Biodegradable graft polymers, their production and their use in agrochemical formulations

Abstract

The present invention relates to an agrochemical composition comprising an agrochemical active ingredient and a cleaning composition comprising a cleaning additive, each further comprising at least one novel graft polymer comprising a polymer main chain (A) as a graft matrix having grafted polymer side chains (B) thereon. The polymer side chain (B) is obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally a further monomer. The polymer backbone (A) comprises a polyalkylene oxide-derived moiety and a moiety derived from a lactone and / or a hydroxy acid, which moieties are mixed such that the polymer backbone contains ester functional groups within the polymer chain. The graft polymers of the compositions of the invention have been found to be suitable as dispersants for pesticidal agents in agrochemical compositions, and also suitable in cleaning compositions for improving cleaning properties. In addition, the graft polymer typically exhibits a suitably high degree of biodegradability and thus allows for a more environmentally friendly formulation. The graft polymer itself and its production are also claimed.

Description

[0001] The present invention relates to novel graft polymers comprising a polymer backbone (A) as a grafting matrix, onto which are grafted polymer side chains (B). The polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally further monomers (B3), and optionally further monomers. The polymer backbone (A) is made up of at least two subunits (a1) and (a2), wherein (a1) is derived from at least one alkylene oxide monomer and (a2) is a unit derived from at least one lactone and / or at least one hydroxy acid.

[0002] The present invention further relates to a process for obtaining such a graft polymer, preferably by polycondensation. Furthermore, the present invention relates to the use of such a graft polymer, for example in agrochemical formulations. Another subject matter of the present invention is a composition comprising at least one graft polymer, such as for use in agrochemical formulations. Background Art

[0003] Agrochemicals (agrochemicals) such as pesticides (pesticide active ingredients) are materials that provide control of agricultural pests including insects, pathogens, rodents and weeds. The pesticide active ingredient is typically applied to plants or their seeds by spraying with a liquid composition containing the active ingredient.

[0004] Pesticides are typically solid particles, quasi-crystal particles, or oily liquids that must be dispersed in a liquid composition for uniform application. Compositions containing finely dispersed pesticidal active ingredients are typically obtained by including a dispersant. Examples of conventional dispersants include salts of naphthalenesulfonate formaldehyde condensates, salts of lignin sulfonates, salts of maleic anhydride copolymers, and salts of condensed phenolsulfonic acid.

[0005] Unfortunately, many dispersants used in agrochemical compositions do not significantly decompose and remain on both the plant or seed and the surrounding area, resulting in undesirable accumulation on the plant or seed and in the soil in which the plant or seed is grown. This problem is particularly prominent for dispersants produced by free radical polymerization based on only carbon backbones (main chains that do not contain heteroatoms such as oxygen), because only carbon backbones are particularly difficult to degrade for microorganisms. Even industrially important graft polymers produced by free radical methods with a polyethylene glycol backbone only show limited biodegradation in wastewater.

[0006] It would be desirable to provide dispersants, particularly biodegradable dispersants, that are useful in agrochemical compositions.

[0007] Many countries have introduced measures to ban microplastics, especially in cosmetic products. In addition to banning insoluble microplastics, there is also an intense dialogue about the future requirements of soluble polymers used in consumer products. Therefore, it is highly expected to identify new and better biodegradable ingredients for such applications. This problem is very serious for polymers produced by free radical polymerization based on only carbon backbones (main chains without heteroatoms such as oxygen), because only carbon backbones are particularly difficult for microorganisms to degrade. Even graft polymers produced by free radical methods with polyethylene glycol main chains of industrial importance only show limited biodegradation in wastewater. However, the polymers described by the present invention are preferably prepared by free radical graft polymerization and provide enhanced biodegradation properties compared to the prior art.

[0008] Polyalkylene oxides are important polymers with a wide range of applications. They have been widely used as a basis for the production of graft polymers, which are used in all kinds of formulations, including agrochemical formulations.

[0009] Similarly, graft polymers of vinyl esters grafted onto polyalkylene oxide polymers such as vinyl acetate grafted onto polyethylene glycol are known polymers. Their use in the field of agrochemical formulations and in many other fields of application is also known.

[0010] However, those polymers lack biodegradability or at least suffer from very limited biodegradability.

[0011] However, a certain amount, if not all, of such agrochemical formulations are carried into the environment during their application and, therefore, if not biodegraded or otherwise permanently absorbed, end up in rivers or the ocean or may be absorbed by plants, animals and ultimately humans, from where they may also end up in sewage treatment plants.

[0012] Therefore, biodegradability is not only one of the upcoming very important features in the field of agrochemical formulations, as biodegradable polymers can avoid such buildup problems, which may no longer be acceptable in certain countries.

[0013] On the other hand, the functionality imparted by such polymers is also of primary importance, since they allow for high formulation efficiency and therefore, among other advantages, low use of agrochemical additives per treatment, thus allowing for savings in the materials used and thus also avoiding environmental pollution. They are therefore desirable for more environmentally friendly agricultural practices.

[0014] Therefore, providing biodegradable polymers for use in the field of agrochemical formulations is of utmost importance to solve the environmental pollution problem without compromising the processing efficiency, as such lower efficiency would not only inevitably pollute the environment.

[0015] The poor biodegradability of polyalkylene oxides decreases in the range of molecular weights from a few hundred g / mol up to a few thousand g / mol. Furthermore, graft polymers based on such polyalkylene oxides can often be even poorer in their biodegradability due to the grafting.

[0016] Prior art graft polymers

[0017] US Pat. No. 5,318,719 A relates to biodegradable, water-soluble graft copolymers having building, anti-filming, dispersing, and threshold crystal inhibition properties, comprising an acid-functional monomer and, optionally, other water-soluble, monoethylenically unsaturated monomers copolymerizable with the acid-functional monomer grafted to a biodegradable substrate comprising a polyalkylene oxide and / or polyalkoxylated material. These graft polymers are believed to be suitable as detergent additives.

[0018] CN 102 030 871 A relates to polyethylene glycol-blocked biodegradable polyester comb-type graft copolymers. These comb-type graft copolymers are homopolymers or copolymers in which a biodegradable polyester with polyethylene glycol blocks serves as the hydrophobic backbone. The polymers are described as self-assembling in water to form nanoparticles that can be used to prepare hydrophobic drug nanoparticles.

[0019] US Pat. No. 31816566 discloses grafted polymers of so-called "lactone polyesters" and their blends with PVC. Lactone polyesters are homopolymers of ε-caprolactone or copolyesters thereof with ε-alkyl-ε-caprolactones. Polymers made of lactones and alkylene oxides, as used as grafting substrates in the present invention, are not disclosed. The lactone polyesters of US Pat. No. 31816566 are grafted with ethylenically unsaturated monomers, and "vinyl esters of aliphatic acids" are also mentioned in a long list, where vinyl formate, vinyl acetate, and vinyl propionate are exemplified. 22 examples show the use of acrylic acid, butyl acrylate, dimethylamino methacrylate, styrene, acrylonitrile, and methyl methacrylate as the only monomers actually employed, all as single monomers only and without graft polymerization of monomer mixtures. Only one example (Example 12) uses vinyl acetate as a monomer and poly-ε-caprolactone as a grafting base (i.e., a grafting base that does not contain any alkylene oxide), employing 200 grams of backbone and 30 grams of vinyl acetate, i.e., 15 wt.% vinyl acetate based on the grafting base, equivalent to 13 wt.% vinyl acetate based on the total polymer weight. US Pat. No. 31,816,566 discloses nothing regarding the biodegradation of this polymer; the only use disclosed is as a plasticizer in PVC polymers. Grafted polymers of the type shown in the present invention are neither disclosed nor suggested.

[0020] BASF's WO 2022 / 136409 discloses amphiphilic alkoxylated polyalkyleneimines or amines; it does not disclose graft polymers comprising a polymer made of lactones and alkylene oxides as a graft backbone grafted with an ethylenically unsaturated monomer comprising at least a vinyl ester in a free radical polymerization. Therefore, his disclosure is completely unrelated to the present invention, except for the fact that it also targets polymer structures for use in fields similar to those of the present invention and that those products contain lactones and alkylene oxides. Lactones and alkylene oxides are polymerized to produce lactone-alkylene oxide copolymers, which are attached to the amine groups of the starting compounds polyethyleneimine or polyamine. After the formation of those side chains, no graft polymerization is carried out. Therefore, these structures and their preparation, as well as these properties and therefore the functions in the application of such compounds, are completely different. Graft polymers of the type shown in the present invention are not disclosed or indicated.

[0021] US2022 / 0056380 discloses cleaning compositions that focus on specific enzymes and therefore do not focus on specific polymers themselves, their structure or preparation or properties. Among the many ingredients of such compositions, grafted polymers are also mentioned as ingredients. However, grafted polymers are typically known grafted polymers (such as the preferably mentioned "BASF's"). HP22" - none of which contain lactones in the main chain of the polymer, so this main chain is made only of alkylene oxides. Those alkylene oxides, and especially the preferred polymers with a main chain molecular weight of about 6000 g / mol, are not very biodegradable at all, while graft polymers prepared using such polyalkylene oxide main chains, as shown in the present invention, have even poorer biodegradation. Graft polymers of the type shown in the present invention are neither disclosed nor suggested.

[0022] At the time of filing the present invention, the problem of improving the biodegradation of graft polymers based on a backbone having polyalkylene oxide units in the backbone had already been addressed in the unpublished patent application PCT / EP2022 / 065983 (now published as WO2022 / 263354), which discloses graft polymers based on a backbone comprising ester functional groups and polyalkylene oxide units as functional units. The backbone is prepared by oxidizing the polyalkylene oxide in a first reaction and then esterifying the oxidized PEG mixture with itself or with additionally added polyalkylene oxide. The backbone is then grafted with vinyl acetate.

[0023] The polymers disclosed herein undergo a two-step backbone synthesis: oxidation, as the first reaction step, is expensive and lengthy, and the resulting composition is difficult to control because, depending on the reaction time, the content of the mixture varies. Typically, the resulting mixture contains unoxidized starting material, a polyalkylene oxide having one hydroxyl group oxidized to a carboxyl function, and a polyalkylene oxide having both terminal ends oxidized. Consequently, the flexibility in designing the backbone is highly limited.

[0024] This patent application also does not disclose the use of nitrogen-containing monomers for preparing graft polymers.

[0025] This patent application discloses the use of such polymers in agrochemical formulations.

[0026] Existing technologies regarding the main chain

[0027] The present invention discloses the use of three main types of polymer backbones comprising (oligo- / poly-)alkylene oxide moieties and (oligo- / poly-)lactone / hydroxy acid derived moieties.

[0028] Such main chains are designated (A1), (A2) and (A3) (see definitions below) and are known in principle to date:

[0029] (A1)

[0030] WO 2002046268 (Cognis, now BASF) discloses biodegradable polymers useful as surfactants, emulsifiers, etc., obtained by reacting an organic initiator with a mixture of 1. an alkylene oxide, 2. an alkylene oxide, and a lactone. "Organic initiator" is defined on page 4 as a monofunctional or polyfunctional alcohol or amine.

[0031] To obtain copolymers from alkylene oxide and caprolactone, suitable starters are reacted with a premixed combination of alkylene oxide and caprolactone.

[0032] To obtain the (A1)-backbone type copolymer from alkylene oxide and lactone such as caprolactone, suitable starters are reacted with a premixed combination of alkylene oxide and caprolactone.

[0033] An alcohol (diol) having two hydroxyl groups is used as a starting material. Examples of such diols are ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and the like.

[0034] Alkylene oxides used in combination with caprolactone are: ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, preferably ethylene oxide and propylene oxide.

[0035] The copolymerization of alkylene oxide and caprolactone is carried out under typical conditions for alkoxylation reactions, using basic catalysts such as potassium hydroxide, sodium hydroxide, sodium methoxide, potassium methoxide.

[0036] (A2)-Backbone polymers can in principle be obtained by alkoxylation of polylactones.

[0037] Polylactones are obtainable, for example, by polymerizing lactones such as caprolactone onto starters having two hydroxyl groups such as diols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

[0038] The polymerization of caprolactone is carried out with various catalysts like the transesterification catalyst tin(II) alkanoate.

[0039] The alkoxylation of such polycaprolactones is carried out under typical alkoxylation conditions. Due to the alkaline reaction conditions used for the alkoxylation, transesterification reactions at the ester bonds of the polycaprolactone can occur.

[0040] US 4281172 describes acrylates from polyester-polyether copolymers. To obtain these structures, polylactones from mono-, di-, tri- or tetra-ols are reacted with alkylene oxides.

[0041] Polylactone esters are synthesized according to US Pat. No. 3,169,945 from hydroxyl-containing components using various catalysts including Ti or Sn catalysts or alkali metal hydroxides.

[0042] The alkoxylation reaction is catalyzed by BF3-etherate or potassium hydroxide.

[0043] JP 07149883 describes a process for obtaining polyester-polyols by reacting a compound having at least two active hydrogen atoms with a lactone and subsequently with an alkylene oxide. Both reactions are carried out using the same catalyst, which is an alkali metal hydroxide or an alkali metal alcoholate.

[0044] WO 9636656 claims biodegradable alkylene oxide-lactone copolymers. These polymers are synthesized from difunctional or polyfunctional starters that react with alkylene oxides and lactones in a copolymerization reaction and are subsequently end-capped with alkylene oxide blocks. The catalyst is an alkali metal hydroxide or alkaline earth metal hydroxide or a Lewis acid. The patent application describes the improved biodegradability of the claimed polymers over polyalkylene oxides, as well as their use as surfactants, emulsifiers, etc., but not as backbones for grafted polymers.

[0045] (A3)-Main-chain polymers can in principle be obtained by polyesterification of polyalkylene glycols with lactones to give simplified triblock polymers.

[0046] Triblock copolymers from caprolactone and alkylene oxide with a central polyalkylene oxide block are synthesized by 1. forming a polyalkoxylate from a diol or water by reaction with an alkylene oxide, and 2. polymerizing caprolactone onto the polyalkoxylate.

[0047] Both reactions can be carried out under typical reaction conditions for alkoxylation reactions (polyalkoxylates) and for caprolactone polymerization (polycaprolactone blocks).

[0048] Such triblock copolymers with a central polyethylene oxide block have been known since about the 1990s. These polymers are used for drug release and dissolution purposes (Z. Zhu et al., Journal of Polymer Science, Part A: Polymer Chemistry 1997, 35(4), 709-714; M. Boffito et al., Journal of Biomedical Materials Research, Part A 2015, 103A(3), 1276-1290).

[0049] (A4)-type backbones are also known:

[0050] WO 96 / 36656 discloses biodegradable oxide-lactone copolymers and copolyesters as already described above for (A3).

[0051] WO 2002046268 (Cornings, now BASF) discloses alkylene oxide-lactone copolymers as already described for (A1).

