Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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USE OF ETHER GROUP-CONTAINING POLYMERS AS SOLUBILIZERS
This patent application claims the priority of
DE 10 2004 031 158.7.
The present invention relates to the use as solubility
promoters of polymers comprising ether groups, in
particular in cosmetics, drugs, foodstuffs, food
supplements and animal fodder, very particularly
preferably in the preparation of plant protection
products, it being possible for the polymers to be
obtained by copolymerization of
(A) optionally at least one ethylenically
unsaturated mono- or dicarboxylic acid or at
least one anhydride derived from an
ethylenically unsaturated mono- or
dicarboxylic acid,
(B) at least one hydrophobic monomer exhibiting
aromatic functional groups and/or aliphatic
functional groups or aromatic and aliphatic
functional groups,
(C) at least one allyl alcohol alkoxylate,
(D) if appropriate, additional monoethylenically
unsaturated monomers.
The most varied polymers for the most varied
applications are known from the state of the art.
The use of copolymers of maleic anhydride and
optionally a second monomer, for example the styrene,
isobutene or vinyl acetate, is disclosed in
EP 0 628 085, the copolymers being reacted with
alkoxylated alcohols before use in retanning and
filling.
EP 0 792 377 discloses a process in which tanning and
if appropriate also pretanning by aldehydes or other
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reactive carbonyl compounds is carried out in the
presence of polymers, for example maleic
anhydride/alpha-olefin/styrene terpolymers (variant I).
US 5 646 225 and US 5 728 777 disclose copolymers of
styrene, methacrylic acid and mono- and dipropoxylated
allyl alcohol and the use of the copolymers in water-
based and solvent-based inks (US 5 728 777).
US 4 847 410 and US 4 959 156 disclose the preparation
of copolymers of allyl alcohol alkoxylates and
(meth)acrylic acid and the use thereof as dispersants.
Furthermore, EP-A-0 601 536 discloses water-soluble
graft copolymers which can be used as dispersants in
aqueous inorganic binders.
WO 01/96007 discloses water-soluble copolymers which
are prepared by copolymerization of (meth)acrylic acid
or of maleic acid hemiesters, an alkyl-capped
alkoxylated hemiester and optionally a dicarboxylic
acid, as well as optionally styrene, and discloses
their use as dispersants for pigments, such as, for
example, CaCO3.
In addition, there are, in the field of active
substances, inclusive of the plant protection field,
numerous polymers with the most varied application
possibilities. Reference may be made, for example, to
WO 03/043420. It discloses the use of copolymers as
adjuvants in the treatment of plants. The copolymers
consist of olefins and/or vinyl ethers, and also of
ethylenically unsaturated dicarboxylic acids or
dicarboxylic acid derivatives and additional
comonomers.
Reference may also be made to DE 103 38 437, which
discloses the formulation of agricultural active agents
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with adjuvants based on block copolymers.
Likewise, DE 103 51 004 discloses random radical
polymers based on sulfonate-comprising acrylates and
their use in active substance formulation, in
particular in the plant protection field.
In addition, EP 002820951 discloses sustained-release
preparations for active substances which are formed
from a copolymer consisting of allyl alcohol
alkoxylates and maleic anhydride.
Finally, it may also be pointed out that US 2 872 369
discloses copolymers which increase the solubility of
sparingly soluble components in polar solvents.
It is the aim of the present invention henceforth to
convert hydrophobic water-soluble active and effect
substances, with the help of polymers, into a stable
aqueous formulation.
Stable is understood as meaning, for the purposes of
the invention, that the formulations are stable towards
sedimentation and creaming over a time period and
temperature range sufficient for the respective use.
The term "creaming" is understood to mean, in this
connection, the enriching of the dispersed oil drops,
which typically are generally lighter, in the upper
part of an oil-in-water emulsion. Thus, the stability
of an active substance formulation over one or more
years is a precondition, for example, for application
in plant protection. In order to enhance the action and
to increase the bioavailability of sparingly water-
soluble active and effect substances, these can, in
extreme cases, be dissolved with the help of the
polymers.
Mention may be made, as an example, of the dissolution
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of active substances in surfactant-like polymer
micelles, by what means the active substances are
stabilized in molecularly dispersed fashion in the
aqueous formulation. The term "molecularly dispersed"
means in this connection that no active substance
crystals can be detected under a transmission electron
microscope.
It was accordingly an object of the present invention
to make available polymers which can be used as
solubility promoters, in particular in cosmetics,
drugs, foodstuffs, food supplements and animal fodder,
particularly preferably in the preparation of plant
protection products.
The object according to the invention is achieved by
the use as solubility promoters of polymers comprising
ether groups, in particular in cosmetics, drugs,
foodstuffs, food supplements and animal fodder, very
particularly in the preparation of plant protection
products, it being possible for the polymers to be
obtained by copolymerization of
(A) optionally at least one ethylenically
unsaturated mono- or dicarboxylic acid and/or
at least one anhydride derived from an
ethylenically unsaturated mono- or
dicarboxylic acid,
(B) at least one hydrophobic monomer exhibiting
aromatic functional groups and/or aliphatic
functional groups or aromatic and aliphatic
functional groups,
(C) at least one allyl alcohol alkoxylate,
(D) if appropriate, additional monoethylenically
unsaturated monomers.
The term "solubility promoter" describes frequently
surface-active materials which, by their presence,
render other compounds, which are virtually insoluble
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in a certain solvent, soluble or emulsifiable in this
solvent (solubilization). There are solubility
promoters which form a molecular compound with the
sparingly soluble substance and those which act by
micelle formation or even those which give a "latent
solvent" its solvating power.
Such polymers are already known from DE 103 33 749.
However, only the use for the treatment of leather is
described in this patent application. Additional
employment possibilities are not mentioned.
It is henceforth surprising according to the invention
that the copolymers described are also suitable as
solubility promoters, in particular in cosmetics,
drugs, foodstuffs, food supplements and animal fodder,
particulary preferably in the preparation of plant
protection products.
The content of active and/or effect substance can be
varied over wide ranges. In particular, the amphiphilic
polymer compositions make possible the preparation of
"active substance concentrates" which comprise the
active substance in an amount of at least 5% by weight,
e.g. in an amount of 5 to 50% by weight and in
particular in an amount of 5 to 20% by weight, based on
the total weight of the composition.
The aqueous active substance compositions according to
the invention can advantageously be formulated in the
form devoid of or low in solvent, i.e. the proportion
of organic solvents in the aqueous active substance
composition is frequently no more than 10o by weight,
in particular no more than 5% by weight and in
particular no more than 1% by weight, based on the
total weight of the composition.
A multitude of different active and effect substances
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can be formulated in the aqueous compositions according
to the invention. A particular embodiment of the
invention relates to the formulation of active
substances for plant protection, i.e. of herbicides,
fungicides, nematicides, acaricides, insecticides and
active substances which regulate plant growth.
