Fluorosurfactants in pesticides

Patent metadata

Field	Value
Publication number	US-9695117-B2
Application number	US-201414895800-A
Country	US
Kind code	B2
Filing date	May 20, 2014
Priority date	Jun 4, 2013
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

The present invention relates to the use of fluorinated surfactants of formula (I) in pesticides.

First claim

The invention claimed is:

1. A pesticide and/or crop-protection agent formulation comprising a pesticide and/or crop-protection agent and at least one compound of the formula (I)

where X is an anionic group X selected from —COO—, —S0 3 , —OSO 3 , —PO32-, —OPO 32 , —(OCH 2 CH 2 )s-O—(CH 2 )—COO—, —(OCH 2 CH 2 )s-O—(CH 2 )t-SO 3 , —(OCH 2 CH 2 )s-O—(CH 2 )t-OSO 3 , —(OCH 2 CH 2 )s-O—(CH 2 )t-PO3 2 —, —(OCH 2 CH 2 )s-O—(CH 2 )t-OP0 32 - or from the formulae A to C,

where s stands for an integer from the range from 1 to 1000, t stands for an integer selected from 1, 2, 3 or 4 and w stands for an integer selected from 1, 2 or 3, having a monovalent cation selected from H+, an alkali metal cation or NR 1 +, where each R is, independently, H or C1-C6-alkyl;
as cationic group selected from —NRR 2 R 3 +Z, —PR 1 R2R 3 +Z—,

where each R stands for H or C 1-4 -alkyl, Z stands for Cl, Br, I, CH 3 SO 3 , CF 3 SO 3 , CH 3 PhSO 3 , PhSO 3 , R 1 , R 2 and R 3 each stand, independently of one another, for H, C 1-30 -alkyl, Ar or —CH 2 Ar and Ar stands for an unsubstituted or mono- or polysubstituted aromatic ring or condensed ring systems having 6 to 18 C atoms in which, in addition, one or two CH groups are optionally replaced by N, a nonionic group selected from: linear or branched alkyl, where one or more non-adjacent C atoms may be replaced by O, S, and/or N; —OH; —SH; —O-(glycoside)o; —S-(glycoside)o; —OCH 2 —CHOH—CH 2 —OH; —OCH 2 Ar(—NCO)p; —OAr(—NCO)p; —CR═CH 2 ; —OCOCR═CH 2 ; amine oxide; a group of one of the following formulae

wherein, u stands for an integer from the range from 1 to 6, o stands for an integer from the range from 1 to 10, p stands for 1 or 2, R1, R2 and R3 each stand, independently of one another, for C 1-30 -alkyl, Ar or —CH 2 Ar, and Ar stands for an unsubstituted, mono- or polysubstituted aromatic ring or condensed ring systems having 6 to 18 C atoms in which, in addition, one or two CH groups are optionally replaced by C═O, and, glycoside stands for an etherified carbohydrate, and R stands for H or methyl; or an amphoteric group selected from the functional groups of the acetyldiamines, the N-alkylamino adds and the betaines.

2. A formulation according to claim 1 , wherein the compound of the formula (I) is a compound of the formulae (II), (III) and/or (IV):

where
X is equal to —SO 3 − , —OSO 3 − , —PO 3 2− or OPO 3 2− ,
Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are equal to O,
Rf l , Rf 2 and Rf 3 are equal to perfluorinated alkyl groups having 1 to 4 C atoms,
n1, n2 and n3 are equal to 1 or 2,
m1, m2 and m3 are equal to 1-4,
L 1 , L 2 and L 3 are equal to linear or branched C3-C6-alkylene, and
R 3 and R 4 are equal to hydrogen or an alkyl group having 1 to 3 C atoms.

3. A formulation according to claim 1 , characterised in that the compounds of the formula (I) are compounds of the formulae (III-1) and/or (III-2):

where the * indicates the point of attachment of the R group.

4. A formulation according to claim 1 , which further comprises at least one compound of the formula (VI)
(RF-(spacer) m ) n M  (VI)

where
RF is a fluorine-containing group,
spacer is a single bond or an organic functional carbon chain,
n is ≧1,
m=0-1 and
M is an anionic, cationic, amphoteric or non-ionic group.