[0052] However, the use of such polymers as backbones for grafted polymers, into which improved biodegradation is introduced via the backbone, is not known.

[0053] Purpose of the Invention

[0054] It was recognized that graft polymers based on conventional polyalkylene oxides (without ester groups in the main chain) show unexpectedly low biodegradation, which is often much lower than the expected percentage biodegradation calculated based on the biodegradation of pure polyalkylene oxide.

[0055] Compared to unmodified polyalkylene oxide and unmodified polyalkylene glycol, graft polymers based on such conventional polyalkylene oxides generally show reduced biodegradation due to the increase in the degree of modification (i.e., the number of side chains on the main chain) of the polyalkylene oxide (usually polyalkylene oxides with two hydroxyl end groups are employed, and therefore such polyalkylene oxides with hydroxyl groups are generally referred to as "polyalkylene glycols") that is grafted onto such a main chain by free radicals with polymerizable monomers. This is sometimes attributed to a blockage of the biodegradation mechanism, as it appears that the polyalkylene oxide / polyalkylene glycol degrades starting from their respective end groups and then along the polymer chain. Therefore, any additional branching on the carbon atoms of the main chain - which occurs when polymer side chains are grafted onto such a main chain - hinders and may completely stop degradation. Therefore, it is suggested that the higher the degree of grafting (i.e., the more side chains attached to the main chain), the lower the percentage of biodegradation of such graft polymers. Unfortunately, it is also often observed that the performance in the desired application improves with a higher degree of branching, since only at higher amounts of side chains does the chemical structure of the main chain change sufficiently to allow the new grafted polymer to develop its specific properties compared to the individual properties of the unmodified main chain in a simple mixture of (unattached / ungrafted) homopolymers constituting the side chains of the grafted polymer.

[0056] Thus, the difficulty of combining the conflicting properties of suitable graft polymers with excellent application properties with the biodegradation percentage of the unmodified backbone (ie, unmodified polyalkylene oxide / polyalkylene glycol) when polyalkylene oxide is used as the backbone has not been solved to date.

[0057] Although the unpublished patent application PCT / EP2022 / 065983 has provided a first solution to the problem of the lack of biodegradation of the polyalkylene oxide backbone, the practical aspects of the solution found remain unsatisfactory, since the two-step reaction is lengthy and expensive, since two completely different types of chemical reactions (oxidation and polymerization) are employed, and the structural changes are not easy to control, since oxidation results in a mixture of compounds that are diols (i.e. the starting material polyalkylene glycol), monoalcohol-monocarbonic acid (i.e. partially oxidized polyalkylene glycol) and dicarboxyl-polyalkylene oxide (i.e. fully oxidized polyalkylene glycol). The structures used here are not obtainable by the process disclosed in this document. Similarly, nitrogen-containing monomers are not disclosed.

[0058] Therefore, there is a need to improve the biodegradation of conventional graft polymers based on polyalkylene oxide by improving the biodegradability of the graft matrix and maintaining the general structure of the graft polymer and thus maintaining the application properties or even improving them, as well as to improve the cost and efficiency of the unpublished patent application PCT / EP2022 / 065983 by reducing the production process to only one reaction step using only one reaction type and at the same time improving the variability of the chemical structure.

[0059] Although polymers of the types (A1 ), (A2) and (A3) as defined herein are known, the use of such polymers as backbones for preparing graft polymers is not known.

[0060] It was therefore an object of the present invention to provide novel graft polymers based on polyalkylene oxide-type graft backbones endowed with ester functional groups.

[0061] Furthermore, these novel graft polymers should have advantageous properties with regard to biodegradability and / or their performance in agrochemical formulations.

[0062] Graft polymer

[0063] The graft polymer of the present invention comprises a polymer main chain as a graft base as a first structural unit and a polymer side chain as a second structural unit.

[0064] First structural unit (main chain)

[0065] The first structural unit of the grafted polymer is a polymer backbone used as a grafting base for the graft polymer used in the present invention, wherein the polymer backbone (A) is obtainable by polymerization of at least one subunit (a1) and at least one subunit (a2).

[0066] Subunit (a1) is composed of at least one alkylene oxide monomer and / or at least one polyoxyethylene having two hydroxyl end groups. Alkane-polymer made, the alkylene oxide monomer is chosen from C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentane oxide or 2,3-pentane oxide; from 1,4-diol or its cyclic or oligomeric analogs, or polymeric ethers based on such 1,4-diols; from 1,6-diol or its cyclic or oligomeric analogs, or polymeric ethers based on such 1,6-diols; or any of their mixtures in any ratio, as blocks of certain polymer units, or as statistical polymer structures, or polymers comprising one or more homopolymeric blocks of a certain monomer and one or more statistical blocks comprising more than one such monomer, and any combination thereof, such as polymers having several different blocks of two or more different monomers, or blocks of two or more different monomers, blocks of statistical mixtures of two or more monomers, etc.

[0067] As used herein, the term "block (co)polymer" means that the corresponding polymer comprises at least two (i.e., two, three, four, five or more) homopolymers or copolymer subunits ("blocks") connected by covalent bonds. A "diblock" copolymer has two different blocks (homopolymers and / or copolymer subunits), while a "triblock" copolymer therefore has three different blocks (homopolymers and / or copolymer subunits), and so on. The number of individual blocks in such block copolymers is not limited; therefore, an "n-block copolymer" comprises n different blocks (homopolymers and / or copolymer subunits). In a single block, the size / length of such a block may vary independently of the other blocks. The minimum length / size of a block is based on two separate monomers (as a minimum), but can be as high as 50 or even 100 or 200, as well as any number between 2 and 200. The corresponding monomers for the separate blocks used to prepare the block copolymer backbone (a1) can be added sequentially. However, it is also possible that there is a transition of the feed from one monomer to another, resulting in a so-called "dirty structure", wherein at the edge / boundary of the respective block, a minority of monomers of the respective adjacent block may be contained in a separate block to be considered (so-called "dirty structure" or "dirty segment"). However, it is preferred that the block copolymer subunits (a1) according to the present invention do not contain any dirty structure at the respective block boundaries, although for commercial reasons (i.e., mainly for efficient use of reactor costs, etc.), a small amount of dirty structure may still be contained (although not intentionally).

[0068] Preferably, at least one monomer in the polymer is derived from the use of ethylene oxide.

[0069] In another embodiment, the structure of the polymer subunit (A1) comprises more than one alkylene oxide monomer; in this case, the polymer backbone is a random copolymer, a block copolymer, or a copolymer comprising a mixed structure of block units (where each block is a homoblock or a random block itself) and a statistical / random part composed of two or more alkylene oxides, one of which is ethylene oxide. Preferably, in addition to ethylene oxide, the additional monomers are propylene oxide (PO) and / or 1,2-butylene oxide (BO), preferably only 1,2-propylene oxide.

[0070] Subunit (a2) is made from at least one lactone and / or at least one hydroxy acid.

[0071] The at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0072] i) lactones, i.e. cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone;

[0073] as well as

[0074] ii) hydroxy acids, which can be derived from any lactone by hydrolysis, in particular from any lactone within the preceding group i), in particular α-, β- or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0075] Preferably it is lactic acid or caprolactone, more preferably caprolactone.

[0076] Depending on how the starting materials are employed and on the relative amounts, subunits (a1) and (a2) can be combined in any order.

[0077] Thus, the polymer backbone (A) obtained by the reaction of (a1) and (a2) can be defined within very wide limits by selecting the desired subunits (a1) and (a2) and - within subunit (a1) by selecting the number of different alkylene oxides, their relative amounts, their reaction sequence, etc., and of course also for (a2) by selecting the compounds, their relative amounts, etc., in this way

[0078] -1) obtaining a first defined (a1)-subunit and then reacting it with an (a2)-subunit,

[0079] -2) reacting monomeric alkylene oxides from subunit (a1) directly with monomeric subunit (a2); or

[0080] -3) Combine the previous methods 1) and 2).

[0081] Therefore, three main chain structures can be defined and obtained:

[0082] (A1):

[0083] The subunits (a2) can be added during the polymerization of the alkylene oxides (a1 units), giving rise to random copolymers; in a variant thereof, polyalkylene oxides having two hydroxyl groups can be added to such a polymerization, thereby introducing specific (a1) subunit blocks; this variant is useful if the alkylene oxide employed differs at least in part from the alkylene oxide used to prepare the polyalkylene oxide also employed, or if the structure of the polyalkylene oxide (i.e. the sequence of the alkyleneoxy units therein) differs from the structure obtained by reacting the at least one alkylene oxide used for the copolymerization with the (a2) subunits and the polyalkylene oxide.

[0084] In a simplified approach, the (A1)-backbone can be described as a random sequence of (a1)-subunits and (a2)-subunits. Depending on the relative amounts of (a1) and (a2) and their reactivities, the block lengths of (a1) and (a2) vary.

[0085] This method can be used to obtain a structure like the one shown below:

[0086] poly[random-{lactone}-{alkylene oxide}]

[0087] (“Oligo / polylactone” depicts the (a2)-subunit and is therefore prepared from lactone / hydroxy acid; “PAG” = polyalkylene glycol is used here to depict the (a1)-subunit)

[0088] Therefore, in a preferred embodiment, the polymer backbone is selected from (A1) to (A4):

[0089] (A1) A main chain consisting of a randomly arranged sequence of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits, wherein more than one subunit (a1) and / or more than one subunit (a2) are present.

[0090] (A2):

[0091] The subunits (a2) can first be oligomerized / polymerized and copolymerized with at least one alkylene oxide to give mixed random / block structures; depending on the degree of oligomerization of the lactone / hydroxy acid and if monomeric lactone / hydroxy acid is also present when the alkylene oxide is added, the structure can be further modified by adjusting the amount and length of the (a2)-subunit chains within the (A2)-backbone.

[0092] Just like (A1), in a further variant thereof, polyalkylene oxides having two hydroxyl groups can also be added to such a polymerization, thereby also introducing specific (a1) subunit blocks; this variant is useful if the alkylene oxide employed is at least partially different from the alkylene oxide used to prepare the polyalkylene oxide also employed, or if the structure of the polyalkylene oxide (i.e. the sequence of the alkyleneoxy units therein) differs from the structure obtained by reacting the at least one alkylene oxide used for the copolymerization with the (a2) subunits and the polyalkylene oxide.

[0093] In a simplified approach, the (A2)-backbone can be described as a triblock polymer with an inner (a2)-block and two outer (a1)-blocks.

[0094] (Switching the sequence in the opposite direction gives structure (A3); see below.)

[0095] A structure like the one shown below (in its simplest form) can be obtained by this method:

[0096] [PAG]-[oligo / polylactone]-[PAG]

[0097] (“Lactone” is used here to denote the (a2)-subunit, thus made from a lactone / hydroxy acid, and can be a single monomeric unit or an oligomeric or polymeric unit made from the monomers in the first reaction step; “PAG” = polyalkylene glycol is used here to depict the (a1)-subunit)

[0098] In the case that the (a2)-subunit starting material has not yet reacted completely, the structure will no longer be a true triblock structure, but will additionally contain further shorter (a2)-units in the chain and will therefore consist of a multiblock structure or even turn into a mixture of block and random structural arrangements.

[0099] Thus, in a preferred embodiment, the polymer backbone is selected from (A2) backbones consisting of oligomeric or polymeric subunits (a2) as inner blocks and two outer blocks of oligomeric and / or polymeric (a1)-subunits, defined as "-[block of (a1)]-[block of (a2)]-[block of (a1)]-", and possibly also higher block polymers such as 5-blocks, 7-blocks and 9-blocks, etc., in which the additional blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as pentablocks "[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]", etc.

[0100] (A3):

[0101] Subunits (a2) can be added after oligomerization or (almost complete) polymerization of the alkylene oxide, resulting in block structures containing larger (a2) chains and larger (a1) chains; in the case where (a1) is fully polymerized before the addition of (a2), the resulting structure can be described as "(a2)-polyalkylene oxide-(a2)"; such structures can also be obtained by directly reacting polyalkylene oxide with (a2). More complex structures can be obtained by only first oligomerizing the alkylene oxide and then reacting a mixture containing alkylene oxide oligomers and monomeric alkylene oxide with (a2), or by polymerizing (a2) with alkylene oxide and with polyalkylene oxide.

[0102] In a simplified approach, the (A3)-backbone can be described as a triblock polymer with an inner (a1)-block and two outer (a2)-blocks:

[0103] (Switching the sequence in the opposite direction gives structure (A2); see above.)

[0104] [Oligo / Polylactone]-[PAG]-[Oligo / Polylactone]

[0105] (“Oligo / polylactone” depicts the (a2)-subunit and is therefore prepared from lactone / hydroxy acid; “PAG” = polyalkylene glycol is used here to depict the (a1)-subunit)

[0106] Thus, in a preferred embodiment, the polymer backbone is selected from (A3) a backbone consisting of an inner block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunits (a2), which are at least in the form of a triblock polymer defined as "-[block of (a2)]-[block of (a1)]-[block of (a2)]-".

[0107] Analogously to the case of (A2), if the (a2)-subunit starting material has not yet reacted completely, the structure will no longer be a true triblock structure, but will additionally contain further shorter (a1)-units in the chain and will therefore consist of a multiblock structure or even turn to a mixture of block and random structural arrangements.

[0108] Similarity between (A1), (A2) and (A3)

[0109] When the corresponding other subunit species are added, there is more unreacted (a2) species (in the case of (A2)-backbone) or more unreacted (a1) species (in the case of (A3)-backbone), and the difference between (A2) and (A3) decreases.

[0110] In the extreme case, the result will be a true copolymerization of subunits (a1) and (a2) and will therefore also be similar or even identical to (A1).

[0111] Thus, (A1), (A2) and (A3) are "just" extremes of the general principle of copolymerizing alkylene oxides, polyalkylene glycols and lactones / hydroxy acids in every conceivable variation of sequence, ratio and reaction time before adding the other starting materials.

[0112] Thus, in a preferred embodiment, the polymer backbone is selected from backbones obtained by the general principle of copolymerizing alkylene oxides, polyalkylene glycols, and lactones / hydroxy acids in every conceivable sequence, ratio, and reaction time variation before adding the other starting materials.

[0113] (A4):

[0114] (A4) is a structure starting from an oligomeric or polymeric subunit (a1) which is capped on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4. This one-side capped oligomer / polymer of subunit (a1) is then subsequently reacted with at least one subunit (a2) and optionally at least one subunit (a1) - wherein the subunits (a1) may be different from those in the starter block or may be arranged in a different order than those in the starter block - to attach a new block comprising a portion of the subunit used from the (co)polymerization to the uncapped side of the starter block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}].