Examples of fungicidal active substances which can be
formulated as aqueous active substance composition
according to the invention comprise:
Pesticides are known to a person skilled in the art
from the literature. The term "pesticide" means here at
least one active substance chosen from the group
consisting of the insecticides, fungicides, herbicides
and/or safeners, growth regulators (see Pesticide
Manual, 13th Ed. (2003)),
Insecticides
= organo(thio)phosphates, such as acephate,
azamethiphos, azinphos-methyl, chlorpyrifos,
chlorpyrifos-methyl, chlorfenvinphos, diazinon,
dichlorphos, dicrotophos, dimethoate, disulfoton,
ethion, EPN, fenitrothion, fenthion, isoxathion,
malathion, methamidophos, methidathion, methyl
parathion, mevinphos, monocrotophos, oxydemeton-
methyl, paraoxon, parathion, phenthoate, phosalone,
phosmet, phosphamidon, phorate, phoxim, pirimiphos-
methyl, profenofos, prothiofos, pirimiphos-ethyl,
pyraclofos, pyridaphenthion, sulprophos,
triazophos, trichlorfon, tetrachlorvinphos or
vamidothion;
= carbamates, such as alanycarb, benfuracarb,
bendiocarb, carbaryl, carbofuran, carbosulfan,
fenoxycarb, furathiocarb, indoxacarb, methiocarb,
methomyl, oxamyl, pirimicarb, propoxur, thiodicarb
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or triazamate;
= pyrethroids, such as allethrin, bifenthrin,
cyfluthrin, cycloprothrin, cyphenothrin, cyper-
methrin and the alpha, beta, theta and zeta
isomers, deltamethrin, esfenvalerate, etofenprox,
fenpropathrin, fenvalerate, cyhalothrin, lambda-
cyhalothrin, imiprothrin, permethrin, prallethrin,
pyrethrin I, pyrethrin II, silafluofen, tau-
fluvalinate, tefluthrin, tetramethrin,
tralomethrin, alpha-cypermethrin, transfluthrin,
zeta-cypermethrin;
= arthropodal growth regulators, such as a) chitin
synthesis inhibitors, e.g. benzoylureas, such as
chlorfluazuron, cyromazine, diflubenzuron, flucy-
cloxuron, flufenoxuron, hexaflumuron, lufenuron,
novaluron, teflubenzuron, triflumuron, buprofezin,
diofenolan, hexythiazox, etoxazole or clofentazine;
b) ecdysone antagonists, such as halofenozide,
methoxyfenozide or tebufenozide; c) juvenile
hormone mimics, such as pyriproxyfen, methoprene or
fenoxycarb; d) lipid biosynthesis inhibitors, such
as spirodiclofen;
= neonicotinoids, such as flonicamid, clothianidin,
dinotefuran, imidacloprid, thiamethoxam, niten-
pyram, nithiazine, acetamiprid or thiacloprid;
= pryazole insecticides, such as acetoprole,
ethiprole, fipronil, tebufenpyrad, tolfenpyrad and
vaniliprole;
= furthermore unclassified insecticides, such as
abamectin, acequinocyl, acetamipirid, amitraz,
azadirachtin, bensutap, bifenazate, cartap, chlor-
fenapyr, chlordimeform, cyromazine, diafenthiuron,
dinetofuran, diofenolan, emamectin, endosulfan,
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ethiprole, fenazaquin, fipronil, formetanate,
formetanate hydrochloride, gamma-HCH, hydra-
methylnon, imidacloprid, indoxacarb, isoprocarb,
metolcarb, piperonyl butoxide, pyridaben,
pymetrozine, spinosad, tebufenpyrad, thiamethoxam,
thiocyclam, XMC and xylylcarb, pyridalyl,
flonicamid, fluacrypyrim, milbemectin, spiro-
mesifen, flupyrazofos, NC 512, tolfenpyrad,
flubendiamide, bistrifluron, benclothiaz, pyra-
fluprole, pyriprole, amidoflumet, flufenerim,
cyflumetofen, acequinocyl lepimectin, profluthrin,
dimefluthrin, metaflumizone, N-R1-2,2-dihalo-l-R2-
cyclopropanecarboxamide 2-(2,6-dichloro-(x,a,a-
trifluoro-p-tolyl)hydrazone, N-R1-2,2,-di-R3-
propionamide 2-(2,6-dichloro-a,a,(x-trifluoro-p-
tolyl)hydrazone, R1 being methyl or ethyl, halo
being chlorine or bromine, R2 being H (hydrogen) or
methyl and R3 being methyl or ethyl, preferably
N-ethyl-2,2-dichloro-l-methyl-
cyclopropanecarboxamide 2-(2,6-dichloro-a,a,(x-tri-
fluoro-p-tolyl)hydrazone, N-ethyl-2,2-dimethyl-
propionamide 2-(2,6-dichloro-a,(x,a-trifluoro-p-
tolyl)hydrazone, acid of the following formula
I
HN I ~ 0
O O~
2 5 = -0
aminoisothiazole of the formula
CI R
N N
R
y N-S O O
in which
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R = -CH20CH3 or H, and
R_ -CF2CF2CF3;
anthranilamide of the formula
O Br
I
CI N N'
H
I
C
O b
N H
and an insecticidal active compound of the following
formula
HN I ~ CF3
O
The following list of fungicides shows possible active
substances but should not be limited to these:
= acylalanines, e.g. benalaxyl, furalaxyl,
metalaxyl, ofurace or oxadixyl;
= amine derivatives, e.g. aldimorph, dodine,
dodemorph, fenpropimorph, fenpropidin, guazatine,
iminoctadine, spiroxamine or tridemorph;
= anilinopyrimidines, e.g. pyrimethanil, mepanipyrim
or cyrodinyl;
= antibiotics, e.g. cycloheximide, griseofulvin,
kasugamycin, natamycin, polyoxin, streptomycin or
validamycin A;
9 azoles, e.g. bitertanol, bromuconazole,
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cyazofamid, cyproconazole, difenoconazole,
dinitroconazole, epoxiconazole, etridiazole,
fenbuconazole, fluquinconazole, flusilazole,
flutriafol, fuberidazole, hexaconazole, hymexazol,
imazalil, imibenconazole, metconazole,
myclobutanil, penconazole, pefurazoate, propi-
conazole, prochloraz, prothioconazole, sime-
conazole, tebuconazole, tetraconazole,
thiabendazole, triadimefon, triadimenol,
triflumizole, triticonazole, 5-chloro-7-(4-
methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-
3-propylchromen-4-one or 3-(3-bromo-6-fluoro-2-
methylindol-1-ylsulfonyl)-[1,2,4]triazole-l-
sulfonic acid dimethylamide;
= dicarboximides, e.g. iprodione, myclozolin,
procymidone or vinclozolin;
= dithiocarbamates, e.g. ferbam, nabam, maneb,
mancozeb, metam, metiram, propineb, polycarbamate,
thiram, ziram or zineb;
= heterocyclic compounds, e.g. anilazine, benomyl,
boscalid, carbendazim, carboxin, oxycarboxin,
cyazofamid, dazomet, dithianon, ethirimol,
dimethirimol, famoxadone, fenamidone, fenarimol,
fuberidazole, flutolanil, furametpyr,
isoprothiolane, mepronil, nuarimol, octhilinone,
picobenzamid, probenazole, proquinazid, pyrifenox,
pyroquilon, quinoxyfen, silthiofam, thiabendazole,
thifluzamide, thiophanate-methyl, tiadinil,
tricyclazole, triforine, 3-[5-(4-chlorophenyl)-
2,3-dimethylisoxazolidin-3-yl]pyridine or
bupirimate;
= copper fungicides, e.g. Bordeaux mixture, copper
acetate, copper hydroxyide, copper oxychloride or
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basic copper sulfate;
= nitrophenyl derivatives, e.g. binapacryl, dinocap,
dinobuton or nitrophtal-isopropyl;
= phenylpyrroles, e.g. fenpiclonil or fludioxonil;
= sulfur;
= organometallic compounds, e.g. fentin salts;
= organophosphorous compounds, e.g. edifenphos,
iprobenfos, pyrazophos, tolclofos-methyl, fosetyl,
fosetyl-aluminum or phosphorous acid;
= other fungicides, e.g. acibenzolar-S-methyl,
benthiavalicarb, carpropamid, chlorothalonil,
cyflufenamid, cymoxanil, dazomet, diclomezine,
diclocymet, diethofencarb, edifenphos, ethaboxam,
fenhexamid, fentin acetate, fenoxanil, ferimzone,
fluazinam, fosetyl, fosetyl-aluminum,
iprovalicarb, hexachlorobenzene, metrafenone,
pencycuron, propamocarb, phthalide, tolclofos-
methyl, quintozene, zoxamide, isoprothiolane,
probenfos, fluopicolide (picobenzamid),
mandipropamid, N-(2-{4-[3-(4-chlorophenyl)prop-2-
ynyloxy]-3-methoxyphenyl}ethyl)-2-
methylsulfonylamino-3-methylbutyramide, N-(2-{4-
[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxy-
phenyl}ethyl)-2-ethylsulfonylamino-3-
methylbutyramide, furametpyr, thifluzamide,
penthiopyrad, fenhexamid, 3,4-dichloroisothiazole-
5-carboxylic acid (2-cyanophenyl)amide,
flubenthiavalicarb, 3-(4-chlorophenyl)-3-(2-
isopropoxycarbonylamino-3-methylbutyrylamino)-
propionic acid methyl ester, {2-chloro-5-[1-(6-
methylpyridin-2-ylmethoxyimino)ethyl]benzyl}-
carbamic acid methyl ester, {2-chloro-5-[l-(3-
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methylbenzyloxyimino)ethyl]benzyl}carbamic acid
methyl ester, flusulfamide, phthalide or
hexachlorobenzene;
amides of the formula
O
H3C-<\ S N
N H
X R1, R2
in which
X is CHF2 or CH3, and
R1 and R2 are, independently of one another,
halogen, methyl or halomethyl;
= strobilurins, e.g. azoxystrobin, dimoxystrobin,
enestroburin, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin or trifloxystrobin;
= sulfenic acid derivatives, e.g. captafol, captan,
dichlofluanid, folpet or tolylfluanid;
= cinnamamides and analogs, e.g. dimethomorph,
flumetover or flumorph;
= amide fungicides, e.g. cyclofenamid or (Z)-N-[a-
(cyclopropylmethoxyimino)-2,3-difluoro-6-
(difluoromethoxy)benzyl]-2-phenylacetamide.
The following list of herbicides demonstrates possible
active substances but should not be limited to these:
compounds which inhibit the biosynthesis of lipids,
e.g. chlorazifop, clodinafop, clofop, cyhalofop,
ciclofop, fenoxaprop, fenoxaprop-P, fenthiaprop,
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fluazifop, fluazifop-P, haloxyfop, haloxyfop-P,
isoxapyrifop, metamifop, propaquizafop, quizalofop,
quizalofop-P, trifop, alloxydim, butroxydim, clethodim,
cloproxydim, cycloxydim, profoxydim, sethoxydim,
tepraloxydim, tralkoxydim, butylate, cycloate, di-
allate, dimepiperate, EPTC, esprocarb, ethiolate,
isopolinate, methiobencarb, molinate, orbencarb,
pebulate, prosulfocarb, sulfallate, thiobencarb,
thiocarbazil, tri-allate, vernolate, benfuresate,
ethofumesate and bensulide;
ALS inhibitors, such as amidosulfuron, azimsulfuron,
bensulfuron, chlorimuron, chlorsulfuron, cinosulfuron,
cyclosulfamuron, ethametsulfuron, ethoxysulfuron,
flazasulfuron, flupyrsulfuron, foramsulfuron, halo-
sulfuron, imazosulfuron, iodosulfuron, mesosulfuron,
metsulfuron, nicosulfuron, oxasulfuron, primisulfuron,
prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron,
sulfosulfuron, thifensulfuron, triasulfuron, tri-
benuron, trifloxysulfuron, triflusulfuron, trito-
sulfuron, imazamethabenz, imazamox, imazapic, imazapyr,
imazaquin, imazethapyr, cloransulam, diclosulam,
florasulam, flumetsulam, metosulam, penoxsulam,
bispyribac, pyriminobac, propoxycarbazone,
flucarbazone, pyribenzoxim, pyriftalid and pyrithiobac;
compounds which inhibit photosynthesis, such as
atraton, atrazine, ametryn, aziprotryn, cyanazine,
cyanatryn, chlorazine, cyprazine, desmetryn,
dimethametryn, dipropetryn, eglinazine, ipazine,
mesoprazine, methometon, methoprotryne, procyazine,
proglinazine, prometon, prometryn, propazine,
sebuthylazine, secbumeton, simazine, simeton, simetryn,
terbumeton, terbuthylazine and terbutryn;
protoporphyrinogen IX oxidase inhibitors, such as
acifluorfen, bifenox, chlomethoxyfen, chlornitrofen,
ethoxyfen, fluorodifen, fluoroglycofen, fluoronitrofen,
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fomesafen, furyloxyfen, halosafen, lactofen, nitrofen,
nitrofluorfen, oxyfluorfen, fluazolate, pyraflufen,
cinidon-ethyl, flumiclorac, flumioxazin, flumipropyn,
fluthiacet, thidiazimin, oxadiazon, oxadiargyl,
azafenidin, carfentrazone, sulfentrazone, pentoxazone,
benzfendizone, butafenacil, pyraclonil, profluazol,
flufenpyr, flupropacil, nipyraclofen and etnipromid;
herbicides, such as metflurazon, norflurazon,
flufenican, diflufenican, picolinafen, beflubutamid,
fluridone, flurochloridone, flurtamone, mesotrione,
sulcotrione, isoxachlortole, isoxaflutole, benzofenap,
pyrazolynate, pyrazoxyfen, benzobicyclon, amitrole,
clomazone, aclonifen, 4-(3-trifluoromethylphenoxy)-2-
(4-trifluoromethylphenyl)pyrimidine and 3-heterocyclyl-
substituted benzoyl derivatives of the formula (cf.
