[go: up one dir, main page]

WO2025223971A1 - Copolymères séquencés amphiphiles de polyacétal, leur production et leur utilisation dans des produits agrochimiques et des formulations agrochimiques - Google Patents

Copolymères séquencés amphiphiles de polyacétal, leur production et leur utilisation dans des produits agrochimiques et des formulations agrochimiques

Info

Publication number
WO2025223971A1
WO2025223971A1 PCT/EP2025/060536 EP2025060536W WO2025223971A1 WO 2025223971 A1 WO2025223971 A1 WO 2025223971A1 EP 2025060536 W EP2025060536 W EP 2025060536W WO 2025223971 A1 WO2025223971 A1 WO 2025223971A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyacetal
diol
acid
agrochemical
unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/060536
Other languages
English (en)
Inventor
Guido Vandermeulen
Frank Bienewald
Huelya KIRCHNER
Pavel TUZINA
Doris KREMZOW-GRAW
Adam BLANAZS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025223971A1 publication Critical patent/WO2025223971A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment
    • C08G2/34—Chemical modification by after-treatment by etherification
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3711—Polyacetal carboxylates

Definitions

  • Amphiphilic polyacetal block copolymers their production, and their use in agrochemical products and agrochemical formulations
  • the present invention relates to amphiphilic polyacetal block copolymers of general structure (a1)-(a2)-(a1), comprising one hydrophobic polyacetal-based middle block (a2) and two hydrophilic polyalkylene oxide-based outer blocks (a1).
  • the hydrophobic polyacetal-based block (a2) is obtainable by polyaddition of at least one vinyl ether monomer and at least one diol.
  • the hydrophilic polyalkylene oxide-based block (a1) comprises polyalkylene-oxide-derived moieties and, optionally, moieties derived from lactone(s) and/or hydroxy acid(s), those moieties being mixed such that the polymer backbone contains ester-functions within the polymer chains.
  • the present invention further relates to a process for obtaining such amphiphilic polyacetal block copolymers, the process being preferably carried out by an acid-catalyzed polyaddition in a first step and an alkoxylation in the second step.
  • the present invention relates to the use of such amphiphilic polyacetal block copolymers in agrochemical products and formulations, and further includes agrochemical compositions and agrochemical formulations comprising such polyacetal block polymers.
  • Agrochemicals such as pesticides (pesticidal active ingredients) are materials that provide large-scale control of agricultural pests including insects, pathogens, rodents, and weeds to optimize harvest yields.
  • Pesticidal active ingredients are typically applied to a plant or its seeds by spraying with a liquid composition comprising the active ingredient.
  • Pesticides are often solid particles, crystal-like particles or oily liquids, which must be dispersed or emulsified in the liquid composition to allow for homogeneous application.
  • Compositions comprising finely dispersed pesticidal active ingredients are typically obtained by the inclusion of dispersants.
  • dispersants include salts of naphthalene sulfonate formaldehyde condensates, salts of lignosulfonates, salts of maleic anhydride copolymers, salts of condensed phenol sulfonic acid and certain ethylene oxide/propylene oxide/ethylene oxide-triblock copolymers.
  • Polyalkylene oxides are important low-cost polymers with a wide range of applications. They have been extensively used as a basis to produce block copolymers which are widely employed in all kinds of formulations, including the use in agrochemical formulations.
  • block polymers (a1)-(a2)-(a1) comprising a hydrophobic polyalkylene oxide subunit (a2) and a hydrophilic polyalkylene oxide subunit (a1) are known polymers.
  • Their use in agrochemical formulations as well as in many other application areas are known as well, in particular triblock copolymers of ethylene and propylene oxide are widely used (e.g.
  • EO-PO-EO triblock copolymers such as Pluronic® PE 6400 and Pluronic® PE10500 by BASF SE. While some of these amphiphilic polyalkylene oxideblock copolymers having lower molecular weights show sufficient biodegradability (e.g. Pluronic® PE 6400), those with higher molecular weights (e.g. Pluronic® PE10400 and 10500 are characterized by very poor biodegradability. There is thus especially a need to find alternatives for the higher molecular weight amphiphilic polyalkylene oxide block copolymers.
  • DE4142130 describes broadly the use of polyacetals with K-values between 8 and 100 prepared via an acid- catalyzed polyaddition of a dihydroxy compound and a divinyl ether as additives to phosphate-free detergents.
  • the polyacetals were not alkoxylated to prepare amphiphilic block copolymers and no biodegradation data for the polyacetals were provided.
  • WO2016/090103 describes acetal-containing polyethylene oxide) polymers for the delivery of a therapeutic agent to a tumor cell.
  • the copolymerization of 1 ,4-butane diol divinyl ether and ethylene glycol is described resulting in a mixed hydrophobic-hydrophilic polyacetal core.
  • a thermoresponsive PEG- polyacetal-PEG ABA triblock copolymer with such a hydrophobic-hydrophilic polyacetal core is mentioned. All copolymers were prepared with pyridinium para-toluene sulfonate as the catalyst, which wass removed after polyaddition using an elaborate extraction process and is thus unfit for industrial purposes.
  • W02006/105123 describes PEG-polyacetal-PEG triblock copolymers, which incorporate an alkylated 1 ,3-propylene oxide building block in the hydrophobic polyacetal block.
  • These block copolymers are prepared using para toluene sulfonic acid in THF and are solely used for drug delivery in pharmaceutical applications. Also, here no biodegradation data are shown.
  • the patent solely highlights the pH-induced polymer degradability: it is well known that the acetal function hydrolyzes in acidic pH. In the current disclosure, degradability is induced by microbial enzymes and/or fungi present in activated sludge and/or soil.
  • DE4237337 describes block copolymers where each block contains acetal functional groups. These polyacetal block copolymers are prepared by the addition of a first polyacetal to a second polyacetal. The resulting polymers are used in phosphate-free detergents. In addition, some block copolymers are used as foam-free surfactants in automatic dishwasher applications. No biodegradation data were provided as well.
  • amides into a polymer backbone increases the stability, but also often lowers the biodegradation. Also, the amide-nitrogen atoms may interact in a different manner compared to the ester-functionalities and certainly different compared to the ether-functionalities of the polyalkylene oxides, typically resulting in poorer application performance.
  • WO2022/263355 has provided a first solution to the problem of insufficient biodegradation of the polyalkylene oxide-type polymers, the practical aspects of the solution found is still not satisfactory, as the two- step-reaction is lengthy and costly, as two completely different types of chemical reactions are employed (oxidation and polymerization) and the structural variations are not easily controlled as the oxidation leads to mixtures of compounds being diols (i.e. the starting material polyalkylene glycols), mono-ol-mono-carbonic acid (i.e. partially oxidized polyalkylene glycol) and di-carboxyl-polyalkylene oxide (i.e. fully oxidized polyalkylene glycol); those mixtures are then to be esterified to yield the “oxidized polyalkylene oxides”.
  • diols i.e. the starting material polyalkylene glycols
  • mono-ol-mono-carbonic acid i.e. partially oxidized polyalkylene glycol
  • the object of the present invention is to provide novel polymers based on polyalkylene-oxide-type polymers which show a significantly improved soil and activated sludge biodegradation while keeping or even improving their application performance, in particular in agrochemical compositions and formulations.
  • amphiphilic polyacetal block polymers described by the current invention are preferably produced by polyaddition of a diol and a vinyl ether resulting in a hydrophobic polyacetal, which subsequently is alkoxylated, preferably comprising the use of ethylene oxide.
  • the hydrophobic PO block is by the presently disclosed method thus exchanged with a hydrophobic polyacetal block. Since the oxygen content of the hydrophobic core is thereby increased, it is important to select certain hydrophobic diol and divinyl ether building blocks to allow for similar agrochemical active dispersing properties in the final amphiphilic triblock polyacetal block copolymers, while introducing soil and activated sludge biodegradation.
  • the inventive polymers exhibit near-identical molecular weights and physico-chemical properties
  • the inventive polymers exhibit significantly improved biodegradation properties, both in soil and in activated sludge, while retaining near-identical agrochemical active dispersing and/or emulsifying properties.
  • the present invention also provides for the use of at least one polyacetal triblock copolymer as defined herein, such polymer may be obtained by or obtainable by the process as also disclosed herein, in a composition, that is an agrochemical formulation or agrochemical product.,
  • composition being an agrochemical formulation or product, comprising at least one agrochemical active ingredient and at least one polyacetal triblock copolymer as defined herein, such polymer may be obtained by or obtainable by the process as also disclosed herein, wherein the agrochemical active ingredient is selected from pesticides, in particular herbicides, fungicides and insecticides.
  • the amphiphilic polyacetal triblock copolymer of this present invention has a general structure (a1)-(a2)-(a1), thus comprising one hydrophobic polyacetal-based block (a2) and two hydrophilic polyalkylene oxide-based blocks (a1 ), with (a1 ) and (a2) being sub-units within the polymer, the sub-units being linked by a chemical bond to form a triblock copolymer with (a2) being the middle block and (a1) being the outer blocks on both sides of the middle block (a2).
  • amphiphilic polyacetal triblock copolymer has the structure (a1)-(a2)-(a1), with (a1) and (a2) being sub-units within the polymer, the sub-units being linked by a chemical bond to form a triblock polymer, with (a2) being the one middle block and (a1) being the two outer blocks, wherein
  • (a1) is a unit comprising moieties derived from a) at least one alkylene oxide monomer (AO), wherein the AO comprises ethylene oxide, and optionally further comprises propylene oxide and/or butylene oxide; b) and optionally at least one moiety derived from at least one lactone and/or hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, such as alpha-lactones (i.e.
  • lactones preferably being beta-propiolactone, gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, delta- decalactone, gamma-decalactone, epsilon-decalactone; more preferably epsilon-caprolactone; and ii) hydroxy acid(s), such as those which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, more specifically an alpha-, beta- or gammahydroxy acid derived from the corresponding lactones by hydrolyzation, and lactic acid, glycolic acid,
  • (a2) is a unit comprising acetal moieties, such moieties being derived from the reaction of at least one diol with at least one divinyl ether, wherein the at least one diol is preferably selected from (mono-, di- or tri-) propylene glycol, (mono-, di- or tri-) butylene glycol, 1 ,2-pentane diol, 1,5-pentane diol, 1 ,4-butane diol, 1 ,2-butane diol, 2,5-dimethyl- 2,5-hexanediol, 2-butyne-1 ,4-diol, 3-hexyne-2,5-diol, butane-2,3-diol, 1,6-hexane diol, neopentyl glycol, polyTHF, polypropylene glycol), poly(butylene glycol), most preferably propylene glycol, butylene glycol or 1
  • block (co)polymer as used herein in any of the embodiments described means that the respective polymer consists of three -homo- or co-polymer subunits (“blocks”) linked by covalent bonds. “Three-block” copolymers have three distinct blocks (homo- and/or co-polymer subunits). Within the individual blocks the size/length of such a block may vary independently from the other blocks. The smallest length/size of a block is based on two individual monomers (as a minimum) but may be as large as 50 or even 100 or 200, and any number in between 2 and 200.
  • block copolymers are distinct from each other; such distinction can lie in their specific monomers being employed in one block but not the other block, in the amount of one monomer over the other monomer, the order of the monomers, or all of them.
  • the respective monomers to be employed for preparing the individual blocks of a block copolymer may be added in sequence. However, it is also possible that there is a transition of the feed from one monomer (or monomer mixture) to the other to produce so called “dirty structures” wherein at the edge/border of the respective block a small number of monomers of the respective neighboring block may be contained within the individual block to be considered (so called “dirty structures” or “dirty passages”). However, it is preferred that the block copolymer according to the present invention do essentially not contain any dirty structures at the respective border of the blocks, although for commercial reasons (i.e. mainly cost for efficient use of reactors etc.) small amounts of dirty structures may still be contained although not deliberately being made.
  • Sub-unit (a1) is a unit comprising moieties derived from a) at least one alkylene oxide monomer (AO), selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides, such as ethylene oxide (EO), 1 ,2-propylene oxide (PO), 1 ,2-butylene oxide (BO), 2,3-butylene oxide, 1 ,2-pentene oxide or 2,3-pentene oxide; from 1 ,4-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,4-diols; from 1 ,6-diols or their cyclic or oligomeric analogs, or being based on polymeric ethers of such 1 ,6-diols; or any of their mixtures in any ratio, either as blocks of certain polymeric units, or as statistical polymeric structures, or as polymers comprising one or more homo-block(s)
  • the sub-unit (a1) of the polyacetal triblock copolymer of the structure (a1)-(a2)-(a1) is an in principle linear polymer chain - which however may contain groups attached to the chain, such groups stemming from the AO employed - bearing one hydroxy end group at the end of each of the two sub-units (a1) in the tri-block copolymer chain.
  • the polymer comprises more than one AO-type
  • the polymer is a random copolymer, a block copolymer or a copolymer comprising mixed structures of block units (with each block being a homo-block or a random block itself) and statistical /random parts comprised of two or more alkylene oxides, with one of the monomers being ethylene oxide.
  • the total amount of AO always adds up to 100 wt.%.