[0115] In a preferred embodiment, the polymer backbone serving as the grafting matrix comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0116] (a1) is a unit comprising, preferably consisting essentially of, a portion derived from at least one alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, and / or at least one polyalkylene oxide polymer having two hydroxyl end groups,

[0117] (a2) is a unit comprising (preferably consisting of) at least one lactone and / or at least one hydroxy acid, this seed unit (a2) being a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0118] Wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0119] i) lactones, i.e. cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone;

[0120] as well as

[0121] ii) hydroxy acids, which can be derived from any lactone by hydrolysis, in particular from any lactone within the preceding group i), in particular α-, β- or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0122] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0123] The polymer backbone is obtained by:

[0124] (A1) copolymerization of at least one subunit (a1) and at least one subunit (a2), wherein optionally, at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and at least one subunit (a2);

[0125] (A2) first oligomerizing / polymerizing subunit (a2) and then polymerizing the product with subunit (a1);

[0126] (A3) first oligomerizing / polymerizing subunit (a1) and then copolymerizing the product with subunit (a2); or

[0127] (A4) first providing an oligomeric or polymeric subunit (a1) carrying a capping group on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4, which - as a starter block - is thereafter reacted with at least one subunit (a2) and optionally at least one subunit (a1) - wherein the subunit (a1) may be different from the one / those in the starter block or may be arranged in a different order compared to those in the starter block - to attach a new block comprising parts from the subunits used for (co)polymerization to the uncapped side of the starter block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0128] Where more than one subunit (a1) and / or more than one subunit (a2) are already present in the oligomer or polymer employed, those subunits may be arranged in any order within such oligomer or polymer employed, and

[0129] Where more than one subunit (a1) and / or more than one subunit (a2) are present for polymerization, those subunits (and optional oligomers / polymers, if employed) may be arranged in any order within the resulting backbone.

[0130] The polymer backbone (A), and in particular (A1), (A2) and (A3), can optionally be terminated at the end groups, using known techniques with C1-C25 alkyl groups, preferably C1 to C4 groups. Such termination will be carried out after the backbone has been generated and can preferably be carried out before grafting.

[0131] In the case of (A4), the end capping is carried out at one end before the condensation polymerization with subunits (a1) and / or subunits (a2), since only then can the structure (A4) be obtained. In another more preferred process, (A4) is produced starting from a monohydric alcohol, which is then reacted with an alkylene oxide to obtain a "single-terminated" oligomer / polymer of subunit (a1) (with one hydroxyl group at the end of the oligo / polyalkylene oxide chain), which is then reacted with subunit (a2) to obtain (A4).

[0132] When preparing oligoalkylene oxides / polyalkylene oxides as starting blocks, diols can be used as starting molecules for preparing the oligoalkylene oxides / polyalkylene oxides, and thus the oligomers / polymers of subunit (a1) can contain moieties derived from such diols in their structures. Diols for such applications and methods for preparing such oligoalkylene oxides / polyalkylene oxides containing diols in their structures are known. Typical diols are ethylene glycol, propylene glycol, and the like. In principle, all commonly known diols can be used for this purpose.

[0133] In another preferred embodiment, the polymer backbone serving as the grafting matrix comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0134] (a1) is a unit comprising, preferably consisting essentially of, a portion derived from at least one alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, and / or at least one polyalkylene oxide polymer having two hydroxyl end groups,

[0135] (a2) is a unit comprising (preferably consisting of) at least one lactone and / or at least one hydroxy acid, this seed unit (a2) being a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0136] Wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0137] i) lactones, i.e. cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone;

[0138] as well as

[0139] ii) hydroxy acids, which can be derived from any lactone by hydrolysis, in particular from any lactone within the preceding group i), in particular α-, β- or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0140] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0141] The polymer backbone as the grafting matrix (A) is selected from

[0142] (A1) a backbone consisting of a randomly arranged sequence of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits, wherein more than one subunit (a1) and / or more than one subunit (a2) are present;

[0143] (A2) a backbone consisting of an inner block of oligomeric or polymeric subunits (a2) and two outer blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as “-[block of (a1)]-[block of (a2)]-[block of (a1)]-” and may also comprise higher order block polymers such as 5-blocks, 7-blocks and 9-blocks, etc., in which further blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as a pentablock “[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]”, etc.;

[0144] (A3) a backbone consisting of an inner block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunits (a2), at least in the form of a triblock polymer defined as "-[block of (a2)]-[block of (a1)]-[block of (a2)]-", and

[0145] (A4) A main chain consisting of:

[0146] The first block has

[0147] (i) a capping group on one end - such a capping group is a C1 to C18-, preferably C1-C4-alkyl group attached to the first block via an ether function; and

[0148] (ii) oligomeric or polymeric subunit (a1); and

[0149] a second block attached to the first block via an ether or ester functionality at the opposite end of the first block ("opposite" with respect to the endcapping on the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1),

[0150] wherein the optional subunits (a1) in the second block may be different from that / those in the first block, or may be arranged in a different order compared to those in the first block, and the order of subunits (A1) and (a2) may also be in any order, including a random structure,

[0151] Such a diblock structure has the following as an idealized structure when only subunit (a2) is used for the second block: [capping group]-[subunit (a1)]-[subunit (a2)]

[0152] Or in the case of using subunits (a1) and (a2) for the second block, the following is the idealized structure:

[0153] [End-capping group]-[Subunit (a1)]-[Random-{Subunit (a2)-Subunit (a1)}.

[0154] In a preferred embodiment, the polymer backbone (A) and in particular (A1 ), (A2) and (A3) are not terminated at the chain ends but carry hydroxyl groups.

[0155] Preferably, the polyalkoxylate-ester backbone comprises a moiety derived from

[0156] (i) an alkylene oxide (AO) comprising at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably at least one of EO and PO,

[0157] wherein the amount of the AO is 40 wt% to 95 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any values and ranges therebetween, each based on the total weight of the backbone,

[0158] The amount of EO is from 0 wt.% to 100 wt.%, preferably 10 wt.%, more preferably 20 wt.%, even more preferably 30 wt.%, even more preferably 40 wt.%, such as 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt.%, based on the total AO, the total amount of PO and / or BO is each from 0 wt.% to 100 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, even more preferably up to 70 wt.%, even more preferably up to 60 wt.% and most preferably up to 50 wt.%, and any values in between, such as up to 5 wt.%, 10 wt.%, 15 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 55 wt.%, 65 wt.%, 75 wt.%, 85 wt.% or up to 95 wt.%, and more preferably 10 wt.%, even more preferably 20 wt.%, even further more preferably 30 wt.%, such as 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO adds up to 100 wt.%, wherein the total amount of AO adds up to 100 wt.%;

[0159] (ii) lactone / hydroxy acid monomers in an amount of 1 wt.% and up to 60 wt.%, preferably up to 50 wt.%, more preferably up to 40 wt.%, most preferably up to 30 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the backbone, preferably caprolactone only;

[0160] The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

[0161] More preferably, the amount of EO is at least 80 wt.%, preferably at least about 85 wt.%, more preferably at least about 90 wt.%, even more preferably at least about 95% and most preferably about 100 wt.%, based on the total weight of AO; the amount of PO and / or BO is each from about 0 wt.% to 50 wt.%, more preferably up to about 30 wt.%, even more preferably up to about 20%, even more preferably about 10 wt.% and most preferably about 0 wt.%, based on the total weight of AO, each based on the total weight of AO; in a more preferred embodiment, the amounts of PO and BO given before this paragraph are the total amount for the sum of PO and BO. In an even more preferred embodiment, the backbone units (a1) are made only of ethylene oxide.

[0162] In an alternative but preferred embodiment, at least two different alkylene oxides are employed for the preparation of / present in the backbone.

[0163] Therefore, in a more preferred embodiment, the polymer backbone consists of

[0164] (i) alkylene oxides (AO) selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO,

[0165] The amount of EO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt% based on the total AO,

[0166] The total amount of PO and BO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt%, each based on the total weight of AO, wherein the total amount of PO and BO adds up to 100 wt.% for the sum of PO and BO, and

[0167] The total amount of AO is 100 wt.%;

[0168] (ii) the amount of lactone / hydroxy acid monomer is 1 wt.% and up to 60 wt.%, preferably up to 40 wt.%, more preferably up to 30 wt.%, even more preferably up to 25 wt.%, even further more preferably up to 20 wt.% and most preferably up to 15 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the backbone, preferably caprolactone only;

[0169] The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

[0170] Therefore, in a more preferred alternative embodiment, the polymer backbone consists of

[0171] (i) Alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, more preferably only EO

[0172] The amount of EO is 20 wt% to 100 wt% based on the total AO,

[0173] The total amount of PO and BO is from 0 wt.% to 80 wt.%, preferably up to 50 wt.%, more preferably up to 30 wt.%, even more preferably up to 20 wt.% and even further preferably up to 10 wt.% and most preferably zero, such as 45 wt.%, 45 wt.%, 45 wt.%, 25 wt.%, 15 wt.%, 7 wt.% and 5 wt.%, and any values therebetween, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO adds up to 100 wt.%,

[0174] The total amount of AO is 100 wt.%;

[0175] (ii) the amount of lactone / hydroxy acid monomer is 5 wt% and up to 50 wt%, preferably up to 40 wt%, more preferably up to 35 wt% and even more preferably up to 30 wt%, and as a lower limit preferably 7 wt%, more preferably 10 wt%, even more preferably 12 wt% and most preferably 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt% and any values therebetween as lower limits and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any values therebetween as upper limits, preferably caprolactone only;

[0176] The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

[0177] In an even more preferred embodiment, the backbone for any embodiment of the graft polymer of the present invention as defined herein is a structure selected from structures (A1 ), (A2), (A3) and / or (A4).

[0178] Second structural unit (grafted side chain)

[0179] Second structural unit of the grafted polymerare polymer side chains (B) grafted onto the polymer backbone (A), wherein the polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), optionally a further monomer (B3) and optionally further monomers in addition to (B1), (B2) and (B3).

[0180] As the vinyl ester monomer (B1), at least one of vinyl acetate, vinyl propionate and / or vinyl laurate is selected. In addition to those, other vinyl ester monomers (B1) known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, and / or vinyl benzoate, may be used.

[0181] As optional monomer (B2), at least one nitrogen-containing monomer selected from the group consisting of vinyl lactams, vinyl imidazoles, 1-vinyltriazole, 4-vinylpyridine, 4-vinylpyridine-N-oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N′-dialkyl(meth)acrylamides; mono- and dialkylamino-alkyl(meth)acrylates, which are preferably vinyl lactam monomers and / or vinyl imidazole monomers, the vinyl lactam being more preferably selected from N-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam and most preferably N-vinylpyrrolidone, and the vinyl imidazole being preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole.

[0182] As optional monomers, additional monomers (B3) may be used, which are different from (B1) and (B2) and are present only in an amount preferably less than 10% of the total amount of monomers used to obtain the polymer side chains (B), and more preferably are present only as impurities and not intentionally added for the polymerization. The (B3) monomer may be any monomer selected from the group consisting of 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amine (if hydrolyzed after polymerization), N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl esters of (meth)acrylic acid and their derivatives.

[0183] In addition to monomers (B1), (B2) and (B3), at least one further monomer (different from the previous ones) may be present for copolymerization to produce side chains (B), wherein such further monomer is only present in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chains (B) and is preferably only present as an impurity and not intentionally added for the polymerization.

[0184] In the case where monomer (B2) is present, the amount of monomer is as follows, based on the total weight of the graft polymer:

[0185] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0186] (B1) (vinyl ester) is 9 to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30% as a percentage by weight, based on the total weight of the graft polymer;

[0187] Measured as a percentage by weight based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and every number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1);

[0188] (B3) (additional monomers) is from 0% to 10%, preferably up to 2%, more preferably up to 1%, even more preferably about 0%, but in any case up to 10% of the amount of (B1) and does not exceed the amount of (B2).

[0189] The amounts of the further monomers besides (B1), (B2) and (B3) are as detailed before.

[0190] In the absence of monomer (B2), the amounts of monomers are as follows, based on the total weight of the graft polymer:

[0191] (B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0192] (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3) expressed as a weight percentage based on the total weight of the grafted polymer;

[0193] (B2) (nitrogen-containing monomer) is 0%;

[0194] (B3) (additional monomer) is 0 to 10, preferably at most 2, more preferably at most 1, even more preferably about 0.

[0195] The amounts of the further monomers besides (B1), (B2) and (B3) are as detailed before.

[0196] In a preferred embodiment, the amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0197] Preferably, the optional additional monomers (B3) are present only as impurities and are not intentionally added for the polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5%, even more preferably less than 0.01% by weight, based on the total weight of monomers (B1). Most preferably, such monomers (B3) are essentially absent, and most preferably, any other monomers besides monomers (B1) and optional monomers (B2) are completely absent. The same applies to the additional monomers besides (B1), (B2) and (B3).

[0198] In a preferred embodiment, the graft polymer of the present invention comprises polymer side chains (B) obtained or obtainable by free radical polymerization of the at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) and optionally at least one further monomer (B3) in the presence of the polymer backbone (A),

[0199] wherein at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of the vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percents based on the total weight of the vinyl ester monomers B1 employed).

[0200] In an even more preferred embodiment of the previous embodiment, substantially no further monomers (B3) are employed.

[0201] In an even more preferred embodiment of the previous embodiment, substantially no further monomers (B2) and (B3) are employed.

[0202] In a preferred embodiment, the graft polymer of the present invention is composed of monomers, wherein

[0203] (B) These monomers are:

[0204] (B1) at least one vinyl ester chosen from vinyl acetate, vinyl propionate and / or vinyl laurate, in an amount ranging from 70% to 100% by weight of the total weight of the monomers grafted onto the backbone (A), preferably only vinyl acetate, and

[0205] (B2) optionally at least one nitrogen-containing monomer in an amount of 0 to 30% by weight of the total amount of monomers grafted onto the backbone (A), which is preferably an N-vinyllactam such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone and / or N-vinylcaprolactam, and most preferably N-vinylpyrrolidone,

[0206] The vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after the polymerization.

[0207] In its preferred embodiment, the vinyl ester is not hydrolyzed.

[0208] In an alternative embodiment, in addition to at least one monomer (B1), at least one vinyl lactam, preferably vinyl pyrrolidone and / or vinyl caprolactam, more preferably only vinyl pyrrolidone, is present as monomer (B2), wherein monomer (B1) preferably comprises vinyl acetate, and even more preferably is only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1) and vinyl pyrrolidone is the only monomer (B2).

[0209] In an alternative embodiment to the embodiment in the immediately preceding paragraph, monomer (B1) may be partially or completely hydrolyzed after the polymerization reaction. In a preferred embodiment thereof, monomer (B1) is partially hydrolyzed, and even more preferably hydrolyzed to a maximum of 80, 70 or 60, 50, 40, 30, 20 or 10 mole percent based on the total amount of monomer (B1).

[0210] Preferably, monomer (B1) is partially hydrolyzed to 20%, and hydrolyzed up to 50%. In the most preferred embodiment of the previous embodiment, vinyl acetate is used as monomer (B1) and vinyl pyrrolidone is used as monomer (B2), and the polymer portion derived from vinyl acetate is partially hydrolyzed after polymerization, preferably in an amount of about 20 mol% to 50 mol%, more preferably about 30 mol% to 45 mol%, such as about 40 mol%, based on the total amount of vinyl acetate.