WO-A-96/26202, WO-A-97/41116, WO-A-97/41117 and
WO-A-97/41118)
R' 3 O Ra
R9
N j I
R,2N OH R
i~
R
in which the substituents RB to R13 have the following
meanings:
R8, R10 represent hydrogen, halogen, C1-C6-alkyl, C1-C6-
haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-
alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
R9 represents a heterocyclic radical from the group
consisting of thiazol-2-yl, thiazol-4-yl, thiazol-5-yl,
isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5-di-
hydroisoxazol-3-yl, 4.,5-dihydroisoxazol-4-yl and
4,5-dihydroisoxazol-5-yl, in which the abovementioned
radicals can carry one or more substituents, e.g. can
be mono-, di-, tri- or tetrasubstituted by halogen,
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C1-Cq-alkyl, C1-C4-alkoxy, C1-Cq-haloalkyl, C1-Cq-halo-
alkoxy or C1-C4-alkylthio;
R11 represents hydrogen, halogen or C1-C6-alkyl;
R12 represents C1-C6-alkyl;
R13 represents hydrogen or C1-C6-alkyl.
Additional suitable herbicides are EPSP synthase
inhibitors, such as glyphosate;
glutamine synthase inhibitors, such as glufosinate and
bilanafos;
DHP synthase inhibitors, such as asulam;
mitosis inhibitors, such as benfluralin, butralin,
dinitramine, ethalfluralin, fluchloralin, isopropalin,
methalpropalin, nitralin, oryzalin, pendimethalin,
prodiamine, profluralin, trifluralin, amiprofos-methyl,
butamifos, dithiopyr, thiazopyr, propyzamide, tebutam,
chlorthal, carbetamide, chlorbufam, chlorpropham and
propham;
VLCFA inhibitors, such as acetochlor, alachlor,
butachlor, butenachlor, delachlor, diethatyl,
dimethachlor, dimethenamid, dimethenamid-P, metaza-
chlor, metolachlor, S-metolachlor, pretilachlor, propa-
chlor, propisochlor, prynachlor, terbuchlor,
thenylchlor, xylachlor, allidochlor, CDEA, epronaz,
diphenamid, napropamide, naproanilide, pethoxamid,
flufenacet, mefenacet, fentrazamide, anilofos,
piperophos, cafenstrole, indanofan and tridiphane;
inhibitors for the biosynthesis of cellulose, such as
dichlobenil, chlorthiamid, isoxaben and flupoxam;
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herbicides, such as dinofenate, dinoprop, dinosam,
dinoseb, dinoterb, DNOC, etinofen and medinoterb;
auxin herbicides, such as clomeprop, 2,4-D, 2,4,5-T,
MCPA, MCPA-thioethyl, dichlorprop, dichlorprop-P,
mecoprop, mecoprop-P, 2,4-DB, MCPB, chloramben,
dicamba, 2,3,6-TBA, tricamba, quinclorac, quinmerac,
clopyralid, fluroxypyr, picloram, triclopyr and
benazolin;
auxin transport inhibitors, such as naptalam and
diflufenzopyr;
in addition: benzoylprop, flamprop, flamprop-M,
bromobutide, chlorflurenol, cinmethylin, methyldymron,
etobenzanid, fosamine, metam, pyributicarb, oxazi-
clomefone, dazomet, triaziflam and methyl bromide.
The term "safener" has the following meaning: it is
known that, in some cases, better herbicidal tolerance
can be achieved by the joint application of herbicides
having a specific action with organic active compounds
which themselves can exert a herbicidal effect. In
these cases, these compounds act as antidote or
antagonist and, because they reduce or avert damage to
useful plants, are described as "safeners".
The following list demonstrates possible safeners but
should not be limited to these:
benoxacor, cloquintocet, cyometrinil, dichlormid,
dicyclonon, dietholate, fenchlorazole, fenclorim,
flurazole, fluxofenim, furilazole, isoxadifen,
mefenpyr, mephenate, naphthalic anhydride, 2,2,5-tri-
methyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148),
4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (AD-67;
MON 4660) and oxabetrinil.
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The following list of compounds with a growth-
regulating effect demonstrates possible active
substances but should not be limited to these:
1-naphthaleneacetamide, 1-naphthaleneacetic acid,
2-naphthoxyacetic acid, 3-CPA, 4-CPA, ancymidol,
anthraquinone, BAP, butifos, tribufos, butralin, chlor-
flurenol, chlormequat, clofencet, cyclanilide,
daminozide, dicamba, dikegulac-sodium, dimethipin,
chlorfenethol, etacelasil, ethephon, ethychlozate,
fenoprop, 2,4,5-TP, fluoridamid, flurprimidol,
flutriafol, gibberellic acid, gibberellin, guazatine,
imazalil, indolebutyric acid, indoleacetic acid,
karetazan, kinetin, lactidichlor-ethyl, maleic
hydrazide, mefluidide, mepiquat chloride, naptalam,
paclobutrazol, prohexadione-calcium, quinmerac,
sintofen, tetcyclacis, thidiazuron, triiodobenzoic
acid, triapenthenol, triazethan, tribufos, trinexapac-
ethyl and uniconazole.
= 2-methoxybenzophenones, such as those disclosed in
EP-A 897 904 by the general formula (I), e.g.
metrafenone;
= 6-aryl-[1,2,4]triazolo[1,5-a]pyrimidines, such as
those disclosed, e.g., in WO 98/46608, WO 99/41255
or WO 03/004465, each time by the general formula
(I).