  • the amount of EO is of from 0 to 100 wt.%, preferably from 10, more preferably from 20, even more preferably from 30, even more preferably from 40, such as from 50, 60, 70, 80 or even from 90 wt%, based on total AO,
  • the AO comprises EO.
  • the amount of another AO besides EO is the difference of the total weight of all AO minus the amount of EO.
  • PO and/or BO are - in a preferred embodiment - also included within the AO besides EO; the amount of PO and BO - if included - is for each separately from 0 to 100 wt.%, preferably up to 90, more preferably up to 80, even more preferably up to 70, even more preferably up to 60, and most preferably up to 50, and any number in between such as up to 5, 10, 15, 25, 30, 35, 40, 45, 55, 65, 75, 85 or up to 95.
  • PO and/or BO are present from 10, even more preferably from 20, even furthermore preferably from 30, such as from 40, 50, 60, 70, 80 or even from 90 wt%, each based on the total weight of AO, with the total amount of PO and BO (and other AO(s) if present) adding up to 100 wt.%.
  • the AO comprises EO and further comprises PO and/or butylene oxide.
  • the AO consists only of EO, and optionally PO and/or butylene oxide.
  • the alkylene oxides (AO) are selected from ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably only EO and PO are comprised, the amount of EO preferably being more than 80 wt%, more preferably being more than 90 wt%, and most preferably being more than 95 wt%, based on total AO, the total amount of PO and BO being up to 20 wt%, more preferably up to 10 wt%, and most preferably up to 5 wt%, each based on the total weight of AO, with the total amount of PO and BO adding up to 100wt.% for the sum of PO and BO, and with the total amount of AO adding up to 100wt.%;
  • the AO consists only of EO.
  • the total amount of all AO of course always adds up to 100%; thus, if the amount of for example EO is chosen, then the amount of the second AO can be chosen (up to 100 for EO plus the second AO), and if the sum is less than 100, a further AO can be chosen, and so on.
  • Sub-unit (a1) may optionally comprise - besides the AO mentioned before - also at least one moiety derived from at least one lactone and/or hydroxy acid, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, such as alpha-lactones (i.e.
  • lactones preferably being beta-propiolactone, gammabutyrolactone, delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, delta- decalactone, gamma-decalactone, epsilon-decalactone; more preferably epsilon-caprolactone; and ii) hydroxy acid(s), such as those which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, more specifically an alpha-, beta- or gamma-hydroxy acid derived from the corresponding lactones by hydrolyzation, and lactic acid, glycolic acid, 4-
  • Sub-unit (a1 ) is covalently linked on one side to sub-unit (a2).
  • the other side i.e. the side not linked to sub-unit (a2)
  • sub-unit (a1) bearing a hydroxy-group may however be modified (“capped” or “end-capped”) with a C1 -C4-alkyl, acetyl or acetal group.
  • Each sub-unit (a1) preferably consists of more than 70 weight percent, more preferably of more than 80 weight percent of ethylene oxide in relation to its total weight.
  • all sub-units (a1) together comprise from 20 to 80, more preferably from 30 to 70 weight percent in relation to the total weight of the polyacetal triblock copolymer.
  • Sub-unit (a2) is a unit comprising acetal moieties, such moieties being derived from the reaction of at least one diol with at least one divinyl ether, wherein the at least one diol is preferably selected from (mono-, di- or tri-) propylene glycol, (mono-, di- or tri-) butylene glycol, 1 ,2-pentane diol, 1,5-pentane diol, 1 ,4-butane diol, 1 ,2- butane diol, 2,5-dimethyl-2,5-hexanediol, 2-butyne-1 ,4-diol, 3-hexyne-2,5-diol, butane-2,3-diol, 1 ,6-hexane diol, neopentyl glycol, polyTHF, polypropylene glycol), polyputylene glycol), most preferably propylene glycol, butylene glyco
  • Sub-unit (a2) has a weight-average molecular weight of 1 ,000 to 20,000 g/mol, preferably 2,000 - 16,000 g/mol, most preferably 2,500 - 15,000 g/mol, as determined by size-exclusion chromatography using THF as an eluent and well-defined polystyrene standards with narrow molecular weight distributions.
  • Mw values are determined by the method as follows: OECD TG 118 (1996), which means in detail
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive and comparative polymers can be determined by size-exclusion chromatography.
  • the mobile phase (eluent) to be used is tetrahydrofuran (>99%), stabilized with ca. 250 ppm butyl hydroxy toluene (BHT).
  • BHT butyl hydroxy toluene
  • the concentration of inventive polymer in tetrahydrofuran is 1.0 g per L. After filtration (pore size 0.2 pm), 100 pL of this solution were injected into the Agilent Technologies 1200 Infinity Series GPC system. A PL-Gel Mixed E 3 pm column is used for separation. The GPC system is operated at a flow rate of 1 mL per min.
  • An Agilent RID G1362A may be used as the detection system.
  • Narrow molecular weight distribution poly(styrene) (PS) standards
  • Sub-unit (a2) comprises between 20 and 80, more preferably between 30 and 70 weight percentage in relation to the total weight of the polyacetal triblock copolymer.
  • (a1) is a unit comprising moieties derived from at least one alkylene oxide monomer (AO), wherein the AO comprises ethylene oxide and at least one moiety derived from at least one lactone and/or hydroxy acid, wherein the at least one lactone and/or hydroxy acid is epsilon-caprolactone, lactic acid or the hydroxy acid from epsilon-caprolactone, more preferably epsilon-caprolactone, and
  • (a2) is a unit comprising acetal moieties derived from at least one diol and at least one divinyl ether, the diol being selected from propylene glycol, butylene glycol, or 1 ,4-butane diol; and the divinyl ether is selected from dipropylene glycol divinyl ether, dibutylene glycol divinyl ether and 1 ,4- butane diol vinyl ether.
  • the polyacetal triblock copolymer of the general embodiment or - preferably - of any of the specifically preferred embodiments before contains sub-unit(s) (a2) having a weightaverage molecular weight of 2,500 - 15,000 g/mol per unit (a2).
  • the polyacetal triblock copolymer of the general embodiment or - preferably - of any of the specifically preferred embodiments before comprises as AO essentially only EO, PO and /or butylene oxide, with EO being required and PO and butylene oxide being optional. In a more preferred embodiment thereof, essentially only EO is comprised.
  • the polyacetal triblock copolymer of the general embodiment or - preferably - of any of the specifically preferred embodiments before comprises in sub-unit (a2) essentially only dipropylene glycol divinyl ether, dibutylene glycol divinyl ether or 1 ,4-butane diol divinyl ether.
  • (a1) is a unit comprising moieties derived from one alkylene oxide monomer (AO), wherein the AO comprises ethylene oxide, and
  • (a2) is a unit comprising acetal moieties derived from at least one diol and at least one divinyl ether, wherein the diol comprises 1 ,4-butane diol, and wherein the divinylether comprises 1 ,4-butane diol vinyl ether.
  • the polyacetal triblock copolymer of the general embodiment or - preferably - of the specifically preferred embodiment before - is end-capped on both ends of the polymer chains; thus, for structure (a1)-(a2)-(a1) the (al)-sub-units both bear an end-cap with the end-capping as defined before in the general description of the polyacetal triblock copolymer and - more preferably - with the preferences defined in that general polymer description and - even more preferably - in the specific embodiments.
  • the polyacetal triblock copolymer contains sub-units (a1) which are capped with a C1-C4-alkyl, acetyl or acetal group.
  • the present invention also encompasses a process to produce a polyacetal triblock copolymer as defined herein before in the general embodiment for the polymer and the specific embodiments thereof, wherein the polymer is obtained in two subsequent steps in either one of the following two alternative routes of Alternative 1 or Alternative 2, wherein in Alternative 1
  • step 1 unit (a2) is obtained by polyaddition of the at least one diol and the at least one divinyl ether; wherein the diol is used in a molar equivalent of 1 .2 to 1 .0 versus the divinyl ether, to obtain a polymer sub-unit (a2) having terminal hydroxyl groups on both ends; and
  • step 2 ethoxylation of the obtained unit (a2) from (step 1), optionally in the presence of at least one further compound selected from the following groups a) to d), with a) one or more lactone (i), b) one or more hydroxy acid (ii), c) propylene oxide, and d) butylene oxide, wherein preferably the at least one lactone and/or hydroxy acid is/are selected from the groups i) and/or ii), with i) lactone(s), i.e. cyclic esters, such as alpha-lactones (i.e.
  • lactones preferably being betapropiolactone, gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, epsilon- caprolactone, delta-decalactone, gamma-decalactone, epsilon-decalactone; more preferably epsilon-caprolactone; and ii) hydroxy acid(s), such as those which may be derived from any lactone by hydrolyzation, specifically from any lactone within group i) before, more specifically an alpha-, beta- or gamma-hydroxy acid derived from the corresponding lactones by hydrolyzation, and lactic acid, glycolic acid,
  • step 1 unit (a2) is obtained by polyaddition of the at least one diol and the at least one divinyl ether; wherein the divinyl ether is used in a molar equivalent of 1 .2 to 1 .0 versus the diol to obtain a polymer sub-unit (a2) having terminal vinyl ether groups; and
  • step 2 addition of at least one poly(alkylene oxide) to and reaction with the unit (a2) obtained in (step 1), wherein the poly(alkylene oxide) is made up from at least one C2-C8-alkylene oxide, preferably C2-C4-alkylene oxide, more preferably ethylene oxide and propylene oxide, most preferably only ethylene oxide, and optionally further bears a C1-C18-, preferably C1-C4-, more preferably C1 -C2-alkyl-ether end- group.
  • the poly(alkylene oxide) is made up from at least one C2-C8-alkylene oxide, preferably C2-C4-alkylene oxide, more preferably ethylene oxide and propylene oxide, most preferably only ethylene oxide, and optionally further bears a C1-C18-, preferably C1-C4-, more preferably C1 -C2-alkyl-ether end- group.
  • the poly(alkylene oxide) is preferably mono-methoxy-poly(ethylene oxide), having preferably a weight-average molecular weight of in between 750 and 10,000 g/mol, more preferably in between 750 and 5,000 g/mol, most preferably in between 750 and 2,500 g/mol.
  • step (1) can be performed using known procedures, conditions, solvents, catalysts, set-ups and equipment.
  • the vinyl ether and diol are mixed in the desired molar ratio in an anhydrous solvent, which acts as a diluent to control reaction temperature.
  • An acidic catalyst is added to start the reaction and reduce reaction time significantly.
  • the vinyl ethers and diols can be used as purchased or are freshly distilled or dried to eliminate water impurities.
  • Suitable catalysts can be any acidic compound, such as acetic acid, formic acid, methane sulfonic acid, sulfuric acid, phosphoric acid, pyridinium para-toluene sulfonate, para-toluene sulfonic acid and trifluoroacetic acid, to name just a few, more preferably trifluoroacetic acid, methane sulfonic acid, para-toluene sulfonic acid and pyridinium para-toluene sulfonate.
  • acetic acid formic acid, methane sulfonic acid, sulfuric acid, phosphoric acid, pyridinium para-toluene sulfonate, para-toluene sulfonic acid and trifluoroacetic acid, to name just a few, more preferably trifluoroacetic acid, methane sulfonic acid, para-toluene sulfonic acid
  • the catalyst can be removed by distillation (such as with trifluoroacetic acid) or by precipitation using a suitable precipitation procedure (sus as with para-toluene sulfonic acid), or the catalyst can also remain in sub-unit (a2) (such as with pyridinium para-toluene sulfonate).
  • Reaction temperature can be from 5 °C up to 80 °C, more preferably from 5 °C up to 50 °C.
  • Suitable solvents include, to name only a few:
  • chlorinated solvents such as chloroform and dichloromethane aliphatic ketones which preferably have from 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; cyclic ethers, in particular tetrahydrofuran.
  • Solvents can be either used as-is, or are freshly distilled or dried to eliminate waterimpurities.
  • Reaction times can be from 1 hour up to 96 hours, more preferably from 1 ,5 hours up to 72 hours, most preferably from 2 hours up to 48 hours, but of course any shorter period such as 47, 46, 45, 44 etc down to about 4 hours in principle is also possible depending on the set-up , reaction conditions etc.
  • the solvent is preferanly removed by distillation.
  • the polyaddition process according to the invention can in principle be carried out in various reactor types.
  • reactor types are generally known, and includes any stirred-type reactor such as vessels, but also includes tube reactors, reactor cascades from vessels and/or various tubes etc.
  • a transparent, viscous liquid product (which is used as sub-unit (a2)) is obtained, which is then used as starting material for the subsequent alkoxylation reaction.
  • the alkoxylation reaction of step (2) can be performed using known procedures, conditions, set-ups and equipment.
  • the alkoxylation process as such, wherein a polymeric alcohol is reacted with alkylene oxides, such as ethylene oxide, is known to a person skilled in the art. The same known methods can be applied for the present invention.
  • the alkoxylation reaction may be carried out as a single-step reaction.
  • the alkoxylation is carried out in the presence of at least one catalyst and in the absence of water.
  • the catalyst is preferably a basic catalyst.
  • Suitable catalysts are alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular sodium and potassium C1-C4- alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
  • Preference is given to the alkali metal hydroxides and the alkali metal alkoxides particular preference being given to potassium hydroxide, sodium hydroxide, potassium methoxide and potassium tert-butoxide.
  • Typical use amounts for the base are from 0.05 to 10% by weight, in particular from 0.1 to 2% by weight, based on the total amount of inventive polymer.
  • the alkoxylation reaction may be undertaken in substance (variant a)) or in an organic solvent (variant b)). However, it is preferred that the alkoxylation reaction is carried out without any solvent.
  • sub-unit (a2) whose terminal hydroxy groups act as starting groups for the alkoxylation, is mixed with the above-described catalyst.
  • a de-watering or de-alcoholisation step is employed by heating to from 80 to 150°C and distilling off the water and/or alcohol under a reduced pressure of from less than 30 mbar for 1 to 6 hours, preferably 1 to 3 hours.
