 1-7 and the percentage by weight composition of copolymers 1-7 are given in Table 1.

(12) The percentage by weight compositions of copolymers 1-7 stated in Table 1 relate to the total amount of the monomers such as were employed for the preparation of the copolymers. They do not relate to the final composition of the copolymers, which deviates from this due to the splitting of water liberated during the condensation.

(13) TABLE-US-00001 TABLE 1 Composition of the copolymer: Coconut Phthalic Coconut Glyc- Phthalic fatty Glycerol acid fatty acid Co- erol acid acid content content content polymer [g] n [g] [g] [wt. %] [wt. %] [wt. %] 1 460 5.0 1.7 408 52.9 0.2 46.9 2 460 5.0 17 408 52.0 1.9 46.1 3 218 9.7 40.4 98.8 61.0 11.3 27.7 4 460 5.0 166 204 55.4 20.0 24.6 5 218 9.7 83 98.8 54.5 20.8 24.7 6 460 5.0 166 408 44.5 16.1 39.5 7 460 5.0 166 712 34.4 12.4 53.2 n: average degree of condensation of the glycerol

B) Examples of Drift-Reducing Compositions

Example DC1

(14) 70 wt. % of copolymer 3 are introduced into 30 wt. % of water, while stirring.

(15) A clear, brown highly viscous solution forms.

Example DC2

(16) 45 wt. % of copolymer 3 and 10 wt. % of dipropylene glycol are introduced into 45 wt. % of water, while stirring. A clear, yellowish solution forms.

Example DC3

(17) 45 wt. % of copolymer 3, 45 wt. % of Synergen GA and 5 wt. % of propylene glycol are introduced into 5 wt. % of water, while stirring. A clear, yellowish solution forms.

Example DC4

(18) 30 wt. % of copolymer 3 and 30 wt. % of Genamin 267 are introduced into 40 wt. % of water, while stirring. A clear, yellowish solution forms.

C) Examples of Drift-Reducing Compositions Comprising Pesticide

Example PC1

Preparation of an Aqueous Pesticide Composition Based on Dicamba

(19) A clear homogeneous aqueous composition was prepared by mixing 86 wt. % of an aqueous solution which comprises 480 g/l (a.e.) of dicamba DGA salt (corresponds to approx. 708 g/l of the dicamba salt) and 14 wt. % of DC1. The composition comprises 10 wt. % of copolymer 3. The composition was storage-stable for at least three months at temperatures of −10° C., 0° C., 25° C. and 50° C.

Example PC2

Preparation of an Aqueous Pesticide Composition Based on IPA Glyphosate

(20) A clear homogeneous aqueous composition was prepared by mixing 68.4 wt. % of an aqueous solution which comprises 565 g/l (a.e.) of IPA glyphosate salt (corresponds to approx. 763 g/l of the glyphosate salt) and 14 wt. % of DC1 and 15 wt. % of Genamin 267, and was topped up to 100 wt. % with water.

(21) The composition was storage-stable for at least three months at temperatures of −10° C., 0° C., 25° C. and 50° C.

Example PC3

Preparation of an Aqueous Pesticide Composition Based on IPA Glyphosate

(22) A clear, homogeneous aqueous composition was prepared by mixing 68.4 wt. % of an aqueous solution which comprises 565 g/l (a.e.) of IPA glyphosate salt (corresponds to approx. 763 g/l of the glyphosate salt), and 14 wt. % of DC1 and 15 wt. % of Synergen GA, and was topped up to 100 wt. % with water.

(23) The composition was storage-stable for at least three months at temperatures of −10° C., 0° C., 25° C. and 50° C.

Example PC4

Preparation of an Aqueous Pesticide Composition Based on Potassium Glyphosate

(24) A clear, homogeneous aqueous composition was prepared by mixing 73.5 wt. % of an aqueous solution which comprises 680 g/l (a.e.) of potassium glyphosate salt (corresponds to approx. 833 g/l of the glyphosate salt), 14 wt. % of DC1 and 10 wt. % of Synergen GA, and was topped up to 100 wt. % with water.

(25) The composition was storage-stable for at least three months at temperatures of −10° C., 0° C., 25° C. and 50° C.

D) Examples of Aqueous Spray Liquors

Examples of Spray Liquors with Dicamba

(26) The composition of spray liquors A1-A6 is given in the following.

(27) TABLE-US-00002 Spray liquor Dicamba DGA [g/l] Copolymer 3 [g/l] A1 3 0 A2 3 0.1 A3 3 0.25 A4 3 0.5 A5 3 1.0 A6 3 1.5

(28) These spray liquors are prepared by mixing aqueous SL formulations which comprise 480 g/l (a.e.) of dicamba DGA salt (e.g. Sterling Blue from Winfield), water or various concentrations of drift-reducing composition DC1 and water.

(29) The spray liquors can also be obtained from pesticide compositions, for example similarly to Example PC1, by dilution with water.

Examples of Spray Liquors with IPA Glyphosate

(30) The composition of spray liquors B1-B6 is given in the following.