Examples of herbicides which can be formulated as
aqueous active substance composition according to the
invention comprise:
= 1,3,4-thiadiazoles, such as buthidazole and
cyprazole;
= amides, such as, allidochlor, benzoylprop-ethyl,
bromobutide, chlorthiamid, dimepiperate,
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dimethenamid, diphenamid, etobenzanid, flamprop-
methyl, fosamine, isoxaben, metazachlor, alachlor,
acetochlor, metolachlor, monalide, naptalam,
pronamide or propanil;
= aminophosphoric acids, such as bilanafos,
buminafos, glufosinate-ammonium, glyphosate or
sulfosate;
= aminotriazoles, such as amitrole;
= anilides, such as anilofos or mefenacet;
= aryloxyalkanoic acids, such as 2,4-D, 2,4-DB,
clomeprop, dichlorprop, dichlorprop-P, fenoprop,
fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P,
napropamide, naproanilide or triclopyr;
= benzoic acids, such as chloramben or dicamba;
= benzothiadiazinones, such as bentazon;
= bleachers, such as clomazone, diflufenican,
fluorochloridone, flupoxam, fluridone, pyrazolate
or sulcotrione;
= carbamates, such as carbetamide, clorbufam,
chlorpropham, desmedipham, phenmedipham or
vernolate;
= quinolinecarboxylic acids, such as quinclorac or
quinmerac;
= dichloropropionic acids, such as dalapon;
= dihydrobenzofurans, such as ethofumesate;
= dihydrofuran-3-ones, such as flurtamone;
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= dinitroanilines, such as benefin, butralin,
dinitramine, ethalfluralin, fluchloralin,
isopropalin, nitralin, oryzalin, pendimethalin,
prodiamine, profluralin or trifluralin;
= dinitrophenols, such as bromofenoxim, dinoseb,
dinoseb acetate, dinoterb, DNOC or minoterb
acetate;
= diphenyl ethers, such as acifluorfen-sodium,
aclonifen, bifenox, chlornitrofen, difenoxuron,
ethoxyfen, fluorodifen, fluoroglycofen-ethyl,
fomesafen, furyloxyfen, lactofen, nitrofen,
nitrofluorfen or oxyfluorfen;
= dipyridyls, such as cyperquat, difenzoquat
metilsulfate, diquat or paraquat dichloride;
= imidazoles, such as isocarbamid;
= imidazolinones, such as imazamethapyr, imazapyr,
imazaquin, imazethabenz-methyl, imazethapyr,
imazapic or imazamox;
= oxadiazoles, such as methazole, oxadiargyl or
oxadiazone;
= oxiranes, such as tridiphane;
= phenols, such as bromoxynil or ioxynil;
= phenoxyphenoxypropionates, such as clodinafop,
cyhalofop-butyl, diclofop-methyl, fenoxaprop-
ethyl, fenoxaprop-P-ethyl, fenthiaprop-ethyl,
fluazifop-butyl, fluazifop-P-butyl, haloxyfop-
ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl,
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isoxapyrifop, propaquizafop, quizalofop-ethyl,
quizalofop-P-ethyl or quizalofop-tefuryl;
= phenylacetic acids, such as chlorfenac;
= phenylpropionic acids, such as chlorophenprop-
methyl;
= ppi active substances, such as benzofenap,
cinidon-ethyl, flumiclorac-pentyl, flumioxazin,
flumipropyn, flupropacil, pyrazoxyfen,
sulfentrazone or thidiazimin;
= pyrazoles, such as nipyraclofen;
= pyridazines, such as chloridazon, maleic
hydrazide, norflurazon or pyridate;
= pyridinecarboxylic acids, such as clopyralid,
dithiopyr, picloram or thiazopyr;
= pyrimidyl ethers, such as pyrithiobac-acid,
pyrithiobac-sodium, KIH-2023 or KIH-6127;
= sulfonamides, such as flumetsulam or metosulam;
= triazolecarboxamides, such as triazofenamide;
= uracils, such as bromacil, lenacil or terbacil;
= furthermore benazolin, benfuresate, bensulide,
benzofluor, bentazon, butamifos, cafenstrole,
chlorthal-dimethyl, cinmethylin, dichlobenil,
endothall, fluorbentranil, mefluidide,
perfluidone, piperophos, topramezone and
prohexadione-calcium;
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= sulfonylureas, such as amidosulfuron,
azimsulfuron, bensulfuron-methyl, chlorimuron-
ethyl, chlorsulfuron, cinosulfuron, cyclo-
sulfamuron, ethametsulfuron-methyl, flazasulfuron,
halosulfuron-methyl, imazosulfuron, metsulfuron-
methyl, nicosulfuron, primisulfuron, prosulfuron,
pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-
methyl, thifensulfuron-methyl, triasulfuron,
tribenuron-methyl, triflusulfuron-methyl or
tritosulfuron;
= plant protection active substances of the
cyclohexenone type, such as alloxydim, clethodim,
cloproxydim, cycloxydim, sethoxydim and
tralkoxydim. Very particularly preferred
herbicidal active substances of the cyclohexenone
type are: tepraloxydim (cf. AGROW, No. 243,
11.3.95, page 21, caloxydim) and
2-(1-[2-{4-chlorphenoxy}propyloxyimino]butyl)-3-
hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-
cyclohexen-l-one, and of the sulfonylurea type:
N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-triazin-
2-yl)amino)carbonyl)-2-(trifluoromethyl)benzene-
sulfonamide.
Examples of insecticides which can be formulated as
aqueous active substance composition according to the
invention comprise:
= pyrethroids, such as bifenthrin, cyfluthrin,
cycloprothrin, cypermethrin, deltamethrin,
esfenvalerate, etofenprox, fenpropathrin,
fenvalerate, cyhalothrin, lambda-cyhalothrin,
permethrin, silafluofen, tau-fluvalinate,
tefluthrin, tralomethrin, alpha-cypermethrin or
zeta-cypermethrin;
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= N-phenylsemicarbazones, such as those disclosed in
EP-A 462 456 by the general formula (I), in
particular compounds of the general formula (IV)
H H
i i
N N ~
NI y ( R13
R11 ~ o ~ (IV),
i ~
R' 2
o in which R" and RlZ are, independently of
one another, hydrogen, halogen, CN, C1-C4
alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or
C1-C4 haloalkoxy and R13 is C1-C4 alkoxy,
C1-C9 haloalkyl or C1-C4 haloalkoxy, e.g.
compound (IV) , in which R' is 3-CF3 and R 2
is 4-CN and R3 is 4-OCF3.
Useful growth regulators are, e.g. chlormequat
chloride, mepiquat chloride, prohexadione-calcium or
the group of the gibberellins. These include, e.g., the
gillberellins GA1, GA3, GA4, GA5 and GA7, and the like,
and the corresponding exo-16,17-dihydrogibberellins and
also the derivatives thereof, e.g. the esters with
C1-C9-carboxylic acids. The exo-16,17-dihydro-GA5
13-acetate is preferred according to the invention.
A preferred embodiment of the invention relates to the
use of the amphiphilic polymer compositions according
to the invention in the preparation of aqueous active
substance compositions of fungicides, in particular
strobilurins, azoles and 6-aryltriazolo[1,5-
a]pyrimidines, such as those disclosed, e.g., in
WO 98/46608, WO 99/41255 or WO 03/004465, each time by
the general formula (I), in particular for active
substances of the general formula (V),
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(L)n
R"
N
\/ N ~
N~ N X Ll
in which:
R" is an NR19R15 group, or linear or branched
C1-C8-alkyl, if appropriate substituted by halogen,
OH, C1-C4 alkoxy, phenyl or C3-C6 cycloalkyl; C2-C6
alkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl,
phenyl or naphthyl, it being possible for the 4
last-mentioned radicals to exhibit 1, 2, 3 or 4
substituents chosen from halogen, OH, C1-C4 alkyl,
C1-C4 haloalkoxy, C1-C4 alkoxy and C1-C4 haloalkyl;
R14 and R15 are, independently of one another,
hydrogen, C1-CB-alkyl, C1-C8_haloalkyl,
C3-Clo-cycloalkyl, C3-C6-halocycloalkyl,
CZ-C$-alkenyl, C9-Clo-alkadienyl, CZ-C8-halo-
alkenyl, C3-C6_cycloalkenyl, CZ-Ca-halo-
cycloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl or
C3-C6-cycloalkynyl;
R19 and R15, together with the nitrogen atom to
which they are bonded, form a five- to eight-
membered heterocyclyl which is bonded via N and
can comprise one, two or three additional
heteratoms from the group consisting of 0, N
and S as ring member and/or can carry one or
more substituents from the group consisting of
halogen, C1-C6-alkyl, C1-C6-haloalkyl,
C2-C6-alkenyl, C2-C6-haloalkenyl, Cl-C6-alkoxy, C1-
C6-haloalkoxy, C3-C6-alkenyloxy, C3-
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C6-haloalkenyloxy, (exo)-C1-C6-alkylene and oxy-
C1-C3-al kylenoxy;
L is chosen from halogen, cyano, C1-C6-alkyl,
C1-Cq-haloalkyl, C1-C6-alkoxy, C1-C9-haloalkoxy and
C1-C6-alkoxycarbonyl;
L1 is halogen, C1-C6-alkyl or C1-C6-haloalkyl and in
particular fluorine or chlorine;
X is halogen, C1-Cq-alkyl, cyano, C1-C9-alkoxy or
C1-Cq-haloalkyl and preferably halogen or methyl,
and in particular chlorine.
Examples of compounds of the formula (V) are:
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(4-methylpiperazin-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(isopropylamino)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(cyclopentylamino)-6-(2,4,6-trifluoro-,
phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(2,2,2-trifluoroethylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(1,1,1-trifluoropropan-2-ylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(3,3-dimethylbut-2-ylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(cyclohexylmethyl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
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5-chloro-7-(2-methylbutan-3-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(3-methylpropan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(4-methylcyclohexan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(hexan-3-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(2-methylbutan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(3-methylbutan-l-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-chloro-7-(1-methylpropan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(4-methylpiperidin-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(4-methylpiperazin-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(morpholin-1-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(isopropylamino)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(cyclopentylamino)-6-(2,4,6-trifluoro-
phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(2,2,2-trifluoroethylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(1,1,1-trifluoropropan-2-ylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(3,3-dimethylbutan-2-ylamino)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(cyclohexylmethyl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(cyclohexyl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
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5-methyl-7-(2-methylbutan-3-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(3-methylpropan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(4-methylcyclohexan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(hexan-3-yl)-6-(2,4,6-trifluorophenyl)-
[1,2,4]triazolo[1,5-a]pyrimidine,
5-methyl-7-(2-methylbutan-1-yl)-6-(2,4,6-trifluoro-
phenyl)-[1,2,4]triazolo[1,5-a]pyrimidine
5-methyl-7-(3-methylbutan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine and
5-methyl-7-(1-methylpropan-1-yl)-6-(2,4,6-
trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine.
An additional preferred embodiment of the invention
relates to the use of the amphiphilic polymer
compositions according to the invention in the
preparation of aqueous active substance compositions of
insecticides, in particular of arylpyrroles, such as
chlorfenapyr, of pyrethroids, such as bifenthrin,
cyfluthrin, cycloprothrin, cypermethrin, deltamethrin,
esfenvalerate, etofenprox, fenpropathrin, fenvalerate,
cyhalothrin, lambda-cyhalothrin, permethrin,
silafluofen, tau-fluvalinate, tefluthrin, tralomethrin,
alpha-cypermethrin or zeta-cypermethrin, of
neonicotinoids and of semicarbazones of the formula
(IV), or of fipronil.
The abovementioned pesticides are used against the
appropriate pests.
Pests
Combating undesirable plant growth means the
combating/destruction of plants which grow in places
where they are undesirable, e.g. of dicotyledonous
plants of the following types: Sinapis, Lepidium,
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Galium, Stellaria, Matricaria, Anthemis, Galinsoga,
Chenopodium, Urtica, Senecio, Amaranthus, Portulaca,
Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania,
Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa,
Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus, Taraxacum;
Monocotyledonous plants of the following types:
Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa,
Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena,
Cyperus, Sorghum, Agropyron, Cynodon, Monochoria,
Fimbristyslis, Sagittaria, Eleocharis, Scirpus,
Paspalum, Ischaemum, Sphenoclea, Dactyloctenium,
Agrostis, Alopecurus, Apera.