  • the subsequent reactions with the alkylene oxide(s) are effected typically at from 70 to 200°C, preferably from 100 to 180°C, and at a pressure of up to 10 bar, in particular up to 8 bar, and a continued stirring time of from about 0.5 to 8 hours at from about 100 to 160°C and constant pressure follows in each case.
  • a post-polymerization time of between 4 and 12 hours is employed, more preferably of between 4 and 8 hours at a temperature between 80 and 140 °C.
  • Suitable reaction media for variant b) are in particular nonpolar and polar aprotic organic solvents.
  • suitable nonpolar aprotic solvents include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene.
  • particularly suitable polar aprotic solvents are ethers, in particular cyclic ethers such as tetrahydrofuran and dioxane, N,N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyllactams such as N-methylpyrrolidone. It is of course also possible to use mixtures of these aprotic solvents.
  • Preferred solvents are xylene and toluene.
  • the solution obtained in the first step after addition of catalyst and solvent, is initially dewatered, which is advantageously done by separating out the water at a temperature of from 120 to 180°C, preferably supported by a gentle nitrogen stream.
  • the subsequent reaction with the alkylene oxide may be effected as in variant a).
  • the alkoxyl ated polyacetal is obtained directly in substance as a viscous or solid product, and may be converted if desired to an aqueous solution.
  • the organic solvent is typically removed and replaced by water. The products may of course also be isolated in substance.
  • polymers of this invention can be employed in any application to replace conventional polymers or to improve the overall performance by adding the inventive polymers in addition, such conventional poylmers being for example commonly employed non-biodegradable EO-PO-EO triblock copolymers of higher molecular weights.
  • Such applications are avoiding or reducing depositioning of solids, dispersion of actives, inhibiting crystal growth, reducing sedimentation and/or agglomeration, improve dispersion stability, etc., all compared to corresponding polymers according to the prior art.
  • inventive polymers as defined herein obtainable by a process as defined herein or obtained by the process as defined herein, can improve the overall bio-degradation ratio of such formulation, compositions and products by replacing non-biodegradable polymers of similar structures or properties. They may thus be advantageously used and can be adjusted in their performance to the specific needs of the specific applications, and thus pose an advantage over simple PEGs, polyalkylene glycols and in particular EO-PO-EO triblock copolymers of higher molecular weights, such as the polymers used in the experimental section below in Comp. Ex. 1 and Comp. Ex. 2.
  • the polymers according to the present invention lead to an improved biodegradability when being employed within such compositions or products, compared to the previously known polymers.
  • another subject matter of the present invention is the use of the polymers of the invention and/or obtained by or obtainable by a process of the invention and/or as detailed before, in agrochemical formulations, as e.g. dispersants, crystal growth inhibitor and/or solubilizer.
  • Another subject-matter of the present invention is, therefore, also an agrochemical composition or agrochemical product, or any other formulation or product in the field of agrochemicals and their formulations and products, each comprising at least one polymer as defined above or obtained by or obtainable by a process of the invention and/or as detailed herein.
  • a preferred subject matter of this invention is also the use of at least one inventive polymer and/or at least one inventive polymer obtained or obtainable by the inventive process in agrochemical compositions.
  • the inventive polymer is employed in such composition/product/formulation for improved dispersion.
  • inventive uses and inventive compositions/products encompass the use of the polymer as detailed herein and/or as obtainable from or obtained from the inventive process, such polymer resembling that as detailed above describing the polymer structure in any of its embodiments disclosed herein before, including any variations mentioned, and more specifically any of the preferred, more preferred etc. embodiments.
  • the agrochemical composition of the invention comprises, besides at least one polymer of the invention, an agrochemical active ingredient. It was found that the inventive polymer is suitable as a dispersant or emulsifier for a broad range of agrochemical active ingredients.
  • agrochemical active ingredient refers to a substance that confers a desirable biological activity to the agrochemical composition.
  • Agrochemical active ingredients include pesticides, safeners, nitrification inhibitors, urease inhibitors, micronutrients, and/or plant growth regulators.
  • the agrochemical active ingredient is a pesticide.
  • Pesticides include insecticides, herbicides, fungicides, algaecides, rodenticides, molluscicides and nematicides.
  • the skilled person is familiar with safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and/or growth regulators.
  • the agrochemical active is an insecticide.
  • the agrochemical active is a herbicide.
  • the agrochemical active is a fungicide.
  • the skilled person is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London.
  • the agrochemical active ingredient is selected from insecticides, fungicides, and herbicides.
  • Suitable insecticides are insecticides from the classes of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, afidopyropene, amidrazones
  • Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides such as fluxapyroxad and diflufenican, carboxylic acid diamides, chloronitriles such as chlorothalonil, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2- amino)pyrimidine
  • Azoxystrobin fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, metyltetraprole, mefentrifluconazole and tebuconazol, in particular azoxystrobin, fluxapyroxad and chlorothalonil, terbutylazin and diflufenican, especially terbutylazin, are especially preferred fungicides.
  • Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, cinmethylin, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids such as glufosinate, phosphoroamidate
  • Atrazine indaziflam, saflufenacil, pyroxasulfone, glufosinate, cinmethylin, terbuthylazine and metribuzine, in particular atrazine, are especially preferred herbicides.
  • a pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • C14 demethylase inhibitors triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefur
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • Inhibitors of 3-keto reductase fenhexamid, fenpyrazamine; other Sterol biosynthesis inhibitors: chlorphenomizole;
  • RNA polymerase I inhibitors benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl; other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;
  • Inhibitors of cell division and cytoskeleton tubulin polymerization inhibitors benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, pyridachlometyl; other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide;
  • Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors cyprodinil, mepanipyrim, pyrimethanil; protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil; mechanism unknown: quinoxyfen, proquinazid;
  • Lipid and membrane synthesis inhibitors Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; compounds affecting cell membrane permeability and fatty acides: propamocarb; inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;
  • inorganic active substances Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid; guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, met
  • Cell wall synthesis inhibitors inhibitors of glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb; cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B.
  • catenulate also named Gliocladium catenulatum
  • Gliocladium roseum also named Lysobacter antibioticus
  • L enzymogenes Metschnikowia fructicola
  • Microdochium dimerum Microsphaeropsis ochracea
  • Muscodor albus Paeni- bacillus alvei
  • Paenibacillus epiphyticus P.
  • anisopliae var. anisopliae M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus,'
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti;
  • Acetylcholine esterase (AChE) inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos,
  • GABA-gated chloride channel antagonists endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole;
  • Sodium channel modulators acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa- bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, f
  • Nicotinic acetylcholine receptor (nAChR) agonists acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;
  • Nicotinic acetylcholine receptor allosteric activators spinosad, spinetoram;
  • Chloride channel activators abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
  • miscellaneous non-specific (multi-site) inhibitors methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
  • Mite growth inhibitors clofentezine, hexythiazox, diflovidazin; etoxazole;
  • Microbial disruptors of insect midgut membranes Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: Cry 1 Ab, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1;
  • Inhibitors of mitochondrial ATP synthase diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
  • Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
  • Octopamin receptor agonists amitraz
  • Mitochondrial complex III electron transport inhibitors hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;
  • Mitochondrial complex I electron transport inhibitors fenazaquin, fen pyroxi mate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;
  • Inhibitors of the of acetyl CoA carboxylase spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;
  • Mitochondrial complex IV electron transport inhibitors aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;
  • Mitochondrial complex II electron transport inhibitors cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide;
  • GABA-gated chloride channel allosteric modulators broflanilide, fluxametamide, isocycloseram; 0.33 Calcium-activated potassium channel modulators: acynonapyr;
  • O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflan
  • - ACC-herbicides alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethy
  • - non ACC herbicides benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
  • - sulfonylureas amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron- ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nico
  • imidazolinones imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;
  • cloransulam cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam;
  • - pyrimidinylbenzoates bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac- methyl, pyrithiobac, pyrithiobac-sodium;
  • - sulfonylaminocarbonyl-triazolinone herbicides flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl;
  • P3) photosynthesis inhibitors amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron,
  • - PDS inhibitors beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;
  • - HPPD inhibitors benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;
  • EPSP synthase inhibitors glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);
  • glutamine synthase inhibitors bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;
  • - group K1 dinitroanilines: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos-methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyzamide and tebutam;
  • - group K2 carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M- isopropyl, flamprop-M-methyl and propham;
  • chloroacetamides acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid- P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,
  • herbicides anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;
  • P11) cellulose biosynthesis inhibitors chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;
  • P12) decoupler herbicides dinoseb, dinoterb and DNOC and its salts
  • auxinic herbicides 2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2- hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl, MCPB and
  • P15 other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tetflupyrolimet, trid
  • the agrochemical active ingredient is selected from azoxystrobin, fluxapyroxad, fludioxonil, chlorothalonil, atrazine, metyltetraprole, mefentrifluconazole, prothioconazole, tebuconazole, terbuthylazine, diflufenican, and metribuzin, preferably from azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, terbuthylazine and atrazine, and is most preferably azoxystrobin.
  • Suitable safeners include (quinolin-8-oxy)acetic acids, 1 -phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carboxylic acids, 1 -phenyl-4,5-dihydro-5-alkyl-1 H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2- phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1 ,8-naphthalic anhydride, 2-halo-4- (haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agricultural
  • Suitable nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6- (trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DI DIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6- methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridiazole), 2-sulfan
  • urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see e.g., US 8,075,659).
  • Such mixtures of NBPT and NPPT may comprise NBPT in amounts of 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances.
  • LIMUS is a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt- % NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
  • Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators.
  • Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine, and molybdenum.
  • the agrochemical composition typically comprises a biologically effective amount, e.g., a pesticidally effective amount of the agrochemical active ingredient.
  • the term “effective amount’ denotes an amount of the composition or of the agrochemical active ingredient, which is sufficient for, e.g., controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as, e.g., the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific agrochemical active ingredient used.
  • the agrochemical composition typically comprises the agrochemical active ingredient in a concentration of 1 to 70% by weight of solids (% w.s.), preferably 1 to 60% w.s., more preferably 10 to 50% w.s., most preferably 20 to 45% w.s., based on the total weight of the agrochemical composition.
  • the agrochemical composition typically contains at least 5% w.s. of the agrochemical active ingredient, preferably at least 15% w.s., more preferably at least 25% w.s., most preferably at least 35% w.s. of the agrochemical active ingredient based on the total weight of the agrochemical composition.
  • the agrochemical composition typically contains up to 95% w.s.