[0211] In an alternative, even more preferred embodiment of the two immediately preceding paragraphs, the vinyl ester is not hydrolyzed at all.

[0212] It will be appreciated that the amounts for (A), (B), (B1), (B2), (B3) and further monomers in addition to the preceding monomers may be selected from the various detailed ranges given independently, i.e. the lower and upper boundaries may also be combined from two different ranges given for one aspect to produce a numerical range which is not explicitly specified in numbers, nevertheless such combined ranges for e.g. (A), (B), (B1), (B2) and (B3) are explicitly intended to be encompassed by the present invention.

[0213] Moreover, in one embodiment of the invention, broad ranges and very particularly preferred narrow ranges can be combined, wherein the choice of the range for one component is chosen independently of the choice of the range for the other component, as long as the total adds up to "100%-polymer": for example, the most preferred ranges for (A) and (B) can be chosen and combined with the broadest possible ranges given for (B1) / (B2) / (B3) and any other possible combination.

[0214] Preferably, for all selections that can be made for (A) / (B) and (B1) / (B2) / (B3)), the same selection is made, e.g. all "preferred" ranges are selected, or - more preferably - all "more preferred" ranges are selected, or - most preferably - all "most preferred" ranges are selected.

[0215] The graft polymers of the present invention as previously detailed have a polydispersity (PDI) Mw / Mn of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, and any number a as an upper or lower limit and any range in between, such as 1.3 to 2.6, 1 to 3, etc. (wherein Mw = weight average molecular weight in g / mol, and Mn = number average molecular weight in g / mol; wherein PDI is unitless), with lower values being preferred, but this depends on the Mn of the polymer backbone used (the higher the Mn of (A), the higher the PDI typically is) and also the amount of (B) (the higher the amount of (B) relative to the amount of (A), the higher the PDI typically is).

[0216] The corresponding values of Mw and Mn can be determined using GPC standard methods (such as the method referenced in the experimental section). However, the molecular weight of the main chain used in the present invention can also be calculated because those reactions are essentially carried out to completion. Therefore, calculating the molecular weight based on the total molar amount of the components used to prepare the reaction is also a feasible approach.

[0217] The grafted polymers of the present invention may contain an amount of ungrafted polymer ("ungrafted side chains") made from monomers that have not reacted with (ie, grafted onto) the polymer backbone.

[0218] The amount of this type of non-grafted polymer can be high or low, depending on reaction conditions, but preferably reduces and is therefore more preferably low. By this reduction, the amount of grafted side chains is preferably increased. This reduction can be achieved by suitable reaction conditions, such as the dosage and relative amount of monomer and free radical initiator, and is also relevant with the amount of the main chain present. This adjustment is well known to those skilled in the art in principle, and hereinafter described in detail for the present invention in the description of the method for obtaining grafted polymers of the present invention.

[0219] It has been found that the graft polymers of the present invention as previously described in detail herein exhibit improved biodegradability of at least 35%, more preferably at least 40%, even more preferably at least 50%, such as 41, 42, 43, 44, 45, etc., 51, 52, 53, etc., 55, 60, 65, etc. and any value in between and up to 100% within 28 days when tested according to OECD 301F.

[0220] The ratio of (A) to (B) used in the examples herein is:

[0221] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer backbone as the grafting matrix, and

[0222] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer backbone (A),

[0223] Each percentage is based on the total weight of the grafted polymer, and the sum of (a) plus (B) is 100 wt.%.

[0224] Subunits (a1), (a2), as defined by their structure or their preparation, the polymer backbones (A), (A1), (A2), (A3) and (A4) as grafting bases, and monomers (B), (B1), (B2), (B3), and any and each of the further monomers other than (B1), (B2), (B3) are as defined herein and in particular as previously defined in all of their embodiments, preferred embodiments, etc. and in the examples; for subunits (a1), (a2), as defined by their structure or their preparation, Any such embodiments of the polymer backbones (A), (A1), (A2), (A3) and (A4) as grafting matrices defined for their preparation, and monomers (B), (B1), (B2), (B3), and further monomers in addition to (B1), (B2), (B3) can be selected individually and combined, provided that such selection is possible and not excluded in this document, i.e. the sum needs to be added up as required and the embodiments are compatible (i.e. an embodiment requiring (B2) is obviously not combined with an embodiment requiring the absence of (B)).

[0225] In a more preferred embodiment, the graft polymer of the present invention and / or as previously described in detail consists of:

[0226] (A) at least one polymer backbone as grafting base, such grafting base being any of the previously defined polymer backbones in any embodiment, preferably any of (a1), (A2), (A3) and (A4) as previously defined,

[0227] in the amounts defined in any of the Examples herein,

[0228] including description, examples and claims,

[0229] as well as

[0230] (B) polymer side chains (B) grafted onto the polymer backbone (A), wherein the polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2) and optionally a further monomer (B3) and optionally further monomers,

[0231] All such monomers are any monomer as defined in any of the Examples herein,

[0232] in the amounts defined in any of the Examples herein,

[0233] Includes description, examples and claims.

[0234] In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the only monomer (B1), and more preferably vinyl pyrrolidone is the only monomer (B2), and most preferably no other monomer (B3) and no additional monomers other than the previous monomers are present.

[0235] In preferred embodiments of the preceding embodiments, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole percent, and most preferably about 40 mole percent.

[0236] In a specific embodiment, the graft polymer of the present invention consists of:

[0237] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer backbone as grafting base, wherein the percentages are given as weight percentages relative to the total weight of the grafted polymer;

[0238] The polymer backbone comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0239] (a1) is a unit comprising, preferably consisting essentially of, a portion derived from at least one alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, and / or at least one polyalkylene oxide polymer having two hydroxyl end groups,

[0240] (a2) is a unit comprising (preferably consisting of) at least one lactone and / or at least one hydroxy acid, this seed unit (a2) being a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0241] Wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0242] i) lactones, i.e. cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone;

[0243] as well as

[0244] ii) hydroxy acids, which can be derived from any lactone by hydrolysis, in particular from any lactone within the preceding group i), in particular α-, β- or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0245] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0246] The polymer main chain

[0247] Obtained through any of the following methods

[0248] (A1) copolymerization of at least one subunit (a1) and at least one subunit (a2), wherein optionally, at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and at least one subunit (a2);

[0249] (A2) first oligomerizing / polymerizing subunit (a2) and then polymerizing the product with subunit (a1);

[0250] (A3) first oligomerizing / polymerizing subunit (a1) and then copolymerizing the product with subunit (a2); or

[0251] (A4) first providing an oligomeric or polymeric subunit (a1) carrying a capping group on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4, which - as a starter block - is thereafter reacted with at least one subunit (a2) and optionally at least one subunit (a1) - wherein the subunit (a1) may be different from the one / those in the starter block or may be arranged in a different order compared to those in the starter block - to attach a new block comprising parts from the subunits used for (co)polymerization to the uncapped side of the starter block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0252] wherein, in case more than one subunit (a1) and / or more than one subunit (a2) are already present in the oligomer or polymer employed, those subunits may be arranged in any order within such oligomer or polymer employed, and wherein, in case more than one subunit (a1) and / or more than one subunit (a2) are present for polymerization, those subunits (and optionally the oligomer / polymer, if employed) may be arranged in any order within the backbone obtained;

[0253] Or selected from

[0254] (A1) a backbone consisting of a randomly arranged sequence of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits, wherein more than one subunit (a1) and / or more than one subunit (a2) are present;

[0255] (A2) a backbone consisting of an inner block of oligomeric or polymeric subunits (a2) and two outer blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as “-[block of (a1)]-[block of (a2)]-[block of (a1)]-” and may also comprise higher order block polymers such as 5-blocks, 7-blocks and 9-blocks, etc., in which further blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as a pentablock “[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]”, etc.;

[0256] (A3) a backbone consisting of an inner block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunits (a2), at least in the form of a triblock polymer defined as “-[block of (a2)]-[block of (a1)]-[block of (a2)]-”; and

[0257] (A4) A main chain consisting of:

[0258] The first block has

[0259] (i) a capping group on one end - such a capping group is a C1 to C18-, preferably C1-C4-alkyl group attached to the first block via an ether function; and

[0260] (ii) oligomeric or polymeric subunit (a1); and

[0261] a second block, which is attached to the first block via an ether or ester functionality at the opposite end of the first block ("opposite" with respect to the end-capping group on the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), wherein the optional subunit (a1) in the second block may be different from that / those in the first block or may be arranged in a different order compared to those in the first block, and the order of the subunits (A1) and (a2) may also be in any order, including a random structure,

[0262] This diblock structure has the following as an idealized structure when only subunit (a2) is used for the second block:

[0263] [Capping group]-[subunit (a1)]-[subunit (a2)]

[0264] Or in the case of using subunits (a1) and (a2) for the second block, the following is the idealized structure:

[0265] [End-capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0266] wherein the amounts of subunits (a1) and (a2) are as defined herein before;

[0267] as well as

[0268] (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60%, most preferably 20 to 50%, of polymer side chains (B) grafted onto the polymer backbone (A), wherein said polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally nitrogen-containing monomers (B2) and optionally further monomers (B3) and optionally further monomers,

[0269] wherein the percentages are given as weight percentages relative to the total weight of the grafted polymer;

[0270] Among these monomers are:

[0271] (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate and any further vinyl esters known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and / or vinyl benzoate;

[0272] Optionally

[0273] (B2) at least one nitrogen-containing monomer selected from the group consisting of vinyllactams, vinylimidazoles, 1-vinyltriazole, 4-vinylpyridine, 4-vinylpyridine-N-oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N′-dialkyl(meth)acrylamides; mono- and dialkylamino-alkyl(meth)acrylates, preferably vinyllactam monomers and / or vinylimidazole monomers, the vinyllactams more preferably being selected from N-vinyllactams such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam and most preferably N-vinylpyrrolidone, and the vinylimidazoles preferably being N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole;

[0274] Optionally

[0275] (B3) at least one additional monomer such as any one or more of 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amine if hydrolyzed after polymerization, N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl (meth)acrylates; and

[0276] Optionally

[0277] at least one additional monomer, which is different from the previous ones, such other monomer being present only in an amount of less than 2% of the total amount of monomers used to obtain the polymeric side chains (B) and preferably being present only as an impurity and not intentionally added for the polymerization;

[0278] The amounts are preferably as follows:

[0279] -If (B2) exists-

[0280] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0281] Measured in weight percent based on the total weight of the graft polymer, (B1) (vinyl ester) is

[0282] 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0283] Measured as a percentage by weight based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and every number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1).

[0284] as well as

[0285] -If (B2) does not exist-

[0286] (B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0287] (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3) expressed as a percentage by weight based on the total weight of the graft polymer.

[0288] (B2) (nitrogen-containing monomer) is 0%,

[0289] And further premise is that in all the previous cases

[0290] (B3) (additional monomers) is from 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in any case at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0291] wherein preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as vinyl ester (weight percents based on the total weight of the vinyl ester monomers B1 employed),

[0292] And optionally the vinyl ester is hydrolyzed after polymerization.

[0293] In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the only monomer (B1), and more preferably vinyl pyrrolidone is the only monomer (B2), and most preferably no other monomer (B3) and no additional monomers other than the previous monomers are present.

[0294] In preferred embodiments of the preceding embodiments, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole percent, and most preferably about 40 mole percent.

[0295] The polymers of the present invention preferably have at least one, preferably two or more of the following additional properties in order to be used more successfully in the various fields of application for the present invention:

[0296] i) the polymer backbone (A) may carry two hydroxyl groups as terminal groups or may be terminated at both ends with C1 to C22-alkyl, preferably C1 to C4-alkyl groups;

[0297] ii) the graft polymer has a polydispersity (PDI) Mw / Mn (wherein Mw = weight average molecular weight and Mn = number average molecular weight [g / mol / g / mol]) of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, and any number a as an upper or lower limit and any range therebetween, such as 1.3 to 2.6, 1 to 3, etc.;

[0298] iii) the biodegradability of the graft polymer is at least 40%, more preferably at least 45%, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75% etc. and any values therebetween and up to 100% within 28 days when tested according to OECD 301F.

[0299] Furthermore, the grafted polymers are preferably water-soluble to a certain extent to enable the use of these polymers in aqueous environments typically found in the various fields of application for which the present invention is generally intended. Preferably, the polymers of the present invention should exhibit moderate to good, more preferably good, solubility in the environment of aqueous formulations, as typically employed in such fields for various formulations, such as dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, and the like.

[0300] Furthermore, the grafted polymer solution preferably has a viscosity such that the solids concentration of the polymer is sufficiently high for handling during and after production and for supplying it to the user, the polymer being dissolveable, for example, as a "pure" (then typically liquid) product in a solvent, typically an aqueous solution containing water and an organic solvent, only water or only an organic solvent, the viscosity of such a polymer or polymer solution being within a range that allows typical technological process steps such as pouring, pumping, dosing, etc. Thus, the viscosity should preferably be in the range of about up to less than 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750 or even 2600 or below, such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPas, at a polymer concentration (based on the total solids content of the polymer in the solution, as defined by the weight percentage of dry polymer within the total weight of the polymer solution) of preferably at least 10 wt.%, more preferably at least 20 wt.% and even more preferably at least 40 wt.% and most preferably at least 50 wt.%, such as at least 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt.%. The viscosity can be measured at 25°C or at an elevated temperature, for example a temperature of 50°C or even 60°C. In this way, the polymer solution can be properly processed on a commercial scale. Of course, it is obvious that, depending on the amount of solvent added, the viscosity is lower when the amount of solvent is increased, and vice versa, thus allowing adjustment if desired. It is also obvious that the measured viscosity depends on the temperature at which it is measured, for example, the viscosity of a given polymer with a given solids content of, for example, 80 wt.% will be higher when measured at a lower temperature, and the viscosity will be lower when measured at a higher temperature. In a preferred embodiment, the solids content is between 70 wt.% and 99 wt.%, more preferably between 75 wt.% and 85 wt.%, and no additional solvent is added in addition to the polymer being prepared. In a more preferred embodiment, the solids content is between 70 wt.% and 99 wt.%, more preferably between 75 wt.% and 95 wt.%, no additional solvent is added besides the prepared polymer, and the viscosity is below 3000 mPas, more preferably 3250, or even below 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500 or even 250 mPas when measured at 60° C. The viscosity can be determined as is generally known for such polymers, preferably as described below in the experimental part.

[0301] Of course, as an additional criterion, it is necessary to evaluate the individual properties of a particular polymer and thus rank each individual formulation in a particular field of application. Due to the wide range of usefulness of the polymers of the present invention, an exhaustive overview or detailed guidance for every field is impossible, but the present description and examples provide guidance on how to prepare and select useful polymers with the desired properties and how to adjust these properties to the desired requirements. One such criterion in the field of home care, and in particular fabric care, is, of course, performance in the wash, e.g., subjecting a material exhibiting certain material stains to a defined wash cycle.