The term "undesirable insect or acarid" describes but
is not limited to the following kinds:
Lepidoptera, for example Agrotis ypsilon, Agrotis
segetum, Alabama argillacea, Anticarsia gemmatalis,
Argyresthia conjugella, Autographa gamma, Bupalus
piniarius, Cacoecia murinana, Capua reticulana,
Cheimatobia brumata, Choristoneura fumiferana,
Choristoneura occidentalis, Cirphis unipuncta, Cydia
pomonella, Dendrolimus pini, Diaphania nitidalis,
Diatraea grandiosella, Earias insulana, Elasmopalpus
lignosellus, Eupoecilia ambiguella, Evetria bouliana,
Feltia subterranea, Galleria mellonella, Grapholitha
funebrana, Grapholitha molesta, Heliothis armigera,
Heliothis virescens, Heliothis zea, Hellula undalis,
Hibernia defoliaria, Hyphantria cunea, Hyponomeuta
malinellus, Keiferia lycopersicella, Lambdina
fiscellaria, Laphygma exigua, Leucoptera coffeella,
Leucoptera scitella, Lithocolletis blancardella,
Lobesia botrana, Loxostege sticticalis, Lymantria
dispar, Lymantria monacha, Lyonetia clerkella,
Malacosoma neustria, Mamestra brassicae, Orgyia
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pseudotsugata, Ostrinia nubilalis, Panolis flammea,
Pectinophora gossypiella, Peridroma saucia, Phalera
bucephala, Phthorimaea operculella, Phyllocnistis
citrella, Pieris brassicae, Plathypena scabra, Plutella
xylostella, Pseudoplusia includens, Rhyacionia
frustrana, Scrobipalpula absoluta, Sitotroga
cerealella, Sparganothis pilleriana, Spodoptera
frugiperda, Spodoptera littoralis, Spodoptera litura,
Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia
ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus,
Agriotes lineatus, Agriotes obscurus, Amphimallus
solstitialis, Anisandrus dispar, Anthonomus grandis,
Anthonomus pomorum, Atomaria linearis, Blastophagus
piniperda, Blitophaga undata, Bruchus rufimanus,
Bruchus pisorum, Bruchus lentis, Byctiscus betulae,
Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus
assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis,
Conoderus vespertinus, Crioceris asparagi, Diabrotica
longicornis, Diabrotica 12-punctata, Diabrotica
virgifera, Epilachna varivestis, Epitrix hirtipennis,
Eutinobothrus brasiliensis, Hylobius abietis, Hypera
brunneipennis, Hypera postica, Ips typographus, Lema
bilineata, Lema melanopus, Leptinotarsa decemlineata,
Limonius californicus, Lissorhoptrus oryzophilus,
Melanotus communis, Meligethes aeneus, Melolontha
hippocastani, Melolontha melolontha, Oulema oryzae,
Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon
cochleariae, Phyllotreta chrysocephala, Phyllophaga
sp., Phyllopertha horticola, Phyllotreta nemorum,
Phyllotreta striolata, Popillia japonica, Sitona
lineatus and Sitophilus granaria;
Diptera, for example Aedes aegypti, Aedes vexans,
Anastrepha ludens, Anopheles maculipennis, Ceratitis
capitata, Chrysomya bezziana, Chrysomya hominivorax,
Chrysomya macellaria, Contarinia sorghicola, Cordylobia
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anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus
oleae, Dasineura brassicae, Fannia canicularis,
Gasterophilus intestinalis, Glossina morsitans,
Haematobia irritans, Haplodiplosis equestris, Hylemyia
platura, Hypoderma lineata, Liriomyza sativae,
Liriomyza trifolii, Lucilia caprina, Lucilia cuprina,
Lucilia sericata, Lycoria pectoralis, Mayetiola
destructor, Musca domestica, Muscina stabulans, Oestrus
ovis, Oscinella frit, Pegomya hysocyami, Phorbia
antiqua, Phorbia brassicae, Phorbia coarctata,
Rhagoletis cerasi, Rhagoletis pomonella, Tabanus
bovinus, Tipula oleracea and Tipula paludosa;
Thysanoptera, for example Frankliniella fusca,
Frankliniella occidentalis, Frankliniella tritici,
Scirtothrips citri, Thrips oryzae, Thrips palmi and
Thrips tabaci;
Hymenoptera, for example Athalia rosae, Atta
cephalotes, Atta sexdens, Atta texana, Hoplocampa
minuta, Hoplocampa testudinea, Monomorium pharaonis,
Solenopsis geminata and Solenopsis invicta;
Heteroptera, for example Acrosternum hilare, Blissus
leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus,
Dysdercus intermedius, Eurygaster integriceps,
Euschistus impictiventris, Leptoglossus phyllopus,
Lygus lineolaris, Lygus pratensis, Nezara viridula,
Piesma quadrata, Solubea insularis and Thyanta
perditor;
Homoptera, for example Acyrthosiphon onobrychis,
Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis
forbesi, Aphis pomi, Aphis gossypii, Aphis
grossulariae, Aphis schneideri, Aphis spiraecola, Aphis
sambuci, Acyrthosiphon pisum, Aulacorthum solani,
Brachycaudus cardui, Brachycaudus helichrysi,
Brachycaudus persicae, Brachycaudus prunicola,
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Brevicoryne brassicae, Capitophorus horni, Cerosipha
gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis,
Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis
radicola, Dysaulacorthum pseudosolani, Dysaphis
plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus
pruni, Hyperomyzus lactucae, Macrosiphum avenae,
Macrosiphum euphorbiae, Macrosiphon rosae, Megoura
viciae, Melanaphis pyrarius, Metopolophium dirhodum,
Myzodes persicae, Myzus ascalonicus, Myzus cerasi,
Myzus varians, Nasonovia ribis-nigri, Nilaparvata
lugens, Pemphigus bursarius, Perkinsiella saccharicida,
Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus
ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi,
Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali,
Schizaphis graminum, Schizoneura lanuginosa, Sitobion
avenae, Trialeurodes vaporariorum, Toxoptera aurantii
and Viteus vitifolii;
Termites (Isoptera), e.g. Calotermes flavicollis,
Leucotermes flavipes, Reticulitermes lucifugus and
Termes natalensis;
Orthoptera, e.g. Acheta domestica, Blatta orientalis,
Blattella germanica, Forficula auricularia, Gryllotalpa
gryllotalpa, Locusta migratoria, Melanoplus bivittatus,
Melanoplus femur-rubrum, Melanoplus mexicanus,
Melanoplus sanguinipes, Melanoplus spretus, Nomadacris
septemfasciata, Periplaneta americana, Schistocerca
americana, Schistocerca peregrina, Stauronotus
maroccanus and Tachycines asynamorus;
Arachnoidea, for example Acarina, e.g. from the
Argasidae, Ixodidae and Sarcoptidae families, e.g.
Amblyomma americanum, Amblyomma variegatum, Argas
persicus, Boophilus annulatus, Boophilus decoloratus,
Boophilus microplus, Dermacentor silvarum, Hyalomma
truncatum, Ixodes ricinus, Ixodes rubicundus,
Ornithodorus moubata, Otobius megnini, Dermanyssus
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gallinae, Psoroptes ovis, Rhipicephalus appendiculatus,
Rhipicephalus evertsi, Sarcoptes scabiei, and
Eriophyidae spp., e.g. Aculus schlechtendali,
Phyllocoptrata oleivora and Eriophyes sheldoni;
Tarsonemidae spp., e.g. Phytonemus pallidus and
Polyphagotarsonemus latus; Tenuipalpidae spp., e.g.
Brevipalpus phoenicis; Tetranychidae spp., e.g.
Tetranychus cinnabarinus, Tetranychus kanzawai,
Tetranychus pacificus, Tetranychus telarius and
Tetranychus urticae, Panonychus ulmi, Panonychus citri
and Oligonychus pratensis;
Nematodes, in particular nematodes which parasitize
plants, e.g. plant root knot nematodes, Meloidogyne
hapla, Meloidogyne incognita, Meloidogyne javanica, and
other Meloidogyne species; cyst-forming nematodes,
Globodera rostochiensis and other Globodera species;
Heterodera avenae, Heterodera glycines, Heterodera
schachtii, Heterodera trifolii, and other Heterodera
species; seed gall nematodes, Anguina species; stem and
foliar nematodes, Aphelenchoides species; sting
nematodes, Belonolaimus longicaudatus and other
Belonolaimus species; pine nematodes, Bursaphelenchus
xylophilus and other Bursaphelenchus species; ring
nematodes, Criconema species, Criconemella species,
Criconemoides species, Mesocriconema species; stem and
bulb nematodes, Ditylenchus destructor, Ditylenchus
dipsaci and other Ditylenchus species; awl nematodes,
Dolichodorus species; spiral nematodes,
Heliocotylenchus multicinctus and other Helicotylenchus
species; sheath and sheathoid nematodes,
Hemicycliophora species and Hemicriconemoides species;
Hirshmanniella species; lance nematodes, Hoploaimus
species; false rootknot nematodes, Nacobbus species;
needle nematodes, Longidorus elongatus and other
Longidorus species; lesion nematodes, Pratylenchus
neglectus, Pratylenchus penetrans, Pratylenchus
curvitatus, Pratylenchus goodeyi and other Pratylenchus
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species; burrowing nematodes, Radopholus similis and
other Radopholus species; reniform nematodes,
Rotylenchus robustus and other Rotylenchus species;
Scutellonema species; stubby root nematodes,
Trichodorus primitivus and other Trichodorus species,
Paratrichodorus species; stunt nematodes,
Tylenchorhynchus claytoni, Tylenchorhynchus dubius and
other Tylenchorhynchus species; citrus nematodes,
Tylenchulus species; dagger nematodes, Xiphinema
species;
and rice pathogens, e.g. rice water weevil
(Lissorhoptrus oryzaphilus), rice stem borer (Chilo
suppresalis), rice leaf roller, rice leaf beetle, rice
leaf miner (Agromyca oryzae), leafhoppers (Nephotettix
spp.; especially smaller brown leafhopper, green rice
leafhopper), planthoppers (Delphacidae; especially
white backed planthopper, brown rice planthopper),
stinkbugs.