(31) TABLE-US-00003 Spray liquor IPA glyphosate [g/l] Copolymer 3 [g/l] B1 7 0 B2 7 0.1 B3 7 0.25 B4 7 0.5 B5 7 1.0 B6 7 1.5

(32) These spray liquors are prepared by mixing an aqueous SL formulation which comprises 565 g/l (a.e.) of IPA glyphosate salt, water or various concentrations of drift-reducing composition DC1 and water.

(33) The composition of spray liquors C.sub.1-C.sub.6 is given in the following.

(34) TABLE-US-00004 Spray liquor Potassium glyphosate [g/l] Copolymer 3 [g/l] C1 10 0 C2 10 0.1 C3 10 0.25 C4 10 0.5 C5 10 1.0 C6 10 1.5

(35) These spray liquors are prepared by mixing an aqueous SL formulation which comprises 680 g/l (a.e.) of potassium glyphosate salt, water or various concentrations of drift-reducing composition DC1 and water.

E) Use Examples

(36) Measurement of the Drop Size Distribution

(37) A Malvern Spraytec “real-time spray sizing system” was used to determine the drop size distribution. For this, the system (STP5321, Malvern Instruments GmbH, Heidelberg, Germany) was mounted in a spray booth of our own construction with the option of being able to select spray applications of conventional practice under a freely adjustable pressure for diverse hydraulic nozzles and freely adjustable distances (nozzle-target surface). The spray booth can be darkened and all interfering parameters can be eliminated. The injector nozzle ID12002 (Lechler) with relatively coarse drop sizes was used for the measurements. The pressure established was varied and an average pressure of 3 bar was kept constant for the measurements reported below. The temperature and relative atmospheric humidity varied between 21.5 and 29° C. and, respectively, 33% and 56%. In each test series tap water and a spray liquor with pesticide but without drift-reducing composition, as internal standards, were always measured. The Spraytec measurement was carried out at the setting of 1 kHz, since measurements at 2.5 kHz or higher, like other influencing variables such as additional suction, proved to be negligible. The measurement in the spray mist was kept constant at a position with distances of exactly 29.3 cm to the nozzle and 0.4 cm from the perpendicular under the nozzle. The measurements were carried out within 5 seconds and the mean of 6 repeats is reported as the volume content of the drops of diameter<90 μm (“vol 90”), <105 μm (“vol 105”) and <150 μm (“vol 150”) (percentage standard error 0.5-2.5%). As a further measurement parameter the volume content of drops of diameter <210 μm was determined (“vol 210”) and related to the volume content of the drops of diameter <105 μm (“vol 210/vol 105”). The percentage reduction in the volume content of the drops of diameter <105 μm using the drift-reducing compositions compared with the use of the comparison compositions A1, B1 and C1 was furthermore calculated (“red 105”).

Use Example 1

(38) Drop size distribution injector nozzle (under 3 bar) using spray liquors A1-A6.

(39) TABLE-US-00005 Red Spray Vol 90 Vol 105 Vol 150 Vol 210/ 105 liquid [vol. %] [vol. %] [vol. %] vol 150 Nozzle [%] Water 2.56 3.92 8.31 3.63 ID12002 — A1 3.72 5.20 9.63 3.17 ID12002 — (comparison) A2 1.71 2.62 4.78 3.16 ID12002 52 (invention) A3 1.75 2.59 4.94 3.10 ID12002 50 (invention) A4 1.59 2.36 4.47 3.10 ID12002 55 (invention) A5 1.58 2.29 4.06 2.83 ID12002 56 (invention) A6 1.40 2.03 3.62 2.93 ID12002 61 (invention)

Use Example 2

(40) Drop size distribution injector nozzle (under 3 bar) using spray liquors B1-B6.

(41) TABLE-US-00006 Red Spray Vol 90 Vol 105 Vol 150 Vol 210/ 105 liquid [vol. %] [vol. %] [vol. %] vol 150 Nozzle [%] Water 2.58 3.93 8.37 3.69 ID12002 — B1 2.20 3.33 6.96 3.63 ID12002 — (comparison) B2 1.66 2.44 4.52 3.01 ID12002 27 (invention) B3 1.55 2.28 4.19 2.94 ID12002 31 (invention) B4 1.44 2.09 3.69 2.82 ID12002 37 (invention) B5 1.30 1.87 3.22 2.86 ID12002 44 (invention) B6 1.21 1.75 3.04 2.94 ID12002 47 (invention)

Use Example 3

(42) Drop size distribution injector nozzle (under 3 bar) using spray liquors C.sub.1-C.sub.6.

(43) TABLE-US-00007 Red Vol 90 Vol 105 Vol 150 Vol 210/ 105 Spray liquid [vol. %] [vol. %] [vol. %] vol 150 Nozzle [%] Water 2.53 3.88 8.26 3.66 ID12002 — C1 2.01 3.03 6.25 3.58 ID12002 — (comparison) C2 1.49 2.22 4.11 2.93 ID12002 27 (invention) C3 1.50 2.22 4.02 2.82 ID12002 27 (invention) C4 1.43 2.10 3.70 2.75 ID12002 31 (invention) C5 1.30 1.88 3.17 2.60 ID12002 38 (invention) C6 1.24 1.79 3.04 2.79 ID12002 41 (invention)