  • agrochemical active ingredient preferably up to 65% w.s., more preferably up to least 45% w.s. of the agrochemical active ingredient based on the total weight of the agrochemical composition.
  • the active substances are employed in a purity of 90% to 100%, preferably 95% to 100%, as determined by nuclear magnetic resonance (NMR) spectroscopy.
  • the agrochemical composition typically comprises at least one inventive polymer in a concentration of 0.5 to 20% w.s., preferably 0.5 to 10% w.s., more preferably 1 to 8% w.s. based on the total weight of the agrochemical composition.
  • the concentration of the inventive polymer is typically up to 15% w.s., more preferably up to 9% w.s., most preferably up to 7% w.s. based on the total weight of the agrochemical composition.
  • the concentration of the inventive polymer is usually at least 2% w.s., preferably at least 2.5% w.s. based on the total weight of the agrochemical composition.
  • the inventive polymer is typically present in the agrochemical composition in dissolved form, in particular if the agrochemical composition is an aqueous agrochemical composition.
  • Typical solvents include those discussed as auxiliaries below.
  • the inventive polymer may be present as solid particles, such as dispersed particles, especially if the agrochemical composition is a non-aqueous composition, such as a solid composition or an agrochemical composition with a continuous organic phase.
  • the weight ratio of the active agrochemical ingredient to the inventive polymer in the agrochemical composition is typically in the range of 1 :1 to 30:1 , preferably 5:1 to 30:1 , more preferably 7:1 to 20:1.
  • the agrochemical composition can be any customary type of agrochemical compositions, including solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g., SC, CD, FS, SE, DC), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EC, ES, ME), capsules (e.g., CS, ZC), pastes, pastilles, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), pressings (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal articles (e.g., LN), as well as gel compositions for the treatment of plant propagation materials such as seeds (e.g.,
  • composition types are suspensions, emulsifiable concentrates (EC), wettable powders or wettable dusts, and granules, in particular suspensions.
  • Preferred suspensions include suspension concentrates (SC), suspo-emulsions (SE) and dispersible concentrates (DC). Most preferred are suspension concentrates (SC).
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • agrochemically active ingredient e.g. one or more pesticides
  • it is usually required to dissolve the agrochemically active ingredient, e.g. one or more pesticides in a solvent, which is then diluted in a larger volume of water in order for it to be applied in the form of a fine spray.
  • some agrochemically active ingredients are salts and thus highly water-soluble, allowing for simply dissolution, many other non-ionic agrochemically active ingredients are hydrophobic and not at all water-soluble.
  • Emulsifiable concentrates are typically optically transparent oily liquid formulations that are prepared by dissolving a certain amount of pesticide in organic solvents (such as benzene, toluene, xylene, and solvent oil), which may also contain surfactants (i.e. emulsifiers) and other additives. These concentrates are suitable for dispersion within an aqueous phase to form an oil-in-water emulsion formulation.
  • Emulsifiable concentrates must be monophasic, i.e., the pesticide and any emulsifiers must be completely soluble in the organic solvent at the concentrations used.
  • An emulsion is a mixture of two or more liquids that are normally immiscible, wherein one liquid forms a dispersed phase, suspended as droplets within the other liquid, which is known as the continuous phase.
  • Emulsions are typically referred to as oil-in-water (i.e. the water is the continuous phase) or water-in-oil (i.e. the oil is the continuous phase).
  • oil-in-water emulsions known as emulsion-in- water formulations are often used to disperse hydrophobic pesticides across fields of crop plants.
  • the agrochemical composition is typically prepared by contacting the inventive polymer and the active agrochemical ingredient. If the agrochemical composition is a suspension, the method typically comprises contacting the active agrochemical ingredient with water to form a mill-base. The premix is then typically submitted to grinding or milling to form the final suspension.
  • the inventive polymer may either be added to the mill-base or to the final suspension, in particular to the mill-base.
  • the agrochemical composition is a granule, it is typically obtained by preparing a premix containing the agrochemical active ingredient, the inventive polymer, a filler, and typically up to 5 wt.-% of water, and the premix is then extruded. The extrudate is then dried and converted to granules.
  • auxiliaries that may be added to the agrochemical composition are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, crystal growth inhibitors, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g., kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • toluene paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g., ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g., cyclohexanone; esters, e.g., lactates, carbonates, fatty acid esters, alkyl esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g., N-methylpyrrolidone, lactamides, alkyl amides, fatty acid dimethylamides; and mixtures thereof.
  • alcohols e.g., ethanol, propanol, butanol, benzylalcohol, cyclohexanol
  • glycols DMSO
  • ketones e.g., cyclohexan
  • Suitable solid carriers or fillers are mineral earths, e.g., silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g., cellulose, starch; fertilizers, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g., cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g., silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g., cellulose, star
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alphaolefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 100 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g., in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, poly acrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation include: i) Water-soluble concentrates (SL, LS)
  • agrochemical active ingredient 5 to 25 wt.-% of the agrochemical active ingredient, 1 to 10 wt.-% of the inventive polymer and optionally further dispersants (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g., cyclohexanone) ad 100 wt.-%. Dilution with water gives a dispersion.
  • organic solvent e.g., cyclohexanone
  • an agrochemical active ingredient 20 to 60 wt.-% of an agrochemical active ingredient are comminuted with addition of 1 to 10 wt.-% the inventive polymer and optionally further dispersants, and wetting agents (e.g., sodium lignosulfonate and alcohol ethoxylate), 0,1 to 2 wt.-% thickener (e.g., xanthan gum) and water ad 100 wt.-% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • binder e.g., polyvinylalcohol
  • a suspension emulsion may be obtained by mixing a suspension with an emulsifiable concentrate or with an emulsion, such as an oil-in-water emulsion (EW).
  • EW oil-in-water emulsion
  • agrochemical active ingredient 50 to 80 wt-% of the agrochemical active ingredient are ground finely with addition of the inventive polymer, optionally further dispersants, and wetting agents (e.g., sodium lignosulfonate and alcohol ethoxylate) ad 100 wt- % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • WP, SP, WS Water-dispersible powders and water-soluble powders
  • an agrochemical active ingredient 50 to 80 wt.-% of an agrochemical active ingredient are ground in a rotor-stator mill with addition of 1 to 5 wt.-% of the inventive polymer and optionally further dispersants (e.g., sodium lignosulfonate), 1 to 3 wt-% wetting agents (e.g., alcohol ethoxylate) and solid carrier (e.g., silica gel) ad 100 wt.-%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g., sodium lignosulfonate
  • wetting agents e.g., alcohol ethoxylate
  • solid carrier e.g., silica gel
  • an agrochemical active ingredient In an agitated ball mill, 5 to 25 wt.-% of an agrochemical active ingredient are comminuted with addition of 3 to 10 wt.-% of inventive polymer and optionally further dispersants (e.g., sodium lignosulfonate), 1 to 5 wt.-% thickener (e.g., carboxymethylcellulose) and water ad 100 wt.-% to give a fine suspension of the active substance. Dilution with water gives a stable gel of the active substance.
  • dispersants e.g., sodium lignosulfonate
  • 1 to 5 wt.-% thickener e.g., carboxymethylcellulose
  • an agrochemical active ingredient 5 to 20 wt.-% of an agrochemical active ingredient are added to 5 to 30 wt.-% organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10 to 25 wt.-% surfactant blend (e.g., alkohol ethoxylate and arylphenol ethoxylate), 1 to 25 wt.-% of the inventive polymer, and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g., fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g., alkohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5 to 50 wt.-% of an agrochemical active ingedient, 0 to 40 wt.-% water insoluble organic solvent (e.g., aromatic hydrocarbon), 2 to 15 wt.-% acrylic monomers (e.g., methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • a protective colloid e.g., polyvinyl alcohol
  • an oil phase comprising 5 to 50 wt.-% of an agrochemical active ingredient, 0 to 40 wt.-% water insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethene-4,4’- diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g., polyvinyl alcohol).
  • a protective colloid e.g., polyvinyl alcohol
  • a polyamine e.g., hexamethylenediamine
  • the addition of a polyamine results in the formation of a polyurea microcapsules.
  • the monomers amount to 1 to 10 wt.-%.
  • the wt.-% relate to the total CS composition.
  • the microcapsules may then be dispersed in an aqueous composition.
  • 1 to 40 wt.-% of the microcapsules are mixed with 2 to 10 wt.-% the inventive polymer and optionally further dispersants, and wetting agents (e.g., sodium lignosulfonate and alcohol ethoxylate), 0,1 to 2 wt.-% thickener (e.g., xanthan gum) and water ad 100 wt.-% to yield a CS composition.
  • wetting agents e.g., sodium lignosulfonate and alcohol ethoxylate
  • 01 to 2 wt.-% thickener e.g., xanthan gum
  • 1 to 10 wt.-% of an agrochemical active ingredient are ground finely and mixed intimately with the 1 to 20 wt.-% of the inventive polymer, and solid carrier (e.g., finely divided kaolin) ad 100 wt.-%.
  • solid carrier e.g., finely divided kaolin
  • agrochemical active ingredient 0.5 to 30 wt.-% of an agrochemical active ingredient is ground finely and associated with 1 to 20 wt.-% of the inventive polymer and with solid carrier (e.g., silicate) ad 100 wt.-%.
  • Granulation is achieved by extrusion, spraydrying or the fluidized bed.
  • organic solvent e.g., aromatic hydrocarbon
  • compositions types i) to xi) may optionally comprise further auxiliaries such as those discussed above, e.g., 0, 1 to 1 wt.-% bactericides, 5 to 15 wt.-% anti-freezing agents, 0,1 to 1 wt.-% anti-foaming agents, and 0,1 to 1 wt.-% colorants.
  • auxiliaries such as those discussed above, e.g., 0, 1 to 1 wt.-% bactericides, 5 to 15 wt.-% anti-freezing agents, 0,1 to 1 wt.-% anti-foaming agents, and 0,1 to 1 wt.-% colorants.
  • the agrochemical composition is a suspension, preferably a suspension concentrate.
  • the agrochemical suspension typically contains the agrochemical active ingredient in a concentration of 1 to 65 wt- %, preferably 10 to 60 wt.-%, more preferably 20 to 50 wt.-%, most preferably 30 to 50 wt.-% based on the total weight of the agrochemical suspension.
  • the agrochemical suspension contains at least a portion of the agrochemical active as solid particles suspended in a continuous phase, which is preferably an aqueous continuous phase.
  • the agrochemical suspension is preferably an aqueous agrochemical suspension containing at least 5 wt.-% of water, preferably at least 10 wt.-%, more preferably at least 15 wt-%, most preferably at least 20 wt.-%, especially preferably at least 25 wt.-%, such as at least 30 wt.-%, in particular at least 40 wt.-%, each time based on the total weight of the suspension.
  • the agrochemical composition may contain up to 95 wt.-% of water, preferably up to 80 wt.-%, more preferably up to 70 wt.-%, most preferably up to 60 wt.-% of water, such as up to 50 wt.-% of water, each time based on the total weight of the suspension.
  • the agrochemical active ingredient typically exhibits low water-solubility.
  • the agrochemical active may have a water-solubility at 20 °C and pH of 7 of up to 10 g/L, preferably up to 5 g/L, more preferably up to 1 g/L, most preferably up to 0.5 g/L, in particular up to 0.1 g/L.
  • the agrochemical active ingredient is present in the form of suspended particles in the agrochemical suspension.
  • the particles may be characterized by their size distribution, which can be determined by dynamic light scattering techniques. Suitable dynamic light scattering measurement units are inter alia produced under the trade name Malvern Mastersizer 3000.
  • the particles of the agrochemical active ingredient may be characterized by their median diameter, which is usually abbreviated as D50 value.
  • the D50 value refers to a particular particle diameter, wherein half of the particle population by volume is smaller than this diameter.
  • the D50 value is typically determined according to ISO 13320:2009.
  • the particles may have an D50 value in the range of 0.05 pm to 25 pm, preferably in the range of 0.1 pm to 20 pm, more preferably in the range of 0.5 to less than 20 pm, most preferably in the range of 0.5 pm to 15 pm, especially preferably in the range of 0.5 pm to 10 pm.
  • the particles typically have a D50 value of at least 0.75 pm, preferably at least 1 pm, and as upper limit preferably at most 3 pm or at most 2 pm.
  • the particles of the agrochemical active ingredient may further be characterized by their D90 value.
  • the D90 value refers to a particular particle diameter, wherein 90% of the particle population by volume is smaller than this diameter.
  • the D90 value is typically determined according to ISO 13320:2009.
  • the particles may have a D90 value of less than 30 to 3 pm, in particular less than 20 pm or less than 15 pm, especially less than 10 pm or less than 8 pm or less than 6 pm or less than 5 pm.
  • the particles of the agrochemical active ingredient may also be characterized by their D10 value.
  • the D10 value refers to a particular particle diameter, wherein 10% of the particle population by volume is smaller than this diameter.
  • the D10 value is typically determined according to ISO 13320:2009.
  • the particles may generally have a D10 value of less than 2 pm, e.g. in the range of 0.05 to ⁇ 2 pm, in particular in the range of 0.1 to 1.5 pm or in the range of 0.1 to 1 pm.