The term "phytopathogenic fungi" describes but is not
limited to the following species:
Blumeria graminis (powdery mildew) on cereals, Erysiphe
cichoracearum and Sphaerotheca fuliginea on cucurbits,
Podosphaera leucotricha on apples, Uncinula necator on
grape vines, Puccinia species on cereals, Rhizoctonia
species on cotton, rice and lawns, Ustilago species on
cereals and sugar cane, Venturia inaequalis on apples,
Bipolaris and Drechslera species on cereals, rice and
lawns, Septoria nodorum on wheat, Botrytis cinerea on
strawberries, vegetables, ornamental plants and grape
vines, Mycosphaerella species on bananas, peanuts and
cereals, Pseudocercosporella herpotrichoides on wheat
and barley, Pyricularia oryzae on rice, Phytophthora
infestans on potatoes and tomatoes, Pseudoperonospora
species on cucurbits and hops, Plasmopara viticola on
grape vines, Alternaria species on fruit and
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vegetables, and also Fusarium and Verticillium species,
Bipolaris and Drechslera species and also Pyricularia
oryzae, Corticium sasakii (syn. Rhizoctonia solani) and
Cochliobolus miyabeanus on rice plants and, if
appropriate, on their seeds, Paecilomyces variotii on
materials such as wood.
In addition, the amphiphilic polymer compositions
according to the invention are suitable for the
preparation of aqueous active substance compositions of
pharmaceutical active substances and prodrugs. These
include benzodiazepines, antihypertensives, vitamins,
cytostatics, in particular taxol, anesthetics,
neuroleptics, antidepressants, antibiotics,
antimycotics, fungicides, chemotherapeutics, urologics,
thrombocyte aggregation inhibitors, sulfonamides,
spasmolytics, hormones, immunglobulins, sera, thyroid
therapeutic agents, psychopharmacological agents,
antiparkinsonians and other antihyperkinetic agents,
ophthalmics, neuropathy preparations, calcium
metabolism regulators, muscle relaxants, narcotics,
antilipemics, hepatic therapeutic agents, coronary
agents, cardiacs, immunotherapeutics, regulatory
peptides and their inhibitors, hypnotics, sedatives,
gynecological agents, antigouts, fibrinolytic agents,
enzyme preparations and transport proteins, enzyme
inhibitors, emetics, circulation-promoting agents,
diuretics, diagnostics, corticoids, cholinergics, bile
duct therapeutics, antiasthmatics, broncholytics, beta-
receptor blockers, calcium antagonists, ACE inhibitors,
antiarteriosclerotics, antiinflammatories, anti-
coagulants, antihypotensives, antihypoglycemics,
antihypertonics, antifibrinolytics, antiepileptics,
antiemetics, antidotes, antidiabetics, antiarrhythmics,
antianemics, antiallergics, anthelmintics, analgesics,
analeptics, aldosterone. antagonists and slimming
agents. Examples of suitable pharmaceutical active
substances are in particular the active substances
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mentioned in paragraphs 0105 to 0131 of US
2003/0157170.
In addition, the amphiphilic polymer compositions
according to the invention are suitable for the
preparation of aqueous compositions of cosmetic active
substances, in particular of cosmetic oils and fats,
such as peanut oil, jojoba oil, coconut oil, almond
oil, olive oil, palm oil, castor oil, soybean oil or
wheat germ oil, essential oils, such as mountain pine
oil, lavender oil, rosemary oil, spruce needle oil,
pine needle oil, eucalyptus oil, peppermint oil, sage
oil, bergamot oil, turpentine oil, Melissa oil, juniper
oil, lemon oil, anise oil, cardamom oil, camphor oil,
and the like, or for mixtures of these oils.
In addition, the amphiphilic polymer compositions
according to the invention are suitable for the
preparation of aqueous compositions of food
supplements, such as water-insoluble vitamins and
provitamins, such as vitamin A, vitamin A acetate,
vitamin D, vitamin E, tocopherol derivatives, such as
tocopherol acetate, and vitamin K.
In addition, the amphiphilic polymer compositions
according to the invention are suitable for the
preparation preferably of aqueous compositions for seed
treatment.
Examples of formulation types are emulsifiable
concentrates, suspensions, soluble concentrates,
dispersible concentrates, pastes, pellets, wettable
powders, dustable powders (DP) or granules (GR, FG, GG,
MG) which can be either soluble or dispersible in
water. Standard formulation types for seed treatment
are FS (flowable concentrates), LS (solutions), DS
(powders for dry treatment), WS (water dispersible
powders for slurry treatment), SS (water-soluble
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powders SS) and ES (emulsions). The preparation of
these formulations and the technology necessary
therefor are known to a person skilled in the art (cf.
US 3 060 084, EP-A 707 445 (for liquid concentrates),
Browning, "Agglomeration", Chemical Engineering, Dec.
4, 1967, 147-48, Perry's Chemical Engineer's Handbook,
4th Ed., McGraw-Hill, New York, 1963, pp. 8-57 and ff.,
WO 91/13546, US 4 172 714, US 4 144 050, US 3 920 442,
US 5 180 587, US 5 232 701, US 5 208 030, GB 2 095 558,
US 3 299 566, Klingman, Weed Control as a Science, John
Wiley and Sons Inc., New York, 1961, Hance et al., Weed
Control Handbook, 8th Ed., Blackwell Scientific
Publications, Oxford, 1989 and Mollet, H., Grubemann,
A., Formulation Technology, Wiley VCH Verlag GmbH,
Weinheim (Federal Republic of Germany), 2001, 2. D. A.
Knowles, Chemistry and Technology of Agrochemical
Formulations, Kluwer Academic Publishers, Dordrecht,
1998 (ISBN 0-7514-0443-8).
The present invention also comprises seeds which have
been treated with pesticide-comprising aqueous polymer
dispersions. The amounts of pesticides expended in the
seed treatment are generally from 0.1 to 10 kg/100 kg
of seeds, preferably 1 to 5 kg/100 kg, in particular 1
to 2.5 kg/100 kg.
In a preferred embodiment according to the invention,
use is made of polymers which can be obtained by
copolymerization of the following monomers:
(A) optionally at least one ethylenically
unsaturated mono- or dicarboxylic acid with 3
to 8 carbon atoms and/or at least one anhydride
derived from a mono- or dicarboxylic acid with
3 to 8 carbon atoms. Examples of ethylenically
unsaturated mono- or dicarboxylic acids with 3
to 8 carbon atoms are (meth)acrylic acid,
maleic acid, fumaric acid or crotonic acid;
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very particular preference is given to acrylic
acid.
Mention may be made, as anhydrides derived from
a mono- or dicarboxylic acid with 3 to 8 carbon
atoms, for example, of maleic anhydride,
itaconic anhydride, citraconic anhydride or
methylenemalonic anhydride, preferably itaconic
anhydride and maleic anhydride and very
particularly preferably maleic anhydride.
Mixed anhydrides are also possible, for example
the mixed anhydride of (meth)acrylic acid and
acetic acid.
(B) At least one vinylaromatic compound, for
example of the general formula (VIII)
H R'5
R14
(R'6)
k
(VIII)
in which R14 and R15, independently of one
another, are each hydrogen, methyl or ethyl, R16
is methyl or ethyl and k is an integer from 0
to 2; preferably, R14 and R15 are each hydrogen
and preferably k = 0.
Use is preferably made, as (B), of a-
methylstyrene and very particularly preferably
of styrene.
(C) At least one alkoxylated unsaturated ether of
the general formula (I)
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R3 R4
~
Y
R 0 On R6
RZ Rs
(I)
in which the variables in formula (I) are
defined as follows:
Rl, Rz and R3 are identical or different and are chosen
from hydrogen or C1-Cq-alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl and tert-butyl, particularly preferably
methyl or hydrogen;
R9 and R5 are each identical or different and are chosen
from hydrogen or C1-C9-alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl and tert-butyl, particularly preferably
methyl or hydrogen;
R6 is chosen from hydrogen, S03M, P03M2 and preferably
organic radicals, such as C1-C30-alkyl, preferably
linear or branched, such as methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl,
neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl,
n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl or n-
eicosyl; particularly preferably C1-C4-alkyl, such
as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl and tert-butyl; CO-H (formyl)
or CO-C1-C20-alkyl, particularly preferably acetyl,
propionyl, n-butyryl, n-stearoyl or n-lauroyl; or
CO-C6-C19-aryl, such as, for example, a-naphthoyl,
0-naphthoyl and preferably benzoyl CO-C6H5,
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M is alkali metal, in particular sodium or
potassium, or NHq+ or CH3,
n is an integer from 3 to 100, preferably from 10 to
40,
y is an integer from 0 to 10, preferably 1 to 10 and
particularly preferably 1 or 2.
Particularly preferably, R 4 and R5 are each hydrogen.