5. A formulation according to claim 4 , characterised in that the group (RF-(spacer) m ) n - in the compounds of the formula (VI) is equal to C n′ F 2n′+1 —, C n′ F 2n′+1 —CH 2 CH 2 —, C n′ F 2n′+1 —OCF 2 CF 2 —, C n′ F 2n′+1 —OC 6 H 4 —, C n′ F 2n′+1 —C(O)NH(CH 2 ) 3 N═, C n′ F 2n′+1 —SO 2 NH(CH 2 ) 3 N═, CF 3 CCl 2 (CF 2 CFCl) n′−1 —CF 2 — or C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 —, where n′=4-12, and M is equal to —OPOO − , —COO − , —SO 3 − , —OSO 3 − , —OP(O)(O − )O— or —OP(O)O 2 2− , and the compound of formula (VI) has H + , Na + , K + , Li + or NH 4 + as counterion.

6. A formulation according to claim 2 , which comprises at least one compound of the formula (III) and at least one compound of the formula (VI)
(RF-(spacer) m ) n M  (VI)

where
RF is a fluorine-containing group,
spacer is a single bond or an organic functional carbon chain,
n is ≧1,
m=0-1 and
M is an anionic, cationic, amphoteric or non-ionic group.

7. A formulation according to claim 1 , which further comprises at least one compound of the formulae (VII) to (X)

where x=1-500, y=1-500 and R=phenyl, methyl or —(O—C 2 H 3 R′) n″ —OR″, where n″=1-1000, R′=linear and branched alkyl radical and R″=linear and branched alkyl radicals,
M 2 D′(E n″′ P)  (IX)

where M=(CH 3 ) 3 SiO—, D′=Si(R′″), E=—OCH 2 CH 2 , n″′=5-40 and P═—OH, —OMe, or —OAc, where R″′=linear and/or branched alkyl chain,

where n=1-100.

8. A formulation according to claim 4 , which further comprises at least one compound of the formulae (VII) to (X)

where x=1-500, y=1-500 and R=phenyl, methyl or —(O—C 2 H 3 R′) n″ —OR″, where n″=1-1000, R′=linear and branched alkyl radical and R″=linear and branched alkyl radicals,
M 2 D′(E n″′ P)  (IX)

where M=(CH 3 ) 3 SiO—, D′=Si(R′″), E=—OCH 2 CH 2 , n″′=5-40 and P═—OH, —OMe, or —OAc, where R″′=linear and/or branched alkyl chain,

where n=1-100.

9. A formulation according to claim 1 , characterised in that it is in the form of a liquid pesticide formulation which can be applied by means of spraying methods.

10. A formulation according to claim 1 , which comprises one or more crop-protection agents.

11. A pesticide and/or crop-protection method which comprises applying a pesticide and/or crop protection agent formulation according to claim 1 to a crop or plant.

12. A method according to claim 11 , which comprises applying the formulation by spraying in the cultivation of a crop or ornamental plant.

13. A method according to claim 11 , wherein the compound of the formula (I) improves the efficacy of the pesticide and/or crop-protection agent and/or acts as dispersant, emulsion stabiliser and/or foam inhibitor.

14. A pesticide and/or crop-protection method which comprises applying a pesticide and/or crop protection agent formulation according to claim 2 to a crop or plant.

15. A pesticide and/or crop-protection method which comprises applying a pesticide and/or crop protection agent formulation according to claim 3 to a crop or plant.

16. A formulation according to claim 1 , wherein, in formula (I), X is: an anionic group X selected from —COO—, —S0 3 , —OSO 3 , —PO32-, —OPO 32 , —(OCH 2 CH 2

Assignees

• Merck Patent Gmbh

Inventors

• Pahnke Joerg
• Jonschker Gerhard
• Schellenberger Steffen

Classifications

• A01N25/30 Primary

  characterised by the surfactants · CPC title

• C07C317/44 Primary

  having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton · CPC title

• A01N41/10

  Sulfones; Sulfoxides · CPC title