[0302] These examples provide some guidance for fabric laundering applications, the general area of fabric care.

[0303] Depending on the individual need for polymers exhibiting a defined degree of biodegradation, water solubility, and viscosity (ie, handling characteristics), the general and specific teachings herein - not intended to be limited to the specific examples given - will guide how to obtain such polymers.

[0304] method

[0305] The present invention also encompasses a process for obtaining a graft polymer according to any previous embodiment as defined herein and in particular in the previous sections but also in any examples disclosed herein, wherein at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomer (B3) and optionally further monomers (in addition to (B1), (B2) and (B3)) are polymerized in the presence of at least one polymer backbone (A) as defined herein, preferably selected from backbones (A1), (A2), (A3) and (A4) as defined herein, wherein the polymer side chains (B) are obtained by free radical polymerization, preferably using a free radical forming compound to initiate the free radical polymerization,

[0306] wherein each of B1, B2 and B3 (and additional monomers in addition to (B1), (B2) and (B3)) and (A), (A1), (A2), (A3) and (A4) are as defined herein before, including in the claims and including in any embodiments as illustrated in the Examples below, wherein each is preferably selected from any hierarchy of preferences thereof, provided that each can be selected individually from its preferences, but always in accordance with general requirements of compatibility of preferences, such as the sum not exceeding 100%, etc.

[0307] It must be noted that the "grafting process" itself (wherein a polymer backbone, such as the polymer backbone (A) described herein above, is grafted with polymer side chains) is known to those skilled in the art. In principle, any method known to the skilled person in this regard can be used in the present invention.

[0308] Free radical polymerization is also known per se to the skilled person. This person is also aware that the process according to the invention can be carried out in the presence of a free radical-forming initiator (C) and / or at least one solvent (D).

[0309] The skilled person knows suitable corresponding components per se.

[0310] The term "free radical polymerization" as used in the context of the present invention comprises, in addition to free radical polymerization, variants thereof, such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each known to the skilled person, including suitable control agents.

[0311] In a preferred embodiment, the process for producing the graft polymers of the present invention and / or as described in detail above comprises at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one further monomer (B3) and optionally further monomers - the latter preferably being present only as impurities and more preferably being substantially absent - in at least one polymer backbone (A) preferably selected from backbones (A1), (A2), (A3) and (A4) as defined above, a free radical forming initiator (C) and, if desired, The polymerization is carried out in the presence of up to 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1), optionally (B2) and optionally (B3) (the further monomers are typically not monitored and are present only in low, therefore negligible, amounts as impurities) and the initiator (C) in the reaction mixture is constantly kept in a quantitative deficit relative to the copolymer backbone (A). In a preferred embodiment, no monomer (B2) is used. In a more preferred embodiment, neither monomer (B2) nor monomer (B3) is used. In an even more preferred embodiment, only monomer (B1) is used. In general, the amount of further monomers other than (B1), (B2) and (B3) is minimized, preferably they are completely absent.

[0312] In a preferred embodiment of any embodiment of the process as detailed in the previous paragraph, at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent and most preferably substantially only (i.e. about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (weight percentages based on the total weight of vinyl ester monomers B1 employed).

[0313] Typically, in addition to the monomers (B1), (B2) and (B3), at least one further monomer (different from the previous ones) can be used in the copolymerization to produce the side chains (B), wherein such further monomer is present only in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chains (B) and is preferably employed only as an impurity—unavoidable in practical terms—and not intentionally added for the polymerization, and most preferably is not present at all.

[0314] In more preferred embodiments of the two previous paragraphs, the following additional provisos 1) (presence of (B2)) and 2) (absence of (B2)) apply to the amounts and ratios of the monomers:

[0315] In the case of using monomer (B2), the amount of the monomer is as follows based on the total weight of the graft polymer:

[0316] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0317] Measured in weight percent based on the total weight of the graft polymer, (B1) (vinyl ester) is

[0318] 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0319] Measured as a percentage by weight based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and every number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1);

[0320] (B3) (additional monomers) is from 0% to 10%, preferably up to 2%, more preferably up to 1%, even more preferably about 0%, but in any case up to 10% of the amount of (B1) and does not exceed the amount of (B2).

[0321] The amounts of the additional monomers besides (B1), (B2) and (B3) are as detailed previously, and the monomers (B1), (B2) and (B3) are as detailed previously herein in any of the Examples disclosed.

[0322] In the case where monomer (B2) is not used, the amounts of monomers are as follows, based on the total weight of the graft polymer:

[0323] B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0324] (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3) expressed as a percentage by weight based on the total weight of the grafted polymer.

[0325] (B2) (nitrogen-containing monomer) is 0%;

[0326] (B3) (additional monomer) is 0 to 10, preferably at most 2, more preferably at most 1, even more preferably about 0.

[0327] The amounts of the additional monomers besides (B1), (B2) and (B3) are as detailed previously, and the monomers (B1), (B2) and (B3) are as detailed previously herein in any of the Examples disclosed.

[0328] In a preferred embodiment, the amount of vinyl ester monomer (B1) employed is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0329] Preferably, the optional additional monomers (B3) are also present only as impurities and are not intentionally added for the polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5%, even more preferably less than 0.01% by weight, based on the total weight of monomers (B1). Most preferably, such monomers (B3) are essentially absent, and most preferably, any other monomers besides monomers (B1) and optional monomers (B2) are completely absent. The same applies to the additional monomers besides (B1), (B2) and (B3).

[0330] In a particularly preferred embodiment, the amounts of monomers employed are as follows, based on the total weight of the grafted polymer:

[0331] (A) is 40% to 90%, preferably 50%, more preferably 60% and preferably up to 80% of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as grafting matrix,

[0332] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0333] (B1) (vinyl ester) is from 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0334] (B2) (at least one vinyllactam, preferably vinylpyrrolidone and / or vinylcaprolactam, more preferably vinylpyrrolidone) is 1 to 25%, preferably up to 20%, more preferably up to 15%, even more preferably up to 10%, such as even only up to 5%, wherein the amount of (B2) is at most not higher than the amount of (B1);

[0335] (B3) (additional monomers) is from 0% to 2%, preferably at most 1%, more preferably 0%, but in any case at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0336] More preferably, the optional additional monomers (B3) and additional monomers in addition to (B1), (B2) and (B3) are preferably present only as impurities and are not intentionally added for the polymerization; more preferably, the amount is less than 1% by weight, more preferably less than 0.5%, even more preferably less than 0.01% by weight, based on the total weight of monomers (B1), most preferably such monomers (B3) and additional monomers are essentially absent, and most preferably any other monomers in addition to monomers (B1) and (B2) are even completely absent.

[0337] The amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0338] In an alternative particularly preferred embodiment, the amounts of monomers employed are as follows, based on the total weight of the grafted polymer:

[0339] (A) is 40% to 90%, preferably 50%, more preferably 80% of a polymer backbone as defined herein before, preferably at least one of (A1), (A2) and (A3), as grafting matrix;

[0340] (B) is 10% to 60%, preferably up to 50% and preferably 20%;

[0341] (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3);

[0342] (B2) is 0%;

[0343] (B3) (additional monomers) is from 0% to 2%, preferably at most 1%, more preferably 0%, but in any case at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0344] The amount of vinyl ester monomer (B1) is usually not less than 10% by weight (relative to the sum of (B1) and (B2));

[0345] Optional additional monomers (B3) and additional monomers in addition to (B1), (B2) and (B3) are preferably present only as impurities and are not intentionally added for the polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5%, even more preferably less than 0.01% by weight, based on the total weight of monomer (B1), and most preferably such monomers (B3) and additional monomers are substantially absent, and most preferably any other monomers in addition to monomer (B1) are even completely absent.

[0346] The amount of (free-radical-forming) initiators (C) is preferably 0.1 to 5% by weight, in particular 0.3 to 3.5% by weight, based in each case on the polymer side chains (B).

[0347] For the process according to the invention, it is preferred that the steady-state concentration of free radicals present at the average polymerization temperature is substantially constant and that the grafting monomers (B) and in particular (B1), more preferably (B1) and (B2), even more preferably (B1), (B2) and (B3) are present in the reaction mixture only constantly in low concentrations (e.g., not exceeding 5% by weight in total). This allows the reaction to be controlled and the graft polymer to be prepared in a controlled manner with the desired low polydispersity.

[0348] However, in order to ensure safe temperature control - especially when the polymerization is started at high solids concentrations or in large quantities and / or with a large amount of monomer present from the outset - it is advisable and therefore preferred to use additional and effective measures to control the temperature. This can be done by external and / or internal cooling; such cooling can be done by internal or external coolers (such as heat exchangers) or by using reflux condensers at the boiling temperature of the solvent or solvent mixture at a given temperature / pressure combination.

[0349] The same measures can of course be used for the previously mentioned preferred embodiment, in which the monomer is added over a prolonged period of time and the monomer concentration in the reaction volume is therefore continuously low over time.

[0350] However, under such conditions, temperature control is generally not a critical point, since the temperature is also controlled at least in part by the progress of the polymerization reaction by controlling the free radical concentration and the available amount of polymerizable monomer. Of course, this depends on the scale of the polymerization reaction. When the scale becomes large enough that the volume to surface ratio of the polymerization mixture becomes very large, such additional cooling as described above may be necessary for both variants - batch or bulk reactions, which have a large amount of monomer present from the beginning, or semi-continuous or continuous polymerization reactions with typically constant low monomer concentrations.

[0351] However, this is well known to those skilled in the art of commercial scale polymerization and can therefore be adapted to these requirements.

[0352] According to the invention, the initiator (C) and the grafting monomer (B) and in particular (B1) and / or (B2) and / or (B3) (preferably twice "and") are advantageously added in such a way that a low and essentially constant concentration of undecomposed initiator and grafting monomer (B) and in particular a constant but low amount of (B1) and in particular even more (B2) (especially in the case when vinylpyrrolidone is selected as (B2)) is present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture, based on the total amount of initiator metered during the monomer addition, is preferably 100% by weight. < 15%, especially by weight < 10%.

[0353] In a more preferred embodiment, the process comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one other monomer (B3) and optionally at least one further monomer, more preferably only monomers (B1) and (B2), in the presence of at least one polymer backbone (A) as defined herein, preferably selected from (A1), (A2) and (A3), a free radical forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one organic solvent (D) at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that unconverted graft monomer (B) and initiator ( C) in the reaction mixture is continuously kept in a quantitative deficit relative to the polymer backbone (A), wherein preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably substantially only (i.e. about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (weight percentages based on the total weight of the vinyl ester monomers B1 employed).

[0354] In even more preferred embodiments of the previously mentioned embodiments, substantially no monomer (B2) is employed in addition to monomer (B1), preferably (B1) comprises vinyl acetate, more preferably comprises substantially only vinyl acetate, all within the ranges and preferred ranges given in the section on "Grafted polymers of the invention".

[0355] In an alternative embodiment to the previous embodiment, in addition to monomer (B1), essentially only monomer (B2) is employed, preferably (B1) comprises vinyl acetate, more preferably essentially only vinyl acetate, and preferably (B2) comprises vinyl lactam, more preferably comprises vinyl pyrrolidone and even more preferably essentially comprises vinyl pyrrolidone, all within the ranges and preferred ranges given in the section on "Graft polymers of the invention".

[0356] The average polymerization temperature for main polymerization and post-polymerization is suitably in the range of 50 to 140° C., preferably 60 to 120° C. and more preferably 65 to 110° C. Typically, the temperature for post-polymerization is 5 to 40° C. higher than that for polymerization.

[0357] The term "average polymerization temperature" is intended herein to mean that, although the process is essentially isothermal, there may be temperature variations due to the exothermic nature of the reaction, which are preferably kept within a range of + / - 10°C, more preferably within a range of + / - 5°C.

[0358] According to the invention, the (free radical forming) initiator (C) should have a decomposition half-life of 40 to 500 min, preferably 50 to 400 min and more preferably 60 to 300 min at the average polymerization temperature.

[0359] Examples of suitable initiators (C) whose decomposition half-life is 20 to 500 min in the temperature range of 50° C. to 140° C. are:

[0360] -Uncle-C4-C 12 -alkyl hydroperoxides and tert-(C9-C 12 -aralkyl) hydroperoxide O-C2-C 12 - acylated derivatives such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and di-tert-butyl diperoxyphthalate;

[0361] -Uncle-C8-C 14 -alkylene diperoxide di-O-C4-C 12 - acylated derivatives such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene;

[0362] -2(C2-C 12 -alkanoyl) and dibenzoyl peroxides such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dioctanoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide, and di(2,4-dichlorobenzoyl) peroxide;

[0363] -tert-C4-C5-alkyl peroxy (C4-C 12 -alkyl) carbonates, such as tert-amylperoxy(2-ethylhexyl) carbonate;

[0364] -peroxydicarbonate (C2-C12 -alkyl) esters, such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0365] Examples of particularly suitable initiators (C) are, depending on the average polymerization temperature:

[0366] - At an average polymerization temperature of 50°C to 60°C:

[0367] tert-Butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-bis(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate, and di(2-ethylhexyl) peroxydicarbonate;

[0368] - At an average polymerization temperature of 60°C to 70°C:

[0369] tert-Butyl peroxypivalate, tert-Butyl peroxyneoheptanoate, tert-Butyl peroxyneodecanoate, tert-Amyl peroxypivalate, and di(2,4-dichlorobenzoyl)peroxide;

[0370] - At an average polymerization temperature of 70°C to 80°C:

[0371] tert-Butyl peroxypivalate, tert-Butyl peroxyneoheptanoate, tert-Amyl peroxypivalate, dipropionyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl)peroxide, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane;

[0372] - At an average polymerization temperature of 80°C to 90°C:

[0373] tert-Butyl peroxyisobutyrate, tert-Butyl peroxy-2-ethylhexanoate, tert-Amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide, and di(4-methylbenzoyl) peroxide;

[0374] -At an average polymerization temperature of 90°C to 100°C:

[0375] tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, and di(4-methylbenzoyl)peroxide;

[0376] - At an average polymerization temperature of 100°C to 110°C:

[0377] tert-Butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, and tert-amyl peroxy(2-ethylhexyl)carbonate;

[0378] - At an average polymerization temperature of 110°C to 120°C:

[0379] tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and tert-amyl peroxy(2-ethylhexyl)carbonate.

[0380] Preferred initiators (C) are tert-C4-C5-alkyl hydroperoxides of O-C4-C 12 -acylated derivatives, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0381] Particularly favorable polymerization conditions can be easily established by precisely adjusting the initiator (C) and the polymerization temperature. For example, when using tert-butyl peroxypivalate, the preferred average polymerization temperature is 60° C. to 80° C., and when using tert-butyl peroxy-2-ethylhexanoate, it is 80° C. to 100° C.