Particularly preferably, R1 and R3 are hydrogen, R2 is
chosen from hydrogen or methyl, and y is 1.
Optionally, one or more additional monoethylenically
unsaturated monomers (D) can be copolymerized.
The monomer of monomers (D) which can optionally be
copolymerized in the polymers used in the process
according to the invention are different from (A)
Mention may be made, as preferred monomers (D), of:
ethylenically unsaturated C3-C8-carboxylic acid
derivatives of the general formula (II)
O
R7 OR9
R$
(II)
acrylamides of the formula (III),
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O R
R' N i
\ R 9
R8
(III)
noncyclic amides of the general formula (IVa) and
cyclic amides of the general formula (IVb)
R7 Rr
N''-R4 ( IVa ) N ( IVb )
Ox $ R (CH2)a ~(CH 2)x
5 O
C1-CZO-alkyl vinyl ethers, such as methyl vinyl ether,
ethyl vinyl ether, n-propyl vinyl ether, isopropyl
vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether,
2-ethylhexyl vinyl ether or n-octadecyl vinyl ether;
N-vinyl derivatives of nitrogenous aromatic compounds,
preferably N-vinylimidazole, 2-methyl-l-vinylimidazole,
N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine,
4-vinylpyridine, 4-vinylpyridine N-oxide, N-
vinylimidazoline or N-vinyl-2-methylimidazoline;
alkoxylated unsaturated ethers of the general formula
(V),
Ra
O
R7 X 0 /m'R
R5
R8
(V)
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esters and amides of the general formula (VI),
0
R7 X R9
~. ~ /
A-N
R 8 R9
(VI)
unsaturated esters of the general formula (VII)
0
0--~
R~o
Ra
(VII)
Monomers comprising sulfonate, phosphate or phosphonate
groups are furthermore suitable, such as, for example,
vinylsulfonic acid and vinylphosphonic acid and
compounds of the general formula (IX)
O
R' O
8
R O+b PO3H2
(IX)
it being possible for phosphate groups, sulfonate
groups or phosphonate groups to be present, if
appropriate, partly or completely in the form of alkali
metal salts.
the variables being defined as follows:
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R' is chosen from unbranched or branched C1-Clo-alkyl,
such as methyl, ethyl, n-propyl, isopropyl, n-
butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-
hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;
particularly preferably C1-Cq-alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
butyl and tert-butyl,
and in particular hydrogen;
R8 is chosen from unbranched or branched C1-Clo-alkyl,
such as methyl, ethyl, n-propyl, isopropyl, n-
butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-
hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;
particularly preferably C1-Cq-alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
butyl and tert-butyl,
in particular methyl
and in particular hydrogen;
R9 are identical or different and are C1-C22-alkyl,
branched or unbranched, such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl,
neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-
decyl, n-dodecyl or n-eicosyl; particularly
preferably C1-C4-alkyl, such as methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, sec-butyl and
tert-butyl, or hydrogen; with the proviso that, in
the formula (II), R9 is not hydrogen;
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A1 is identical or different and is CZ-C6-alkylene, for
example -CH2-, -CH (CH3) -, - (CHZ) Z-, -CH2-CH (CH3) -,
- ( CH2 ) 3-. -CHZ-CH ( CzHs ) -. - ( CHZ ) 9-, - (CH2 ) s-, - ( CHz ) 6-,
preferably C1-C3-alkylene; in particular -(CH2) Z-,
-CHZ-CH ( CH3 ) - and -CHZ-CH ( CZH5 ) -;
x is an integer ranging from 2 to 6, preferably 3 to
5;
a is an integer ranging from 0 to 6, preferably
ranging from 0 to 2;
b is an integer ranging from 1 to 40, preferably 1 to
10;
m is an integer ranging from 2 to 200, preferably 10
to 40;
R10 and R" are identical or different and are chosen
from hydrogen or unbranched or branched C1-Clo-
alkyl, unbranched and branched C1-Clo-alkyl being
defined as above;
X is oxygen or N-R12;
RlZ is chosen from unbranched or branched C1-Clo-alkyl,
such as methyl, ethyl, n-propyl, isopropyl, n-
butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-
hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-
hexyl; and in particular hydrogen or methyl;
phenyl.
The remaining variables are defined as above.
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Compounds of the formula (III) chosen by way of example
are (meth)acrylamides, such as acrylamide, N-
methylacrylamide, N,N-dimethylacrylamide, N-
ethylacrylamide, N-propylacrylamide, N-(tert-
butyl)acrylamide, N-(tert-octyl)acrylamide, N-undecyl-
acrylamide or the corresponding methacrylamides.
Compounds of the formula (IVa) chosen by way of example
are N-vinylcarboxamides, such as N-vinylformamide,
N-vinyl-N-methylformamide, N-vinylacetamide or
N-vinyl-N-methylacetamide; representatives of compounds
of the formula (IVb) chosen by way of example are
N-vinylpyrrolidone, N-vinyl-4-piperidone and
N-vinyl-epsilon-caprolactam.
Compounds of the formula (VI) chosen by way of example
are (meth)acrylates and (meth)acrylamides, such as
N,N-dialkylaminoalkyl (meth)acrylates or
N,N-dialkylaminoalkyl(meth)acrylamides; examples are
N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl
methacrylate, N,N-diethylaminoethyl acrylate,
N,N-diethylaminoethyl methacrylate, N,N-dimethyl-
aminopropyl acrylate, N,N-dimethylaminopropyl meth-
acrylate, N,N-diethylaminopropyl acrylate, N,N-diethyl-
aminopropyl methacrylate, 2-(N,N-dimethyl-
amino)ethylacrylamide, 2-(N,N-dimethylamino)ethyl-
methacrylamide, 2-(N,N-diethylamino)ethylacrylamide, 2-
(N,N-diethylamino)ethylmethacrylamide, 3-(N,N-dimethyl-
amino) propylacrylamide and 3-(N,N-dimethylamino)propyl-
methacrylamide.
Compounds of the formula (VII) chosen by way of example
are vinyl acetate, vinyl propionate, vinyl butyrate,
vinyl 2-ethylhexanoate or vinyl laurate.
Preference is given to the use as monomers (D) of
acrylic esters.
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Use is very particularly preferably made, as monomer
(D), of methyl acrylate, methyl methacrylate,
acrylamide, vinyl n-butyl ether, vinyl isobutyl ether,
N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole,
4-vinylpyridine, vinylphosphonic acid or vinylsulfonic
acid.
In one embodiment of the present invention, the
monomers (A) to (D) are copolymerized as follows:
(A) 0 to 50% by weight of at least one ethylenically
unsaturated mono- or dicarboxylic acid with 3 to 8
carbon atoms or at least one anhydride derived from
a mono- or dicarboxylic acid with 3 to 8 carbon
atoms, preferably 5 to 30% by weight,
(B) 5 to 80% by weight of at least one hydrophobic
monomer, preferably 8 to 50% by weight,
(C) 10 to 90% by weight of at least one alkoxylated
unsaturated ether of the general formula (I),
preferably 40 to 75% by weight,
(D) 0 to 20% by weight of at least one additional
monomer, preferably 2 to 10% by weight, very
particularly preferably 1 to 5% by weight,
the monomers being defined as above.
The polymers described can be prepared as follows. It
is possible to copolymerize the monomers (A) , (B), (C)
and, if appropriate (D) with one another by solution
polymerization, precipitation polymerization or,
preferably, under solvent-free conditions by bulk
polymerization. In this connection, (A), (B), (C) and,
if appropriate, (D) can copolymerize in the form of
random copolymers or as block copolymers.
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Pressure and temperature conditions for a
copolymerization of (A), (B), (C) and, if appropriate,
(D) are generally not critical. The temperatures, for
example, range from 60 to 200 C, preferably 90 to
160 C, and the pressure, for example, ranges from 1 to
bar, preferably 1 to 3 bar.
Possible reaction times are, for example, 0.5 hour to
12 hours, although even shorter and longer reaction
10 times can be envisaged.
Possible solvents are preferably those solvents which
are regarded as inert with regard to anhydrides derived
from dicarboxylic acids with 3 to 8 carbon atoms, in
particular acetone, tetrahydrofuran or 1,4-dioxane.
Aromatic and aliphatic hydrocarbons, for example
toluene, ortho-xylene, meta-xylene, para-xylene,
ethylbenzene or mixtures of one or more of the
abovementioned aromatic hydrocarbons, n-hexane,
petroleum ether or isododecane are suitable as
precipitants. Mixtures of aromatic and aliphatic
hydrocarbons are also suitable. In addition, water can
also be used as solvent.
Preferably, polymerization is carried out in the form
of a bulk polymerization without the addition of
solvents.
If R6 is chosen to be hydrogen, it can be advantageous
to add certain amounts, for example 1 to 30% by weight,
based on the weight of all monomers, of water and thus
to prevent the formation of crosslinked copolymers.
Modifiers can be used, for example mercaptoethanol or
n-dodecyl mercaptan. Suitable amounts are, for example,
0.1 to 6% by weight, based on the weight of all
monomers.
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The copolymerization is advantageously started by
initiators, for example peroxides or hydroperoxides.
Mention may be made, as peroxides or hydroperoxides,
for example, of di(tert-butyl) peroxide, tert-butyl
peroctoate, tert-butyl perpivalate, tert-butyl per(2-
ethylhexanoate), tert-butyl permaleate, tert-butyl
perisobutyrate, benzoyl peroxide, diacetyl peroxide,
succinyl peroxide, p-chlorobenzoyl peroxide or
dicyclohexyl peroxydicarbonate. The use of redox
initiators is also suitable and furthermore azo
compounds, such as 2,2'-azobis(isobutyronitrile),
2,2'-azobis(2-methylpropionamidine) dihydrochloride and
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).