  • the particles have D50 value in the range of 0.5 to 10 pm, especially in the range of 0.5 to 3 pm or in the range of 0.75 to 2 pm and a D90 value in the range of 3 to less than 10 pm.
  • the suspended particles may be present in the form of crystalline or amorphous particles which are solid at 20 °C.
  • At least 50 wt.-% of the agrochemical active ingredient may be present as solid particles based on the total weight of the agrochemical active ingredient in the agrochemical suspension, preferably at least 70 wt.-%, more preferably at least 90 wt.-%.
  • the agrochemical suspension may contain a further active ingredient, which may be selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biopesticides, nitrification inhibitors, urease inhibitors, and/or growth regulators.
  • the further active ingredient may be present in dissolved form or as suspended particles in the agrochemical suspension.
  • the concentration of the further active ingredient is typically from 1 to 50 wt.-%, preferably from 10 to 25 wt.-% based on the total weight of the agrochemical suspension.
  • the agrochemical suspension may be prepared at any pH value.
  • agrochemical suspensions according to the invention have a pH below 9, more preferably from 4 to below 9
  • the agrochemical suspension typically contains a thickener.
  • thickener(s) usually refers to inorganic clays (organically modified or unmodified), such as bentonites, attapulgite, hectorite and smectite clays, and silicates (e.g., colloidal hydrous magnesium silicate, colloidal hydrous aluminium silicate, colloidal hydrous aluminium magnesium silicate, hydrous amorphous silicon dioxide); and organic clays, such as polycarboxylates (e.g., poly(meth)acrylates and modified poly(meth)acrylates), polysaccharides (e.g., xanthan gum, agarose, rhamsan gum, pullulan, tragacanth gum, locust bean gum, guar gum, tara gum, Whelan cum, casein, dextrin, diutan gum, cellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose), polyvinyl
  • the invention also relates to the use of the inventive polymer as a dispersant for agrochemical active ingredients in agrochemical compositions, such as in suspensions. It is understood that all embodiments regarding the agrochemical composition herein relate to both the inventive agrochemical composition and the inventive use of the inventive polymer as a dispersant for agrochemical active ingredients in agrochemical compositions.
  • Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • These compositions give, after two-to-tenfold dilution, active substance concentrations of 0.01 to 60 wt.-%, preferably 0.1 to 40 wt.-%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying the agrochemical composition on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the agrochemical composition applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the invention also relates to a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the agrochemical composition is allowed to act on the phytopathogenic fungi, undesired plant growth or undesired insects or mites; and/or on the habitat of the phytopathogenic fungi, undesired plant growth or undesired insects or mites; and/or on the plants to be protected, and/or on the soil of the plants to be protected; and/or on the useful plants and/or their habitat.
  • the method is for controlling phytopathogenic fungi. In another embodiment, the method is for controlling undesired plant growth. In another embodiment, the method is for controlling undesired attach by insects or mites. These methods typically comprise the treatment of the plant to be protected, its locus of growth, the phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites with the agrochemical composition.
  • Suitable methods of treatment include inter alia soil treatment, seed treatment, in furrow application, and foliar application.
  • Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection.
  • Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting.
  • furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.
  • the amounts of agrochemical active applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • amounts of active substance of 0.1 to 1000 g, preferably 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the invention also relates to a seed comprising the agrochemical composition of the invention in an amount of 0.1 g to 10 kg per 100 kg of seed.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the agrochemical composition as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g., herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1 .
  • the user applies the agrochemical composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane or a spray drone, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2,000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • the invention also relates to a method for combating or controlling invertebrate pests, which method comprises contacting the invertebrate pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of the agrochemical composition.
  • the invention relates to a method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of the agrochemical composition.
  • the invention relates to a method for treating or protecting an animal from infestation or infection by invertebrate pests, which method comprises bringing the animal in contact with a pesticidally effective amount of the agrochemical composition.
  • Invertebrate pests according to the present invention are typically arachnids, mollusca, or insects, in particular insects.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user itself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • composition according to the invention can be applied jointly (e.g., after tank mix) or consecutively.
  • At least one polyacetal triblock copolymer according to any embodiment disclosed herein throughout the description and the examples, either as described in its structure or as obtainable or obtained by the process according to any embodiment disclosed herein throughout the description and the examples is used in a composition, that is an agrochemical formulation.
  • a composition being an agrochemical formulation comprising at least one agrochemical active ingredient and at least one polyacetal triblock copolymer according to any embodiment disclosed herein throughout the description and the examples, either as described in its structure or as obtainable or obtained by the process according to any embodiment disclosed herein throughout the description and the examples, wherein the agrochemical active ingredient is selected from pesticides, in particular herbicides, fungicides and insecticides.
  • the agrochemical active ingredient is selected from azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, metyltetraprole, mefentrifluconazole, tebuconazole, atrazine, indaziflam, saflufenacil, pyroxasulfone, glufosinate, cinmethylin, terbuthylazine, oxyfluorfen, pyraclostrobin, difenoconazole, trifloxystrobin, flufenacetat, pinoxaden, metaflumizon, terbutylazin and metribuzin, preferably from azoxystrobin, diflufenican, terbutylazin, fluxapyroxad, fludioxonil, prothioconazole, tebuconazo
  • the composition is a suspension such as a suspension concentrate, an emulsifiable concentrate, a suspo-emulsion or a dispersible concentrate, a wettable powder, a wettable dust, or a granule, preferably a suspension, most preferably a suspension concentrate or an emulsifiable concentrate.
  • the amount of the sum of all active agrochemical ingredients is from 0,5 to 80, preferably 5 to 50, more preferably 10 to 40 weight percent (based on the formulation).
  • the amount of the polyacetal triblock copolymer of the invention in the agrochemical composition is typically from 1 to 30, preferably 1 ,5 to 15, more preferably up to 10, and any number in between 5 and 30 as the upper limit.
  • the present invention relates to a liquid or semi-liquid detergent composition (in the following also described as the composition or product according to the invention) comprising at least one aqueous polymer dispersion as detailed herein before, and/or an aqueous polymer dispersion obtainable from the process as detailed herein before, such composition being preferably a laundry detergent, a hand-dish detergent, an automated dish wash detergent, or a hard-surface cleaner, more preferably for the area of home and fabric care.
  • a liquid or semi-liquid detergent composition comprising at least one aqueous polymer dispersion as detailed herein before, and/or an aqueous polymer dispersion obtainable from the process as detailed herein before, such composition being preferably a laundry detergent, a hand-dish detergent, an automated dish wash detergent, or a hard-surface cleaner, more preferably for the area of home and fabric care.
  • the liquid or semi-liquid detergent composition according to the invention may be in, but may not limited to, the form of a cleaning composition, a fabric care and home care product, preferably a laundry cleaning composition, a laundry treatment product or laundry care product or laundry washing product.
  • compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind, more preferably compositions for Fabric and Home Care. “Cleaning compositions” are defined in more detail in paragraphs [0001], [0002], [0004] and [0007] of Reference RF1. “Compositions for Fabric and Home Care” include cleaning compositions and formulations including but not limited to laundry cleaning compositions and detergents and hard surface cleaning compositions including dish washing compositions, more preferably liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions. “Compositions for Fabric and Home Care” are defined in more detail in paragraph [0003] of Reference RF1 .
  • the cleaning compositions of the invention including the inventive polymer(s) may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.
  • adjunct cleaning additives also abbreviated herein as “adjuncts”
  • Suitable adjunct cleaning additives include further polymers, surfactants or surfactant systems, builders, cobuilders, enzymes, enzyme stabilizing systems, structurants or thickeners, clay soil removal/anti-redeposition agents, solubilizing agents, chelating agents, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes.
  • the cleaning compositions comprise the inventive polymer(s) and an additional polymer, preferably cleaning polymers and/or soil release polymers.
  • “Cleaning polymers and soil release polymers” are defined in more detail in paragraphs [0032] to [0034] of Reference RF1. These polymers include polycarboxylates, alkoxylated polyalkylenamines, alkoxylated polyalkylenimines, polyether-based polymers, rheology-modifying polymers, dye inhibition polymers and soil release polymers as defined in more detail in paragraphs [3035] to [3044] of Reference RF2.
  • the additional polymers may include, without limitation, “multifunctional alkoxylated polyethylene imines”, “multifunctional alkoxylated diamines” and also terephthalic acid-based polyesters like Clariant’s TexCare®, such as TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN 260 SG Terra and TexCare® SRA 300 as well as distinct combinations of all of the before mentioned polymers. Also included are graft polymers comprising a polyalkylene oxide based backbone with grafted side chains of vinyl ester monomer and optionally N-vinylpyrrolidone monomers.
  • the cleaning compositions comprise the inventive polymer(s) and a surfactant or surfactant system.
  • surfactants are anionic, non-ionic, cationic, amphoteric and zwitter-ionic surfactants defined in more detail in paragraphs [3008] to [3034] of Reference RF2. In addition, these surfactants are also described in more detail in paragraphs [0008] to [0013] of Reference RF1 .
  • Anionic surfactants for inventive cleaning compositions include linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl alkoxy sulfates (AES), alkyl alkoxy carboxylates, modified alkylbenzene sulfonate (MLAS), methyl ester sulfonate (MES), alkyl sulfosuccinates, alpha-olefin sulfonate (AOS), alkyl polyglycosides (APG) and biosurfactants, such as rhamnolipids and sophorolipids.
  • LAS linear alkylbenzenesulfonates
  • AS alkyl sulfates
  • AES alkyl alkoxy carboxylates
  • MLAS modified alkylbenzene sulfonate
  • MES methyl ester sulfonate
  • alkyl sulfosuccinates alpha-olefin s
  • Non-ionic surfactants for inventive cleaning compositions include alkoxylates, alkoxylated alcohols, alkoxylated fatty acids and alkoxylated (poly-)saccharides.
  • Cationic surfactants for inventive cleaning compositions include surfactants comprising a quaternary ammonium.
  • Amphoteric surfactants for inventive cleaning compositions include amine oxides.
  • Zwitter-ionic surfactants for inventive cleaning compositions include betaines.
  • the cleaning compositions comprise the inventive polymer(s) and a builder.
  • Builders are defined in more detail in paragraphs [0014] to [0018] of Reference RF1. These builders include nonphosphate based builders (NPB) and phosphonates (CoP) described in more detail in paragraphs [3001] to [3005] of Reference RF2.
  • NPB nonphosphate based builders
  • CoP phosphonates
  • MGDA methylglycinediaceticacid
  • EDDS ethylenediaminedisuccinic acid
  • GLDA glutamic acid diacetate
  • citric acid and salts thereof.
  • the cleaning compositions comprise the inventive polymer(s) and an enzyme. “Enzymes” are defined in more detail in paragraphs [0020] to [0027] of Reference RF1 .
  • Enzymes may include hydrolases, such as proteases, amylases, lipases, DNases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases.
  • the cleaning composition comprises, in addition to the inventive compound(s), a protease and a protease stabilizing system comprising a peptide aldehyde.
  • the cleaning compositions comprise the inventive polymer(s) and a biocide.
  • Biocides are defined in more detail in paragraphs [0035] and [0036] of Reference RF1. These biocides also include compounds as defined in more detail in paragraphs [3006] and [3007] of Reference RF2.
  • Biocides may include, without limitation, 2-phenoxyethanol and 4,4’-dichoro 2-hydroxydiphenylether.
  • Liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions comprising inventive polymer(s) are defined in more detail in paragraph [0041] of Reference RF1 .
  • compositions of the present disclosure can “comprise” (i.e. contain other ingredients), “consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of’ (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure.
  • the terms “substantially free of... or” substantially free from...” or “(containing/comprising) essentially no... may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1%, or even less than 0.1 %, or even more less than 0.01 %, or even 0%, by weight of the composition.
  • the term “obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process de-scribed in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process.
  • the term “obtainable by” also comprises the more limiting term “obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.