[0382] The polymerization reaction according to the invention can be carried out in the presence of a (preferably small amount of) solvent (D). Of course, mixtures of different solvents (D) can also be used. Preference is given to using water-soluble or water-miscible organic solvents. However, the use of water as the sole solvent is in principle also possible, but not preferred.

[0383] When solvents (D) are used as diluents, generally 1 to 40% by weight, preferably 1 to 35% by weight, more preferably 1.5 to 30% by weight, most preferably 2 to 25% by weight, based in each case on the sum of components (A), (B1), optionally (B2), optionally (B3) and optional further monomers and (C) are used.

[0384] Examples of suitable solvents (D) include:

[0385] -monohydric alcohol, preferably aliphatic C1-C 16 -alcohols, more preferably aliphatic C2-C 12 - alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol;

[0386] -polyols, preferably C2-C 10 - diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol;

[0387] -alkylene glycol ethers, preferably alkylene glycol mono(C1-C 12-alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether and propylene glycol monomethyl ether and propylene glycol monoethyl ether;

[0388] - polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2 to 20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2 to 20 ethylene glycol units and polypropylene glycols having 2 to 10 propylene glycol units, most preferably polyethylene glycols having 2 to 15 ethylene glycol units and polypropylene glycols having 2 to 4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol;

[0389] - polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C4-alkylene) glycol monoethers having 2 to 20 alkylene glycol units 25 -alkyl) ethers, more preferably poly(C2-C4-alkylene) glycol mono(C1-C4-alkylene) ethers having 2 to 20 alkylene glycol units 20 -alkyl) ethers, most preferably poly(C2-C3-alkylene) glycol mono(C1-C 16 -alkyl) ether;

[0390] - carboxylic acid esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as ethyl acetate and ethyl propionate;

[0391] - aliphatic ketones preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;

[0392] - cyclic ethers, in particular tetrahydrofuran.

[0393] Solvents (D) are advantageously those solvents which are also used for formulating the graft polymers according to the invention for use (for example in washing and cleaning compositions) and which can therefore remain in the polymerisation product.

[0394] Preferred examples of these solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units and, in particular, alkoxylation products of C6-C8-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0395] Particularly preferred are C8-C 16Alkoxylation products of alcohols, which allow the formulation of polymer mixtures which flow freely at 40° C. to 70° C. and have a very low polymer content at a relatively low viscosity. Branches can be present in the alkyl chain of the alcohol and / or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of these alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide, C 2-ethylhexanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 or C 16 / C 18 Fatty alcohols which come into consideration preferably are 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide.

[0396] In an alternative embodiment, the polymerization is carried out using a mixture of at least one organic solvent and water.

[0397] In a preferred embodiment the amount of water during the polymerisation is low, preferably at most 10 wt. %, more preferably at most 5 wt. %, more preferably at most 1 % based on the total solvent.

[0398] In another alternative embodiment, the polymerization is carried out using water as (D). However, water as the only solvent is not preferred.

[0399] The free radical initiator (C) is preferably used in the form of a concentrated solution in one of the solvents mentioned above. Of course, the concentration depends on the solubility of the free radical initiator. Preferably, the concentration is as high as possible to allow as little organic solvent as possible to be introduced into the polymerization reaction. In the case where the initiator is soluble in water and therefore water is used as the solvent for introducing the initiator, the concentration is not important from the perspective of the residual water content.

[0400] Preferably, the amount of water during the polymerization is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on the total weight of the graft polymer (at the end of the polymerization) or based on the total weight of (A) and (B) (at the beginning of the polymerization).

[0401] In the process according to the invention, the polymer backbone (A), the grafting monomers (B), the initiator (C) and, if appropriate, the solvent (D) are generally heated in a reactor to the chosen average polymerization temperature.

[0402] According to the invention, the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and the grafted polymer formed) is continuously present in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally > 10:1, preferably > 15:1 and more preferably > 20:1.

[0403] The polymerization process according to the invention can in principle be carried out in various reactor types. Such reactor types are generally known and include any stirred type reactor, such as a vessel, but also tubular reactors, reactor cascades from vessels or various tubes, etc.

[0404] The reactor used is preferably a stirred tank into which the polymer backbone (A), if appropriate, together with a portion of generally up to 15% by weight of the specified total amount of graft monomers (B), initiator (C) and solvent (D) are initially charged completely or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably individually. > 2h, more preferably > 4h and most preferably > 5h time periods are included.

[0405] In the case of the particularly preferred, essentially solvent-free process variant, the entire amount of the polymer backbone (A) is initially charged as a melt, and the grafting monomers (B1) and, if appropriate, (B2) and / or (B3) and also the initiator (C), preferably in the form of a 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled such that the selected polymerization temperature is maintained on average during the polymerization, in particular in a range of + / -10° C., in particular + / -5° C.

[0406] In a further particularly preferred low-solvent process variant, the procedure is as described above, except that the solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is also possible to start with metered addition of the solvent only at a later time by means of advanced polymerization, or to add it in portions.

[0407] The polymerization can be carried out under standard pressure or under reduced or elevated pressure. When the boiling point of the monomers (B1) and / or (B2) (and also monomer (B3) if employed) and / or any solvent (D) used is exceeded at the selected pressure, the polymerization is carried out under reflux cooling.

[0408] A post-polymerization process step can be added after the main polymerization reaction. For this purpose, an additional amount of initiator (dissolved in a solvent) can be added over a period of 0.5 hours and typically up to 3 hours, preferably about 1 to 2 hours, and more preferably about 1 hour (however, this duration also depends on the scale of the reactor), wherein the free radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization reaction. Of course, different free radical initiators and / or different solvents can also be used.

[0409] The temperature of the post-polymerization process step can be the same as the temperature in the main polymerization reaction (which is preferred in the present invention) or can be increased. In the case of increase, it can typically be about 5°C to 40°C higher, preferably 10°C to 20°C higher.

[0410] Between the postpolymerization and the main polymerization, a certain period of time may be waited, during which the main polymerization continues, before the postpolymerization is started by commencing the addition of further free-radical initiator.

[0411] For solvents having a boiling point of approximately less than 110°C-120°C at atmospheric pressure, such solvents can - as a purification step - be partially or essentially completely removed by hot distillation or vacuum distillation, all at ambient pressure or reduced pressure, or stripping with a gas such as water vapor or nitrogen (such as stripping with water vapor made from water), preferably vacuum distillation, while the higher boiling point solvent will generally remain in the obtained polymer product.

[0412] When mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred purification step. Consequently, higher boiling point solvents like 1-methoxy-2-propanol, 1,2-propylene glycol and tripropylene glycol will remain in the polymer product and therefore when such solvents are used only to introduce the initiator, their amount should be minimized as much as possible by using the highest possible concentration of free radical initiator, unless such solvents also form part of the formulation in which the grafted polymer is to be used.

[0413] The grafted polymers of the invention prepared using the process as defined herein may contain a certain amount of ungrafted polymers made of vinyl esters ("ungrafted side chains"), for example in the case of employing only vinyl acetate, polyvinyl acetate, and / or - when employing further monomers - homopolymers and copolymers of vinyl esters with other monomers. Depending on the reaction conditions, the amount of such ungrafted vinyl ester homopolymers and copolymers may be high or low, but is preferably reduced and therefore low. By this reduction, the amount of grafted side chains is preferably increased. Such a reduction can be achieved by appropriate reaction conditions, such as the dosage of vinyl ester and free radical initiator and their relative amounts, and is also related to the amount of main chain present. Such reaction control and the necessary process steps are generally known to those skilled in the art, and specific guidance is given herein.

[0414] Such adjustment of the degree of grafting and the amount of ungrafted polymer can be used to optimize the properties in specific areas of interest, such as certain (eg detergent) formulations, areas of application or desired cleaning properties.

[0415] It is believed that favorable conditions are thought to promote - supposedly - a higher degree of grafting; such a higher degree of grafting is associated with better performance. However, this supposedly higher degree of grafting does not impair biodegradation - it is due to the ester bonds in the main chain, which can "compensate" for the lower biodegradation of graft polymers with a higher degree of grafting - which is seen in "conventional graft polymers" based on polyalkylene oxide as the main chain.

[0416] The disadvantage is that it is extremely difficult, if not impossible, to actually verify such a degree of grafting on a polymer, especially as the molecular weight of the polymer increases, since the total number of grafting sites in the polymer is typically very low compared to the molecular weight; therefore, the signal-to-noise ratio is unfavorable for polymers given current analytical tools.

[0417] In another alternative embodiment of the present invention, after the polymerization reaction and thus after obtaining such a grafted polymer, the polymer side chains (B) of the grafted polymer according to the invention are completely or partially hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mol% and preferably 20 mol%, more preferably 20 mol% to 50 mol%, even more preferably 30 mol% to 45 mol%, such as about 40 mol%, based on the total moles of (B1) employed. This means that the complete or at least partial hydrolysis of the polymer side chains (B) of the grafted polymer is carried out in a further process step after completion of the polymerization process of the polymer side chains (B) (including after the optional post-polymerization step, if employed).

[0418] In another alternative embodiment, no hydrolysis is performed on the grafted polymer after the polymerization process of the polymer side chains (B) is completed.

[0419] Due to this complete or at least partial hydrolysis of the polymer side chains (B) of the graft polymer according to the invention, the corresponding side chain units derived from the at least one vinyl ester monomer (B1) are converted from corresponding ester functions to alcohol functions in the polymer side chains (B). It should be noted that, due to the stability of the "vinyl alcohol" monomer, the corresponding vinyl alcohols are not suitable for use as monomers in the polymerization of the polymer side chains (B). To obtain alcohol functions (hydroxy substituents) in the polymer side chains (B) of the graft polymer according to the invention, the alcohol functions are typically introduced by hydrolysis of the ester functions of the side chains.

[0420] From a theoretical point of view, each ester function of the polymer side chain (B) can be partially or completely replaced by an alcohol function (hydroxyl group). In this case, the polymer side chain is completely hydrolyzed ("saponified").

[0421] The hydrolysis can be carried out by any method known to those skilled in the art. For example, the hydrolysis can be induced by adding a suitable base, such as sodium hydroxide or potassium hydroxide. Such hydrolysis methods are known in the art.

[0422] In a preferred embodiment of the preceding embodiment, vinyl acetate is employed as monomer (B1) and vinyl pyrrolidone is employed as monomer (B2) and no further monomers are employed besides (B1) and (B2), and the polymer portion derived from vinyl acetate is partially hydrolyzed after the polymerization, preferably in an amount of 20 to 50 mol %, more preferably 30 to 45 mol %, such as - most preferably - about 40 mol %, based on the total moles of (B1) employed.

[0423] The grafted polymer of the invention, ie the polymer solution obtained from the process, may also be subjected to concentration and / or drying measures.

[0424] The obtained graft polymer solution can be concentrated to increase the solid polymer concentration by subjecting the polymer solution to a means for removing some of the volatiles and in particular the solvent. This can be achieved by a distillation process (such as heat or vacuum distillation) or by stripping with a gas (such as steam or an inert gas such as nitrogen or argon) until the desired solid content is obtained. Such a process can be combined with a purification step as previously disclosed, wherein the obtained graft polymer solution is purified by removing some or all of the volatile components such as volatile solvents and / or unreacted volatile monomers, by removing the desired amount of solvent.

[0425] The graft polymer solution can also be further concentrated or dried after the main polymerization and / or optional post-polymerization step and the optional purification step by subjecting the graft polymer solution to a means of partially or completely removing volatiles, such as - for concentration - a distillation process such as heat or vacuum distillation, or stripping using a gas such as steam or an inert gas such as nitrogen or argon, until the desired solids content is obtained, and / or drying such as drum drying, spray-drying, vacuum drying or freeze-drying, preferably - mainly for cost reasons - spray-drying. Such a drying process can also be combined with an agglomeration or granulation process, such as spray-agglomeration, granulation or drying in a fluidized bed dryer.

[0426] Therefore, the process according to the invention preferably encompasses at least one further process step selected from i) to iv), among which i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

[0427] More preferably, the method as detailed herein in any of the embodiments defined comprises at least one further method step selected from:

[0428] i) a post-polymerization process step, which is carried out after the main polymerization, wherein a further amount of initiator (optionally dissolved in the solvent) is added, preferably within a time period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, wherein the free-radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization; and wherein after the polymerization and before the post-polymerization, there is preferably a waiting period, during which the main polymerization is allowed to proceed, before the post-polymerization is started by starting the addition of the further free-radical initiator, such period being preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerization process step is - preferably - the same as in the main polymerization or increased, such increase preferably being about 5°C to 40°C, preferably 10°C to 20°C higher than the temperature of the main polymerization;

[0429] ii) a step of subjecting the graft polymer as obtained from the main polymerization or, if carried out, the post-polymerization process step, to purification, concentration and / or drying means in order to remove a part or substantially all of the remaining solvents (as long as they are removable due to their boiling point) and / or volatiles such as residual monomers, wherein

[0430] a. the concentration is carried out by removing a portion of the solvent and optionally also volatiles by preferably applying a distillation process such as heat or vacuum distillation, preferably vacuum distillation, and / or applying stripping with a gas such as steam or an inert gas such as nitrogen, preferably using steam from water - whereby this step additionally serves as a means for purification - to increase the solid polymer concentration - and optionally also for purification, allowing it to proceed until the desired solid content and optionally also purity is obtained, preferably allowing it to proceed until the desired part or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed;

[0431] b. the drying is carried out by subjecting the graft polymer, which contains at least residual amounts of volatiles such as remaining solvent and / or unreacted monomers, etc., to means for removing the volatiles, such as drying using rollers, a spray dryer, vacuum drying or freeze drying, preferably - primarily for cost reasons - spray drying; and optionally combining this drying method step with means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such a process preferably being selected from spray-agglomeration, granulation or drying in a fluidized bed dryer, spray-granulation apparatus, etc.

[0432] use

[0433] In principle, the graft polymers of the invention can be used in any application to replace conventional graft polymers of the same or very similar composition (with respect to the relative amounts of polymer backbone and graft monomers, especially when the types and amounts of graft monomers are similar or comparable).

[0434] Such applications are, for example: redeposition of soils and removal of stains, avoidance or reduction of re-soiling or graying or deposition of solids, dispersion of active substances in formulations of agrochemicals, pigments, pigments, inorganic salts, etc., inhibition of crystal growth, including for inhibiting gas hydrate formation and / or reducing sedimentation and / or agglomeration, improvement of pigment dispersion stability, hydrophobization of surfaces, reduction of microbial growth on surfaces, and / or odor control, etc., all compared to corresponding polymers or graft polymers according to the prior art.

[0435] Typical applications are:

[0436] Technical applications: Such compositions and formulations include any kind of non-aqueous and - preferably - water-based liquid formulations or gums of solid formulations, used as dispersants in any kind of dispersions, such as in oilfield applications, automotive applications, typically applications where a solid or liquid is to be dispersed in another liquid or solid.