Generally, these initiators are used in amounts of 0.1
to 20% by weight, preferably 0.2 to 15% by weight,
calculated with regard to the weight of all monomers.
Polymers are obtained by the copolymerization described
above. The precipitated polymers may comprise compounds
of the general formula (I) and they can be subjected to
the purification according to conventional methods,
for example reprecipitation or extractive removal of
nonreactive monomers. However, the purification can be
omitted and the copolymers described above can be used
in the mixture with compound (I). If a solvent or
precipitant has been used, it is possible to remove
this after the copolymerization has ended, for example
by distillation.
The polydispersity of the polymers described above
generally lies between 2 and 10, preferably up to 7,
but higher values can be accepted.
The K values of the polymers described above come to 6
to 100, preferably 10 to 60 (measured according to
H. Fikentscher at 25 C in, for example, water or
tetrahydrofuran and a polymer concentration of 1% by
weight).
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The preparation of monomers of the general formula (I)
is known per se.
R 3 R4
1 ~~
R yO 0 JnR6
RZ R
5 (I)
If it is desired to prepare derivatives with R6 equal
to -CO-H (formyl) or -CO-C1-C20-alkyl or -CO-C6-C14-aryl,
the starting material is advantageously the
corresponding derivative with R6 equal to hydrogen and
it is reacted, for example, with mixed anhydrides or
symmetrical anhydrides. Particularly preferred
anhydrides are acetic anhydride, benzoic anhydride or
H-CO-O-COCH3.
The invention is described more fully below with
reference to the examples.
Examples:
Various substances with a poor solubility in water were
used in order to test the suitability of the polymers
according to the invention as solubility promoters.
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Substance Solubility in
distilled water (mg/1)
Pyrene 0.13
Uvinul T150 (octyl 0.007
triazone)
Cl Solvent Red (colorant) < 0.001
Cinidon-ethyl (herbicide) 0.057
Piroxicam (painkiller) 23
Pyraclostrobin (fungicide) 2.4
Metconazole (fungicide) 15
Table 1
The following measures were taken in order to test the
suitability of the polymers as solubility promoters:
Process 1: Solid solution
0.5 g of a polymer and 0.1 g of a chosen substance were
dissolved in DMF (ca. 20 ml). The mixture was stirred
and DMF was completely evaporated so that a liquid
dispersion of the organic molecules in the polymer was
obtained. A buffered aqueous solution (100 ml, pH 6.8)
was added and the mixture was stirred for 24 hours.
Stable solutions or dispersions are obtained, i.e. no
sedimentation could be observed even after ca. one
week. After filtration, the solution was analyzed by
means of HPLC (UV detector) and the concentration of
the substances was determined.
Process 2: Melt emulsification
10 g of active substance melt were stirred into 90 g of
aqueous polymer solution at a temperature of 65 C
comprising 30 g of polymer. Depending on the viscosity
of the polymer solution and active substance, a
magnetic stirrer or an UltraTurrax was used for the
dissolution. The time required up to dissolution
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equilibrium depends on the polymer and active substance
and can last from seconds to hours. Stable solutions or
dispersions are obtained, i.e. no sedimentation could
be observed even after ca. one week.
Process 3: Phase inversion
g of the liquid or solid active substance and 30 g
of polymer were dissolved in an organic solvent with a
10 boiling point of less than 100 C. Water was then added
with stirring and the organic solvent was subsequently
removed on a rotary evaporator. As much water was added
to give the resulting aqueous formulation an active
substance content of 10% and a polymer content of 30%.
Stable solutions or dispersions are obtained.
Examples of the preparation of the polymers
Preparation example 1: Preparation of a terpolymer
(Pluriol AlOR/acrylic acid/styrene) (1:1:1)
373.5 g (0.75 mol) of Pluriol A010R and 78 g (0.77 mol)
of acetic anhydride were heated to 150 C with stirring
and maintained at 150 C for one hour. Subsequently,
54 g (0.75 mol) of acrylic acid, 78.0 g (0.75 mol) of
styrene and 10.1 g of di(tert-butyl) peroxide were
metered in in five hours. Subsequently, the mixture was
heated at 150 C for a further half hour.
K value = 17 (1% in water)
Preparation example 2: Preparation of a terpolymer
(Pluriol AlOR/acrylic acid/styrene) (1:1:3)
373.5 g (0.75 mol) of Pluriol AO10R were placed in a 21
vessel and heated to 150 C under a slight nitrogen
stream. After reaching this temperature, 54 g
(0.75 mol) of acrylic acid, 234.0 g of styrene and
13.23 g of di(tert-butyl) peroxide were metered in in
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five hours. Subsequently, the batch was maintained at
150 C for half an hour.
K value (1% in water) = 23
GPC in N,N-dimethylacetamide (PMMA standard):
Mn = 3100, Mw = 63 000
Formulation examples
Formulation example 1:
Dissolution results with polymer from preparation
example 1 according to process 1:
Active substance Solubility in Solubility in the
distilled water presence of
[mg/1] polymer [mg/1]
Uvinul T150 0.007 2.3
Cinidon-ethyl 0.057 0.5
Pyrene 0.13 7
Piroxicam 23 92
Table 2
Formulation example 2:
Dissolution results with polymer from preparation
example 2 according to process 1:
Active substance Solubility in Solubility in the
distilled water presence of
[mg/1] polymer [mg/1]
Uvinul T150 0.007 79
Cinidon-ethyl 0.057 57
Pyrene ' 0.13 63
CI Solvent Red < 0.001 0.2
Piroxicam 23 167
Table 3
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Formulation example 3:
Dissolution of pyraclostrobin with polymer from
preparation example 2 according to process 3
10 g of the fungicide pyraclostrobin were dissolved in
100 g of THF together with 30 g of polymer from
example 2. As much water was then added with stirring
(magnetic stirrer) to give, after removal of the
organic solvent on a rotary evaporator, the resulting
aqueous formulation an active substance content of 10%
and a polymer content of 30%.
The active substance pyraclostrobin is, at 70 C, a
satisfactorily fluid melt (viscosity 2200 mPa.s) and
can also be formulated according to process 2. The
formulation is in both cases homogeneous, is stable
towards sedimentation for at least several months and
can be diluted with water (tested with demineralized
water and water of 10 German hardness) without
resulting in sedimentation and crystallization.
The polymer/active substance particles are spherical
and have a diameter of ca. 30 nm. No active substance
crystals can be detected under an electron microscope
(TEM).
The nanoparticulate fungicidal formulation, which
comprised only water, polymer and active substance, was
compared, with regard to the biological action, with a
commercial formulation of the active substance
pyraclostrobin in a greenhouse.
For this, the active substance formulations were
diluted with faucet water to the desired active
substance concentrations (between 4 and 250 ppm).
Application on tomato plants was carried out in a spray
booth with a volume of 25 ml, which corresponds to an
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amount of water conventionally used in practice of
ca. 500 1/ha. The standard fungus (phytophthora
infestans) was inoculated 7 days after treatment. The
test plants were placed in a greenhouse at 18-20 C and
90% relative humidity. Scoring was carried out 5 days
after inoculation by determination of the infestation
of the leaves in percent.
The results of the biological testing are summarized in
the following table (table 4).
Table 4: Phytophthora infestans - Infestation [%] on
tomatoes after five days as a function of the active
substance content
Infestation [%] Infestation [o]
Amount expended Formulation Commercial
[ppm] example 3 productl
250 0 0
63 0 0
16 0 0
4 3 4
1) EC formulation:
23.5% by weight of pyraclostrobin,
4.7% by weight of anionic wetting agent and
4.7% by weight of nonionic wetting agent in
67.1% by weight of an aromatic solvent
Formulation example 4:
Dissolution of pyraclostrobin from preparation
example 2 according to process 2
Pyraclostrobin is, at 70 C, a satisfactorily fluid melt
(viscosity 2200 mPa.s) and was also formulated
according to the general method 2 at a temperature of
70 C. The active substance composition obtained was
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homogeneous, was virtually transparent visually, was
stable towards sedimentation for at least several
months and could be diluted with water (both with
demineralized water and water with a German hardness of
10 ) without sedimentation or crystallization of the
active substance occurring. Depending on the active
substance/polymer ratio (between 1:2.5 and 1:1), mean
diameters of between 30 and 65 nm were measured by
dynamic light scattering. No active substance particles
could be detected under a transmission electron
microscope.
The nanoparticulate fungicidal formulation, which
comprised only water, polymer and active substance, was
compared, with regard to the biological action, with a
commercial formulation of the active substance
pyraclostrobin in a greenhouse.
For this, the active substance formulations were
diluted with faucet water to the desired active
substance concentrations (between 4 and 250 ppm).
Application on tomato plants was carried out in a spray
booth with a volume of 25 ml, which corresponds to an
amount of water conventionally used in practice of
ca. 500 1/ha. The standard fungus (phytophthora
infestans) was inoculated 7 days after treatment. The
test plants were placed in a greenhouse at 18-20 C and
90% relative humidity. Scoring was carried out 5 days
after inoculation by determination of the infestation
of the leaves in percent.
Table 4: Phytophthora infestans - Infestation [%] on
tomatoes after five days as a function of the active
substance content
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Infestation [o] Infestation [o]
Amount expended Formulation Commercial
[ppm] example 4 product'
250 0 0
63 0 0
16 0 0
4 6 4
1) EC formulation:
23.5% by weight of pyraclostrobin,
4.7% by weight of anionic wetting agent and
4.7% by weight of nonionic wetting agent in
67.1% by weight of an aromatic solvent