  • number of carbon atoms refers to the total number of carbon atoms in said compound or substituent of a compound.
  • alkyl ether with at least 8 carbon atoms comprising alkylene oxide groups the total number of at least 8 carbon atoms needs to be the sum of the number of carbon atoms of the alkyl moiety and the number of carbon atoms of the alkylene oxide moieties.
  • containing one hydroxy group means that only one group -OH is present. Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group. This applies in analogy to any other functional group being discussed herein.
  • containing at least two hydroxy groups means that two or more -OH groups are present.
  • hydroxy group is equal to the term “hydroxyl group” or “-OH group”.
  • Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group. This applies in analogy to any other functional group being discussed herein.
  • the term “about” as used herein encompasses the exact number “X” mentioned as e.g. “about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations.
  • X is already “100%” (such as for purity etc.) then the term “about” clearly can and thus does only mean deviations thereof which are smaller than “100”.
  • free of water means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the term “inventive compound” may be used instead of the “inventive polymer” and “polymer of this (present) invention”, meaning those compounds being disclosed herein as invention, defined by their structure and/or their process to produce and/or obtainable by the process defined herein, specifically the “polyacetal triblock copolymer” as disclosed and claimed herein.
  • the following examples shall further illustrate the present invention without restricting the scope of the invention.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the polydispersity Mw/Mn of the inventive and comparative polymers can be determined by size-exclusion chromatography.
  • the mobile phase (eluent) to be used is tetrahydrofuran (>99%), stabilized with ca. 250 ppm butyl hydroxy toluene (BHT).
  • BHT butyl hydroxy toluene
  • the concentration of inventive polymer in tetrahydrofuran is 1.0 g per L. After filtration (pore size 0.2 m), 100 piL of this solution were injected into the Agilent Technologies 1200 Infinity Series GPC system. A PL-Gel Mixed E 3 pm column is used for separation. The GPC system is operated at a flow rate of 1 mL per min.
  • An Agilent RID G1362A may be used as the detection system.
  • Narrow molecular weight distribution poly(styrene) (PS) standards
  • Cloud points were determined according totechnisch A in DIN EN 1890, since all inventive polymers show a turbidity in aqueous solution (1 g polymer plus 100 g water) at a temperature between 10 °C and 90 °C. All cloud points were determined in duplicate.
  • the surface tension (SFT) was determined using the Wilhelmy-Plate method.
  • a 0,1 % polymer solution is prepared in distilled water and adjusted to pH 7. 30 mL of this solution is added to a glass sample vessel with a diameter of 50 mmm and a temperature of 25 °C is set using the temperature control unit of the DCAT 25 (Dataphysics) unit.
  • the interfacial tension (I FT) between oil and an aqueous solution of the polymer was determined using the Pendant-Drop Method.
  • a 0,1 % polymer solution is prepared in distilled water and adjusted to pH 7.
  • a 1 mL Braun plastic syringe is rinsed and subsequently filled with an oil having a known density.
  • the glass cell (20 x 20 x 20 mm) of the OCAH 150pro measurement unit is filled with the polymer solution.
  • the needle of the syringe is bent and immersed into the solution.
  • the oil is squeezed into the aqueous solution until a drop is formed at the outlet of the needle (pendant drop).
  • SST Static surface tension
  • I FT interfacial tension
  • CP cloud point
  • T g glass transition temperature
  • T m melting temperature
  • n.d. not determined
  • n.s. not soluble.
  • the triblock copolymer was prepared in three steps:
  • a mixture of 100 g dipropylene glycol (0.75 mol) and 2.50 g potassium hydroxide (0.04 mol) are charged into a 0.3-liter autoclave, and acetylene was introduced until the pressure reached 17 bar.
  • the reaction was conducted at 160°C, 17 bar, and with a stirrer speed of 700 rpm. After absorbing approximately 38 liters of acetylene (approximately after 6.5 hours), the reaction was stopped, and the autoclave was depressurized and cooled to room temperature. Subsequently, distillation was carried out at 120°C and 20-60 mbar, resulting in a yield of 75%.
  • Step 3 Ethoxylation of the polyacetal from step 2
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical as in Inv. 1.
  • Step 2 Polyacetal of DPG-DVE and PG
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 0.4 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 90 g of EC and 10 g of CL are dosed into the reactor within six hours.
  • the reaction mixture is allowed to postreact for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours.
  • 186 g of a brownish solid product were obtained in a yield of 93%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 2.
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 0.4 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 80 g of EC and 20 g of CL are dosed into the reactor within six hours.
  • the reaction mixture is allowed to postreact for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours.
  • 185 g of a brownish solid product were obtained in a yield of 93%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 Polyacetal of DPG-DVE and PG
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • 39 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1.2 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 27.3 g of EC and 11.7 g of CL are dosed into the reactor within six hours.
  • the reaction mixture is allowed to post- react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 64 g of a brownish solid product were obtained in a yield of 82%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 2.
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 105 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 2.16 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 245 g of EO are dosed into the reactor within eight hours.
  • the reaction mixture is allowed to post-react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 330 g of a brownish solid product were obtained in a yield of 94%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 Polyacetal of DPG-DVE and PG
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 108.4 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .54 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 162.6 g of EO are dosed into the reactor within eight hours.
  • the reaction mixture is allowed to post-react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 255 g of a brownish solid product were obtained in a yield of 94%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 6.
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .02 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 66.7 g of EO are dosed into the reactor within two hours.
  • the reaction mixture is allowed to post-react for fifteen hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 160 g of a brownish solid product were obtained in a yield of 96%.
  • Example 8 (Inv. 8)
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 4.
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • step 2 108 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 0.36 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 54 g of EC and 18 g of CL are dosed into the reactor within one hour.
  • the reaction mixture is allowed to postreact for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 153 g of a brownish solid product were obtained in a yield of 86%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 2.
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 127 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .12 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 55 g of EC are dosed into the reactor within eight hours.
  • the reaction mixture is allowed to post-react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 161 g of a brownish solid product were obtained in a yield of 88%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 1.
  • Step 2 is identical to step 2 in Inv. 4.
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • 120 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .1 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 42.9 g of EC and 8.8 g of CL are dosed into the reactor within one hour.
  • the reaction mixture is allowed to post- react for ten hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for 2 hours. 145 g of a brownish solid product were obtained in a yield of 84%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 Synthesis of 1 ,4-BDO-DVE
  • 1 ,4-Butanediol divinyl ether (1 ,4-BDO-DVE) and 1 ,4-Butanediol (1 ,4-BDO) are commercially available and were obtained from BASF SE and used as is.
  • Step 2 Polyacetal of 1 ,4-BDO-DVE and 1 ,4-BDO
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .23 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 100 g of EO are dosed into the reactor within two hours.
  • the reaction mixture is allowed to post-react for ten hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for two hours. 182 g of a brownish solid product were obtained in a yield of 91 %.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 11.
  • Step 2 Polyacetal of 1,4-BDO-DVE and 1 ,4-BDO
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .23 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and a mixture consisting of 90 g of EO and 10 g of CL are dosed into the reactor within five hours.
  • the reaction mixture is allowed to post- react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for two hours. 183 g of a brownish solid product were obtained in a yield of 91 %.
  • the triblock copolymer was prepared in three steps:
  • Step 1 is identical to step 1 in Inv. 11.
  • Step 2 is identical to step 2 in Inv. 12.
  • Step 3 Ethoxylation of the polyacetal from step 2 in the presence of CL
  • the triblock copolymer was prepared in three steps:
  • Step 2 Polyacetal of 1 ,4-BDO-DVE and 1 ,4-BDO
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .2 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 100 g of EO are dosed into the reactor within six hours.
  • the reaction mixture is allowed to post-react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for two hours. 195 g of a brownish solid product were obtained in a yield of 97%.
  • the triblock copolymer was prepared in three steps:
  • Step 1 Synthesis of DPG-DVE was synthesized according to the procedure described under Inv. 1
  • Step 2 Polyacetal of DPG-DVE and PG
  • Step 3 Ethoxylation of the polyacetal from step 2
  • 100 g of polyacetal obtained in step 2) are filled into a steel pressure reactor and 1 .2 g of potassium methoxide (32.5 wt% in methanol) are added. Volatiles are removed at 20 mbar at 90 °C.
  • the reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set.
  • the reactor is heated to 120 °C and 100 g of EO are dosed into the reactor within two hours.
  • the reaction mixture is allowed to post-react for six hours at 120 °C and subsequently any volatiles are removed at the rotary evaporator at 90 °C and 20 mbar for two hours. 181 g of a brownish solid product were obtained in a yield of 90%.
  • Table 2 Biodegradation data of comparative and inventive polymers measured with the OECD 301 F and DIN EN ISO 17556 test method.
  • the inventive polymers show a significantly improved percentage of biodegradation in the OECD 301 F and in the DIN EN ISO 17556 test versus the comparative polymers.
  • the emulsion was tested for its dispersibility by the effect known as blooming.
  • the emulsions were assessed according to their spontaneous emulsification when the concentrate (EC) is added to water (known in the art as "blooming") with a visual assessment given on a scale of 1 to 5, whereby 1). Excellent, “cloud of emulsion”, does not sink to bottom of cylinder. 2). Good, “cloud of emulsion”, but sinks to bottom of cylinder 3). Okay, “poor emulsion cloud”, larger droplets 4). Poor, “no emulsion cloud”, small “particles” observed 5).
  • Emulsifiable concentrates were prepared in the following examples and the resulting 5% w/w emulsions in various water hardness at 21 °C after 24 hours were assessed. Emulsion stability was determined as a function of time, with the amount of either cream or sediment measured.
  • emulsion stability To measure emulsion stability, 5.0 mL of the emulsifiable concentrate was diluted in 95.0 mL CIPAC D water in a 100 mL measuring cylinder. The resulting oil-in-water emulsion stability was assessed after 1 , 2, 4 and 24 hours. A highly stable emulsion does not form cream or sediment, or has less than 1 .5 mL cream or sediment after 24 hours, and can be readily re-emulsified after 24 h of standing without the formation of cream or sediment, with such re-emulsified emulsions assessed 30 minutes after re-emulsification. Both the initial emulsification and the re-emulsification were achieved by gently inverting the emulsion 10 times.
  • Suspension concentrates were prepared by grinding a) 40 wt.-% of solids (w.s.) active ingredient, 5% w.s. dispersant, 0.3% w.s. Agnique DFM 111 S (polydimethylsiloxane emulsion defoamer) with fully demineralized water b) 40 wt.-% of solids (w.s.) active ingredient, 5% w.s. dispersant, 0.3% w.s.
  • Agnique DFM 111 S (silicon emulsion defoamer), 7% ws propylene glycol with fully demineralized water c) 40 wt.-% of solids (w.s.) active ingredient, 1 ,6% ws Tamol® DN (phenol sulfonic acid, polymer with formaldehyde, phenol and urea, sodium salt), 2,5% w.s. dispersant, 0.3% w.s.
  • Agnique DFM 111 S (silicon emulsion defoamer) with fully demineralized water d) 40 wt.-% of solids (w.s.) active ingredient, 1 ,6% ws Tamol® DN, 2,5% w.s.
  • dispersant 0.3% w.s. Agnique DFM 111 S (silicon emulsion defoamer), 7% ws propylene glycol with fully demineralized water in a disperser “DAS 200”, Lau GmbH with glass balls (diameter: 2 or 3 mm) such that the dispersed pesticide particles reached a particle size distribution characterized by a D90 of ⁇ 10 pm and a D50 ⁇ 3 pm and a D10 ⁇ 1 pm.
  • the filled measuring cylinder from Method III was taken and more suspension concentrate was added until the cylinder comprised 5 g thereof. Subsequently, the cylinder content was homogenized by ten times 180° inversion, and allowed to stand for 30 min. Next, the top nine-tenths of the content were removed and the remaining tenth was then dried (ca. 50 °C / 500 mbar), assayed gravimetrically, and the suspensibility was calculated according to the following method:
  • Preparation a 40 wt.-% of solids (w.s.) active ingredient, 5% w.s. dispersant, 0.3% w.s. Agnique DFM 111 S (silicon emulsion defoamer) with fully demineralized water.
  • DFM 111 S sicon emulsion defoamer