[0437] Lacquers, Paints and Stain Formulations: Such compositions and formulations include non-aqueous and - preferably - water-based lacquers and stains, paints, finishes.

[0438] Agricultural formulations: Such compositions and formulations include formulations and compositions containing an agrochemically active substance in a liquid, semisolid, mixed liquid-solid or solid environment.

[0439] Aroma chemical formulations: Such compositions and formulations include formulations in which the aroma chemical is dissolved or dispersed in a liquid or solid composition to disperse it evenly and / or maintain its stability so as to retain its aromatic properties over an extended period of time; also encompassed are compositions that show release of the aroma chemical over time, such as delayed-release or sustained-release formulations.

[0440] Fabric and home care applications, industrial and institutional cleaning: Compositions and formulations of this type include cleaning compositions for fabrics and for solid surfaces such as dishware, cutlery, but also leather, metal, and the like.

[0441] The graft polymers of the invention as defined herein, obtainable by or obtained by the methods as defined herein, can improve the overall biodegradability of such formulations, compositions and products by replacing non-biodegradable polymers of similar structure or properties. They can therefore be advantageously used, depending in part on the monomers B used for grafting, and thus on their properties being adjusted to the specific needs of a particular application; such monomer substitution patterns may also be derived from the prior art of similar graft polymers based on simple PEG and polyalkylene glycols.

[0442] In particular, and beyond the performance in certain types of applications, the graft polymers according to the invention, when used in such compositions or products, result in improved biodegradability compared to previously known graft polymers.

[0443] Therefore, another subject of the present invention is the use of the graft polymers according to the invention and / or obtained or obtainable by the process according to the invention and / or as described in detail above in agrochemical formulations as, for example, dispersants, crystal growth inhibitors and / or solubilizers. Therefore, another subject of the present invention is also an agrochemical composition or an agrochemical product, or any other formulation or product in the field of agrochemicals and their formulations and products, each comprising at least one graft polymer as defined above or obtained or obtainable by the process according to the invention and / or as described in detail herein.

[0444] Another subject of the present invention is the use of the graft polymers of the invention and / or obtained or obtainable by the process of the invention and / or as described in detail above in any of the aforementioned applications in this chapter: such as fabric care and home care products, in cosmetic and personal care formulations, as crude oil demulsifiers, in technical applications (including in pigment dispersions for inkjet inks), in formulations for electroplating, in cementitious compositions, in paint and colorant formulations, for textile and leather treatment products for use during or after production, formulations containing inorganic salts such as, in particular, silver salts, in mining, metal production and processing (including metal refining and metal quenching), purification of liquids such as wastewater from industry, production or consumers, preferably in agrochemical compositions and cleaning compositions and in fabric and home care products.

[0445] Therefore, a preferred subject matter of the present invention is also the use of at least one graft polymer according to the invention and / or at least one graft polymer obtained or obtainable by the process according to the invention in fabric care and home care products, industrial and institutional cleaning products, agrochemical formulations, or formulations or products for any of the aforementioned applications and fields of application, preferably in agrochemical compositions. In particular, the graft polymers according to the invention are used for improved dispersion in such compositions / products / formulations.

[0446] Such inventive uses and inventive compositions / products encompass the use of grafted polymers as detailed herein and / or as obtainable or obtained by the process of the invention, such grafted polymers being similar to the grafted polymers as detailed above describing the polymer structure in any embodiment thereof disclosed herein before (including any variants mentioned, and more particularly any preferred, more preferred etc. embodiments).

[0447] Detailed description of the agrochemical composition

[0448] The agrochemical compositions of the present invention contain an agrochemically active ingredient in addition to the grafted polymer. It has been found that the grafted polymers of the compositions of the present invention are suitable as dispersants for a wide range of agrochemically active ingredients. The term "agrochemically active ingredient" refers to a substance that imparts the desired biological activity to the agrochemical composition.

[0449] Agrochemical active ingredients include pesticides, safeners, nitrification inhibitors, urease inhibitors, micronutrients, and / or plant growth regulators. Typically, an agrochemical active ingredient is a pesticide. Pesticides include insecticides, herbicides, fungicides, algaecides, rodenticides, molluscicides, and nematicides. Technicians are familiar with safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides, and / or growth regulators. In one embodiment, the agrochemical active substance is an insecticide. In another embodiment, the agrochemical active substance is a herbicide. In another embodiment, the agrochemical active substance is a fungicide. Technicians are familiar with such pesticides, for example, which can be found in Pesticide Manual, 16th edition (2013), British Crop Protection Council, London.

[0450] Preferably, the agrochemical active ingredient is selected from insecticides, fungicides, and herbicides.

[0451] Suitable insecticides are insecticides from the following classes: carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, bisacylhydrazides, METI acaricides and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargyl, triclofur, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydrazone, acequinoxaline, pyrimidifen, rotenone, afidopyropene, amidrazone, dimpropyridaz, fipronil or derivatives thereof.

[0452] Suitable fungicides are fungicides from the following classes: dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides such as fluopyrab-amid and diflufenican, carboxylic acid diamides, chloronitriles such as chlorothalonil, cyanoacetamide oxime, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonate, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates such as azoxystrobin, methoxycarbamates, morpholine, N-phenylcarbamates, oxazolidinediones, oximinoacetic acid esters , oxime acetamides, peptidyl pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles such as fludioxonil, phenylureas, phosphonates, phosphorothioates, o-carbamoylbenzoic acid, phthalimide, piperazine, piperidine, propionamide, pyridazinones, pyridine, pyridylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfonamides, sulfamoyltriazoles, tetrazolinones such as metyltetraprole, thiazolecarboxamides, thiocarbamates, thiophanate, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, and conazole fungicides, in particular triazoles such as mefentrifluconazole, triticonazole, prothioconazole and tebuconazol. Azoxystrobin, fluopyram, fludioxonil, prothioconazole, thiophanate-methyl, diflufenac, tetracyclam, clofoconazole and tebuconazole, in particular azoxystrobin, fluopyram and thiophanate-methyl and diflufenac, especially azoxystrobin, are particularly preferred fungicides.

[0453] Suitable herbicides are herbicides from the following classes: acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acid, benzothiadiazinones, bipyridylium, carbamates, cyproconazole, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroaniline, dinitrophenol, diphenyl ether, glycine, imidazolinone, isoxazole, isoxazolidinone, nitrile, N-phenylphthalimide, oxadiazole, oxazolidinedione, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids such as glufosinate, phosphoramidites, ate), dithiophosphates, o-carbamoylbenzoates, pyrazoles such as pyroxasulfone, pyridazinones, pyridines, picolinic acid, pyridinecarboxamides, pyrimidinediones, (thio)benzoic acid pyrimidine esters, quinolinecarboxylic acid, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines (such as atrazine, indaziflam and terbuthylazine), triazinones such as metribuzin, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils (including aryl uracils such as saflufenacil), and ureas. Atrazine, indaziflam, saflufenacil, pyroxasulfone, glufosinate, cyproconazole, terbuthylazine and metribuzin, especially atrazine, are particularly preferred herbicides.

[0454] A pesticide is generally a chemical or biological agent (such as a pesticidal active ingredient, compound, composition, virus, bacteria, antimicrobial agent, or disinfectant) that, through its effect, deters, disables, kills, or otherwise thwarts pests. Target pests can include insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms), and microorganisms that damage property, cause nuisances, spread disease, or are vectors of disease. The term "pesticide" also includes plant growth regulators that alter the desired growth, flowering, or reproductive rate of a plant; defoliants that cause leaves or other foliage to fall from a plant, typically to facilitate harvesting; desiccants that promote the drying of living tissue, such as unwanted aerial parts of a plant; plant activators that activate plant physiology to defend against certain pests; safeners that reduce the unwanted herbicidal effects of pesticides on crop plants; and plant growth promoters that affect plant physiology, for example, to enhance plant growth, biomass, yield, or any other quality parameter of harvestable items of a crop plant.

[0455] The following list of pesticides suitable for use in the compositions of the present invention is intended to illustrate possible combinations but does not limit them:

[0456] A) Respiratory depressants

[0457] -In Q oComplex III inhibitors of the site: azoxystrobin, carboxystrobin, syringosterone, kadoxstrobin, enestrobin, enestrobin, fenoxystrobin (fenoxystrobin / flufenoxystrobin), fluoxastrobin, kresoxstrobin, mandestrobin, fenoxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, trifloxystrobin, pyraclostrobin, trifloxystrobin, pyraclostrobin, trifloxystrobin, triclopyricarb (triclopyricarb / chlorodincarb), oxadiazon, fenamid, pyrimidine, pyrimethanil, pyrifloxystrobin, tetracycline;

[0458] -In Q i Complex III inhibitors of the site: cyazofamid, indazolesulfamide, fenpicoxamid, pyridoxamide, and pyridoxamide;

[0459] - Complex II inhibitors: oxadixanil, benzovinflupyr, bixafen, boscalid, carboxin, furamide, fluopyram, flutolanil, fluopyram, furazolidone, isopyram, pyraclostrobin, mefenadil, oxycarboxin, fluopyram, penthiopyrad, fluopyram, bixafen, flutolanil, chlorothalonil, thiofuran, inpyrfluxam, pyrapropoyne, fluinoxam, isoflucypram, triflupyramide;

[0460] - Other respiratory inhibitors: diflumetorim; nitrophenyl derivatives: binapacryl, diflubenzuron, diclofenac, fluazinam, nitrostrobin; ferimzone; organometallic compounds: triphenyltin salts, for example, triphenyltin acetate, triphenyltin chloride or triphenyltin hydroxide; silthiopyrad;

[0461] - Quinone exo-inhibitor stigmatellin binding type: ametoctradin;

[0462] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0463] -C14 demethylase inhibitors: triazoles: azaconazole, bifenthiazolin, oxadiazole, cyproconazole, difenoconazole, diniconazole, R-diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imipenem, picronil, metconazole, myclobutanil, oximidazole, paclobutrazol, penconazole, propiconazole, prothioconazole, silyclofazole, tebuconazole, fluconazole, triadimefon, triadimenol, triticonazole, uniconazole, fluopyram, ipfentrifluconazole, clofoconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: clofofenamide, pyrimidine oxime, triflumizol;

[0464] -δ14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, isotridemorph, fenpropidin, spiroxathiapiprolin, spiroxathiapiprolin;

[0465] -3-Ketoreductase inhibitors: fenacet, fenacet-3-pyraclostrobin;

[0466] -Other sterol biosynthesis inhibitors: clofentoxazole;

[0467] C) Nucleic acid synthesis inhibitors

[0468] - RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, furamide, oxadixyl;

[0469] - Other nucleic acid synthesis inhibitors: oxamexazole, octhiocarb, oxolinic acid, pyrimethanol sulfonate, 5-flucytosine, isoflurane, and flutolanil;

[0470] D) Inhibitors of cell division and cytoskeleton

[0471] - Tubulin polymerization inhibitors: benomyl, carbendazim, thiophanate-methyl, thiophanate-methyl, pyridachlometyl;

[0472] - Other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopyram, zoxamide, mefenacet, fenpyrad, cyproconazole, cyproconazole, fluopyram;

[0473] E) Amino acid and protein synthesis inhibitors

[0474] -Methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;

[0475] - Protein synthesis inhibitors: blasticidin, kasugamycin, kasugamycin hydrochloride hydrate, midonomycin, streptomycin, oxytetracycline;

[0476] F) Signal transduction inhibitors

[0477] -MAP / histidine kinase inhibitors: fluazifop, iprodione, procymidone, vinclozolin, fludioxonil;

[0478] -Mechanism unknown: fluphenoxyquin, propoxyiodoquin;

[0479] G) Lipid and membrane synthesis inhibitors

[0480] - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyraclostrobin, isoprothiolane;

[0481] -Lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, and etridiazole;

[0482] -Compounds and fatty acids that affect cell membrane permeability: propamocarb;

[0483] - Oxysterol-binding protein inhibitors: fluoxapiprolin, fluoxapiprolin;

[0484] H) Inhibitors with multi-site action

[0485] - Inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

[0486] -Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;

[0487] -Organochlor compounds: difop-butyl, chlorothalonil, captol, captan, folpet, bacteriostatic, dichlorophen, hexachlorobenzene, pentachlorophenol and its salts, phthalide, tolylfluanid;

[0488] -Guanidine and others: guanidine, dodine, dodine free base, guazatine, guazatine acetate, guazatine octylamine, guazatine octylamine triacetate, guazatine trioctylbenzenesulfonate, dithianon, fluazifop, sulfamethoxazole, and chloranil;

[0489] I) Cell wall synthesis inhibitors

[0490] - Glucan synthesis inhibitors: validamycin, polyoxin B;

[0491] -Melanin synthesis inhibitors: pyroquilon, tricyclazole, cyproconazole, dicyclomet, pyraclostrobin, trifluomethiocarb;

[0492] - Cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benzathiapyr, valinomycin, and valosin;

[0493] J) Plant defense inducers

[0494] -Acibenzolar-S-methyl, probenazol, isothiocyanate, tiadinil, prohexadione-calcium; phosphonates: fosetyl acid, fosetyl-aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlorobenzothiazole;

[0495] K) Unknown mode of action

[0496] - bronopol, cyfluanid, cymoxanil, dazomethanil, imidacloprid, dichlorocyanamide, pyraclostrobin, diflubenzuron, diflubenzuron methyl sulfate, diphenylamine, chloranil, flumetover, flumetylsulforim, sulfamethoxam, fluthiazolinone, hypersensitive protein, chlorpyrifos, phthalocyanine, copper quinoline, seboctylamine, isobutylethoxyquin, phthalocyanine, imidazolin, pyraclostrobin, thiabendazole, bromothionil, aminopyrifen, flufenoxadiazam;

[0497] L) Biopesticides

[0498] L1) Microbial pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: Parasiticidal spores, Aspergillus flavus, Aureobasidium brevis, Bacillus spp., Bacillus amyloliquefaciens, Bacillus amyloliquefaciens plantarum (also known as Bacillus velez), Bacillus megaterium, Bacillus mohaievii, Bacillus mycoides, Bacillus pumilus, Bacillus simplex, Bacillus haloterreus, Bacillus subtilis, Bacillus subtilis var. amyloliquefaciens, Bacillus velez, Candida oleifera, Candida saitoana, Clavibactermichiganensis (bacteriophage), Cleometheus spp., Cryptococcus parasiticus, Cryptococcus albus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea. catenulate (also known as Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticum, Lysobacter mold-producing, Mycobacterium drupe, Microdochium dimerum, Sphaeroides microsporum, Muscodor albus, Bacillus alveoli, Paenibacillus epiphyticus, Paenibacillus polymyxa, Pantoea agglomerans, Penicillium bilaireae, Pseudomonas species, Pseudomonas viridis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces glaucum, Streptomyces lydicus, Streptomyces violaceus, Streptomyces leucoderma, Trichoderma spp. asperelloides), Trichoderma acanthophorum, Trichoderma amurensis, Trichoderma apical, Trichoderma gaimsii, Trichoderma harmatum, Trichoderma harzianum, Trichoderma polysporum, Trichoderma stromaticum, Trichoderma virens, Trichoderma viride, Typhula phacorrhiza, Typhula serrata, Verticillium dahliae, and zucchini yellow mosaic virus (avirulent strain);