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Dispersion Chemistry (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne des polymères séquencés amphiphiles de polyacétal (a1)-(a2)-(a1), comprenant un bloc à base de polyacétal hydrophobe (a2) et deux blocs à base d'oxyde de polyalkylène hydrophile (a1). Le bloc à base de polyacétal hydrophobe (a2) peut être obtenu par polyaddition d'au moins un monomère d'éther vinylique et d'au moins un diol. Le bloc à base d'oxyde de polyalkylène hydrophile (a1) comprend des fractions dérivées d'oxyde de polyalkylène et, éventuellement, des fractions dérivées d'un ou de plusieurs lactones et/ou d'un ou de plusieurs acides hydroxy, ces fractions étant mélangées de telle sorte que le squelette polymère contienne des fonctions ester à l'intérieur des chaînes polymères. L'invention concerne en outre un procédé de production de tels polymères séquencés de polyacétal, l'utilisation de tels polymères séquencés de polyacétal dans des formulations et des compositions agrochimiques.
PCT/EP2025/060536 2024-04-26 2025-04-16 Copolymères séquencés amphiphiles de polyacétal, leur production et leur utilisation dans des produits agrochimiques et des formulations agrochimiques Pending WO2025223971A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24172736 2024-04-26
EP24172736.1 2024-04-26

Publications (1)

Publication Number Publication Date
WO2025223971A1 true WO2025223971A1 (fr) 2025-10-30

Family

ID=90922516

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/060536 Pending WO2025223971A1 (fr) 2024-04-26 2025-04-16 Copolymères séquencés amphiphiles de polyacétal, leur production et leur utilisation dans des produits agrochimiques et des formulations agrochimiques

Country Status (1)

Country Link
WO (1) WO2025223971A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4142130A1 (de) 1991-12-20 1993-06-24 Basf Ag Verwendung von polyacetalen auf basis von vinylethern und dihydroxyverbindungen in wasch- und reinigungsmitteln und polyacetale
DE4237337A1 (de) 1992-11-05 1994-05-11 Basf Ag Blockcopolyacetale, Verfahren zu ihrer Herstellung und ihre Verwendung in Wasch- und Reinigungsmitteln
WO2006105123A2 (fr) 2005-03-31 2006-10-05 Ap Pharma, Inc. Copolymeres dibloc et tribloc de polyethyleneglycol-polyacetal et compositions pharmaceutiques associees
US8075659B2 (en) 2006-02-16 2011-12-13 Basf Se Preparations with improved urease-inhibiting effect and urea-containing fertilizers containing the latter
WO2016090103A1 (fr) 2014-12-04 2016-06-09 The Trustees Of Columbia University In The City Of New York Polymères thermoréactifs biodégradables et leurs utilisations
WO2022263355A1 (fr) 2021-06-18 2022-12-22 Basf Se Polymère d'ester d'oxyde de polyalkylène, sa préparation et son utilisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4142130A1 (de) 1991-12-20 1993-06-24 Basf Ag Verwendung von polyacetalen auf basis von vinylethern und dihydroxyverbindungen in wasch- und reinigungsmitteln und polyacetale
US5330675A (en) * 1991-12-20 1994-07-19 Basf Aktiengesellschaft Use of polyacetals based on vinyl ethers and dihydroxy compounds in detergents and cleaners and polyacetals
DE4237337A1 (de) 1992-11-05 1994-05-11 Basf Ag Blockcopolyacetale, Verfahren zu ihrer Herstellung und ihre Verwendung in Wasch- und Reinigungsmitteln
WO2006105123A2 (fr) 2005-03-31 2006-10-05 Ap Pharma, Inc. Copolymeres dibloc et tribloc de polyethyleneglycol-polyacetal et compositions pharmaceutiques associees
US8075659B2 (en) 2006-02-16 2011-12-13 Basf Se Preparations with improved urease-inhibiting effect and urea-containing fertilizers containing the latter
WO2016090103A1 (fr) 2014-12-04 2016-06-09 The Trustees Of Columbia University In The City Of New York Polymères thermoréactifs biodégradables et leurs utilisations
WO2022263355A1 (fr) 2021-06-18 2022-12-22 Basf Se Polymère d'ester d'oxyde de polyalkylène, sa préparation et son utilisation

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
"Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography", OECD, no. 118, 1996
"Journal of Polymer Science: Polymer Letters Edition", vol. 18, 1980, pages: 293 - 297
"OECD Guidelines for the Testing of Chemicals", 2013, THE BRITISH CROP PROTECTION COUNCIL
"Technical Monograph", May 2008, CROPLIFE INTERNATIONAL, article "Catalogue of pesticide formulation types and international coding system"
KNOWLES: "Agrow Reports DS243", 2005, T&F INFORMA, article "New developments in crop protection product formulation"
KNOWLES: "Agrow Reports DS256", 2006, T&F INFORMA, article "Adjuvants and additives"
KOBERSTEIN ET AL., MACROMOLECULES, vol. 49, 2016, pages 1858 - 1864
MCCUTCHEON'S, vol. 1
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
OECD TG, vol. 118, 1996

Similar Documents

Publication Publication Date Title
UA129880C2 (uk) Композиції, що мають пестицидну дію, і способи, пов'язані з ними
UA127242C2 (uk) Суміші й композиції, які містять штами paenibacillus або фузарицидини і хімічні пестициди
US20240309022A1 (en) Metal-Organic Frameworks with Pyrazole-Based Building Blocks
US12075780B2 (en) Use of alkoxypyrazoles as nitrification inhibitors
CN105705016A (zh) 包含活性物和由n-乙烯基内酰胺、乙烯基酯和醇烷氧基化物制成的接枝共聚物的组合物
WO2020020765A1 (fr) Utilisation d'un composé de thiazolidine substitué en tant qu'inhibiteur de nitrification
EP3493672A1 (fr) Formulation agrochimique de microcapsules avec un codispersant c6-c10 anionique
KR102730587B1 (ko) 질화작용 저해제로서의 n-관능화 알콕시 피라졸 화합물의 용도
CN111683528B (zh) 吡唑炔丙基醚作为硝化抑制剂的用途
UA128276C2 (uk) Сільськогосподарський або садовий інсектицид або засіб для боротьби з ектопаразитами або ендопаразитами тварин, кожен з яких включає конденсовану гетероциклічну сполуку, яка містить заміщену циклопропаноксадіазольну групу, або її сіль як активний інгредієнт, і спосіб застосування вказаного інсектициду або засобу для боротьби
WO2024126271A1 (fr) Polymères greffés biodégradables, leur production et leur utilisation dans des formulations agrochimiques
WO2025223971A1 (fr) Copolymères séquencés amphiphiles de polyacétal, leur production et leur utilisation dans des produits agrochimiques et des formulations agrochimiques
KR102705587B1 (ko) 질화작용 저해제로서의 실릴에티닐 헤타릴 화합물
WO2023203066A1 (fr) Action synergique en tant qu'inhibiteurs de nitrification d'oligomères de dicyandiamide (dcd) avec l'alcoxypyrazole et ses oligomères
JP2025541215A (ja) 生分解性グラフトポリマー、それらの製造、及び農薬製剤におけるそれらの使用
EP4011208A1 (fr) Compositions de microparticules comprenant du fluopyram
WO2024126115A1 (fr) Formulations agrochimiques
WO2025242698A1 (fr) Formulation agrochimique à base d'émulsion huile-dans-eau
RU2838138C2 (ru) Применение n-функционализированных алкоксипиразольных соединений в качестве ингибиторов нитрификации
EP4598348A1 (fr) Concentré émulsifiable ayant un système de solvant à base de lactone
WO2025093527A1 (fr) Concentré émulsifiable ayant un système de solvant amide/ester/co-solvant
WO2025037008A1 (fr) Concentré émulsifiable ayant un système de solvant à base de benzaldéhyde
WO2025233453A1 (fr) Nouvelles formulations agrochimiques
WO2025131970A1 (fr) Nouvelles formulations agrochimiques
WO2025119715A1 (fr) Nouvelles formulations pesticides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25720360

Country of ref document: EP

Kind code of ref document: A1