[0499] L2) biochemical pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: hypersensitive proteins, Knotweed extracts;

[0500] L3) Microbial pesticides with insecticidal, acaricidal, snail-killing and / or nematicidal activity: Agrobacterium radiobacterium, Bacillus cereus, Bacillus firmus, Bacillus thuringiensis, Bacillus thuringiensis subsp. ayuzawa, Bacillus thuringiensis subsp. israelensis, Bacillus thuringiensis subsp. wax moth, Bacillus thuringiensis subsp. kurstak, Bacillus thuringiensis subsp. pseudolobatus, Beauveria bassiana, Beauveria bassiana, Burkholderia species, Chromobacterium subtsugae, codling moth granulovirus, pseudocodling moth granulovirus, Flavobacterium species, cotton bollworm nuclear polyhedrosis virus, zea armyworm nuclear polyhedrosis virus, zea armyworm single capsid nuclear polyhedrosis virus, bacteriotrophic nematode Heterorhabditis elegans, Coryneformis fumosorum, Lecanicillium longisporum longisporum), L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae microspore var., Metarhizium anisopliae locust var., Nomura leishmanii, Paecilomyces fumosoroseus, Paecilomyces lilacinus, Paenibacillus japonicus, Pasteurella species, Pasteurella szabalais, Pasteurella penetrantis, Pasteurella ramosa, Pasteurella listeri, Pasteurella usgae, Pseudomonas fluorescens, Spodoptera nuclei nuclear polyhedrosis virus, Steinberger nematode, Steinberger nematode, Sawfly nematode, Streptomyces luteus, Streptomyces tenuis;

[0501] L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-decadienoic acid ethyl ester (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavandulyl senecioate, cis-jasmone, 2-methyl-1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-acetic acid -2,13-octadecadien-1-ol ester, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, termite pheromone (pentatermanone), (E,Z,Z)-3,8,11-tetradecadien-1-yl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, neem oil, Quillay extract;

[0502] L5) Microbial pesticides with plant stress-reducing, plant growth regulator, plant growth-promoting and / or yield-enhancing activity: Azospirillum agalactiae, Azospirillum brasiliensis, Azospirillum lipogenicum, Azospirillum iraqium, Azospirillum euryhaline, Bradyrhizobium sp., Bradyrhizobium elsdenii, Bradyrhizobium glycines, Bradyrhizobium liaoningensis, Bradyrhizobium lupini, Delftia acidovorans, arbuscular mycorrhizal fungi, Mesorhizobium sp., Rhizobium leguminosarum biotype bean, Rhizobium leguminosarum biotype trifolium, Rhizobium leguminosarum biotype faba bean, Rhizobium tropicalis, and Sinorhizobium meliloti;

[0503] O) Insecticides from categories O.1 to O.29

[0504] O.1 Acetylcholinesterase (AChE) inhibitors: aldicarb, cotton boll carb, benfuracarb, benfuracarb, butanone carb, butanone sulfone carb, carbaryl, carbofuran, butanfuracarb, ethiofencarb, fenbutacarb, fenthiocarb, furamicarb, isoprocarb, methiocarb, methomyl, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, long-lasting carb, mixed carb, XMC, methomyl, triazolam; acephate, methyl pyriphos, ethyl azinphos-methyl, azinphos-methyl, cadusofos, chlorpyrifos, chlormethylphos, chlorpyrifos, methyl chlorpyrifos, coumaphos, cypermethrin, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, methyl chlorpyrifos, ethyl Azophos, EPN, ethion, propamiphos, fenamiphos, fenamiphos, fenitrothion, fenthion, thiamethoxam, heptenophos, cyanimiphos, isopropylamidophos, O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, methamidophos, methidathion, mevinphos, monocrotophos, dibromophos, omethoate, parathion, methyl parathion, fenamiphos, phorate, phosalone, phosmet, phosphamidon, phoxim, methyl pirimiphos, profenofos, methoprene, profenofos, pyraclofos, pyridazinphos, quinalphos, butyl pirimiphos, tebufos, terbufos, chlorpyrifos, methyl thiophos, triazophos, trichlorfon, aphidox;

[0505] O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, butenefipronil, pyrafluprole, pyriprole;

[0506] O.3 Sodium channel modulators: flumethrin, allethrin, dextro-cis-trans allethrin, dextro-trans allethrin, bifenthrin, k-bifenthrin, bio-allethrin, bio-allethrin S-cyclopentenyl, bio-resmethrin, acetothrin, cypermethrin, β-cypermethrin, flucypermethrin, λ-cypermethrin, γ-cypermethrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, phenothrin, deltamethrin, Cypermethrin, esfenvalerate, etofenprox, cypermethrin, fenvalerate, flucythrin, flumethrin, fluvalinate, bromofluthrin, tefluthrin, iminothrin, chlorfluthrin, metofluthrin, methifluthrin, ε-metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), pyrethrum, silafluthrin, tefluthrin, kappa-tefluthrin, tetrafluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;

[0507] O.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloheximide, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyralid, trifluanid, bithiazol, flufenoxam;

[0508] O.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, ethyl spinosad;

[0509] O.6 Chloride channel activators: abamectin, avermectin benzoate, ivermectin, lepidomectin, and mitramectin;

[0510] O.7 Juvenile hormone simulants: methoprene, methoprene, methoprene; fenoxycarb, pyriproxyfen;

[0511] O.8 Various nonspecific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfonyl fluoride, borax, tartar emetic;

[0512] O.9 String organ TRPV channel modulators: diprofenoic acid, pymetrozine, and flubendiamide;

[0513] O.10 Mite growth inhibitors: clofentezine, hexythiazox, fluazifop; etoxazole;

[0514] O.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaericus, and insecticidal proteins produced by them: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis; Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;

[0515] O.12 Mitochondrial ATP synthase inhibitors: diafenthiuron; azoxatin, cyhexatin, fenbutatin, propargite, and fenbutalin;

[0516] O.13 Oxidative phosphorylation decouplers via proton gradient interference: chlorfenapyr, DNOC, sulfluramid;

[0517] O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: sulfamethoxazole, cartap, thiophanate-methyl, and dimethoate;

[0518] O.15 Chitin biosynthesis inhibitors type 0: bistrifluanuron, chlorfluazuron, diflubenzuron, flufenoxuron, flufenoxuron, hexaflumuron, lufenuron, flufenoxuron, perfluanidone, flubendiamide, fluazifop-urea;

[0519] O.16 Chitin biosynthesis inhibitor type 1: thiazolinone;

[0520] O.17 Molting disruptor: cyromazine;

[0521] O.18 Ecdysone receptor agonists: methoxyfenozide, tebufenozide, chlorfenozide, furofenozide, chlorfenozide;

[0522] O.19 Octopamine receptor agonist: amitraz;

[0523] O.20 Mitochondrial complex III electron transport inhibitors: hydrazone, acequinoxaline, pyrimidifen, bifenazate;

[0524] O.21 Mitochondrial complex I electron transport inhibitors: quinazofen, fenpyraclostrobin, pyrimidifen, pyridabenz, tebufenpyrad, tolfenpyrad; rotenone;

[0525] O.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone;

[0526] O.23 Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, methoxyfenethyl, spirodiclofen, spidoxamat;

[0527] O.24 Mitochondrial complex IV electron transport inhibitors: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0528] O.25 Mitochondrial complex II electron transport inhibitors: cypermethrin, cyfluthrin, ethoxyfen, pyrazoanilide;

[0529] O.28 Rianodin receptor modulators: chlorantraniliprole, cyantraniliprole, cyclobromofenapyr, flubendiamide, flufenapyr; tetrazolyl fenpropiamide; thiofenapyr;

[0530] O.29 String organ regulator: flonicamid;

[0531] O.30 GABA-gated chloride channel allosteric modulators: bromofenac, chlorfluanid, isoxathiapyr;

[0532] O.33 Calcium-activated potassium channel modulator: acynonapyr;

[0533] O.34 Mitochondrial complex III electron transport inhibitor at the Qi site: flometoquin;

[0534] O.UN Insecticide compounds with unknown or uncertain mode of action: afolan, azadirachtin, sulfamethoxam, benzyl methacrylate, bromopyralid, chlorfenapyr, cryolite, cyprodinil, dichlorothiazide, dicofol, fenthiocarb, flumethoxam, fluometoquin, flufenoxolone, fluhexapram, fluopyram, flurelana, metaldehyde, flufenoxone, piperonyl butoxide, flupyralid, flutolane, flutolane, umifoxolaner, active substance based on Bacillus firmus (Votivo); triflumilastamide; chlorpyrifos; sarolana, lotirana; benzpyrimoxan; tigolaner; oxaflutamide; cyprodinil, nicofluprole; indole.

[0535] P) Herbicides from categories P1 to P15

[0536] P1) Lipid biosynthesis inhibitors:

[0537] -ACC-herbicides: fenpyroxene, fenpyroxene-sodium, fenpyroxene, clethodim, clodinafop-butyl, clodinafop-butyl, cyhalofop-butyl, cyhalofop-butyl acid, cyhalofop-butyl, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene acid, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene, fenpyroxene;

[0538] - Non-ACC herbicides: benfuresate, butylate, cycloate, dalapon, pyraclostrobin, EPTC, pentocarb, ethoxyfuroxate, tetrafluoropropionic acid, molinate, orbencarb, pebulate, prosulfocarb, TCA, pyraclostrobin, pyraclostrobin, and vernolate;

[0539] P2) ALS inhibitors:

[0540] -Sulfonylureas: amidosulfuron-methyl, tetrazosulfuron-methyl, benzylsulfuron-methyl acid, benzylsulfuron-methyl, chlorimuron-methyl acid, chlorimuron-methyl ... , metazosulfuron, metsulfuron-methyl acid, metsulfuron-methyl, nicosulfuron-methyl, pyrimidinesulfuron-methyl, epoxysulfuron-methyl, primisulfuron-methyl acid, primisulfuron-methyl, promazinesulfuron-methyl, prosulfuron, pyrazosulfuron-methyl acid, pyrazosulfuron-methyl, sulfonesulfuron-methyl, sulfosulfuron-methyl acid, sulfosulfuron-methyl, thifensulfuron-methyl acid, thifensulfuron-methyl, ethersulfuron-methyl, tribenuron-methyl acid, tribenuron-methyl, trifloxysulfuron, trifloxysulfuron-methyl acid, trifloxysulfuron-methyl and trifloxysulfuron-methyl;

[0541] - Imidazolinones: imazamox, imazamox methyl, imazamox, imazamox-methyl, imazapyr, imazapyr, imazaquin and imazamox;

[0542] - triazolopyrimidine herbicides, and sulfonanilides: clofosulphonic acid, clofosulphonamide, diclofosulphonamide, fluazifop, fluazifop, penoxsulam, pyrimisulfan and pyrimisulfan;

[0543] - Pyrimidinyl benzoates: bispyribac-sodium, bispyribac-sodium, pyrimidoxifen, pyrimidoxifen-sodium, pyrimidoxifen acid, pyrimidoxifen-sodium, pyrimidoxifen-sodium;

[0544] -Sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiathionyl acid and thiathionyl;

[0545] - and fluazifop;

[0546] P3) Photosynthesis inhibitors:

[0547] Amicarbazone, inhibitors of photosystem II, triazine herbicides including chlorotriazines, triazinones, triazindiones, methylthiotriazines, and pyridazinones such as ametryn, atrazine, chlorpyrifos, cyanazine, dichlorvos, isopentanol, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryn and trietazin, aryl ureas such as chlorbromide, chlorotoluron, chloroxuron, oxazoluron, diuron, fluuron, isoproturon, isoproturon, oxazolidinone, linuron, metamitron, methylbenzimidazole, pyranuron, methoxuron, chlorothiazuron, thiocarb, lenauron, tebuthiocarb and thiadiazuron, phenylcarbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uracils such as bromophenoxim, lenauryl and ternacil, as well as bentazone and bentazone-sodium, pyridate, pyridafol, meclofenamide and propanil, and inhibitors of photosystem I such as diquat, diquat-dibromide, paraquat, paraquat-dichloride and paraquat-bismethylsulfate;

[0548] P4) Protoporphyrinogen-IX oxidase inhibitors:

[0549] Acifluorfen, Acifluorfen sodium, Fenpyrazone, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron, Fenpyrasulfuron-butyl ...

[0550] P5) Bleach Herbicides:

[0551] -PDS inhibitors: fluazifop, flufenacet, flupyridone, flurochloridone, fluchloridone, norflurazon, flupyridone, rimisoxafen;

[0552] -HPPD inhibitors: benzobicyclon, benzofenap, flupyralid, isoxaflutole, fenquinone, isoxaflutole, mesotrione, oxotrione, pyrazolynate, pyrazoxyfen, sulfotrione, tefuryltrione, cyproconazole, pyraclostrobin, benzyltrione, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxypyrithione;

[0553] - bleaching agents, unknown target: aclonifen, chlorfenapyr, flumeturon, bixlozone;

[0554] P6) EPSP synthase inhibitors:

[0555] glyphosate, glyphosate-isopropylammonium, glyphosate-potassium, and glyphosate-trimethylsulfonate (glufosinate);

[0556] P7) Glutamine synthase inhibitors: bialaphos (bialaphos), bialaphos-sodium, glufosinate, glufosinate-supplement, and glufosinate-ammonium;

[0557] P8) DHP synthase inhibitors: asulam;

[0558] P9) Mitosis inhibitors:

[0559] -K1 group: Dinitroanilines: fluazifop, butralin, dimethalin, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, and trifluralin; Phosphamides: fenamiphos, fenamiphos-methyl, and butamiphos; Benzoic acid herbicides: chlorthal, chlorthal-methyl; Pyridines: dithiopyr and thiapyr; Benzamides: propyzamide and tebutam;

[0560] -K2 group: carbetamide, chlorpropamine, chlorpyrifos, chlorpyrifos-isopropyl, chlorpyrifos-methyl, chlorpyrifos-isopropyl, chlorpyrifos-methyl and chlorpyrifos;

[0561] P10) VLCFA inhibitors:

[0562] - Chloroacetamides: acetochlor, alachlor, acetamiprid, butachlor, dimethachlor, dimethenamid, dimethenamid-S, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propisochlor, propisochlor, and thenylchlor,

[0563] -Oxyacetanilides: flufenacet and mefenacet;

[0564] - Acetanilides: diphenamid, naproxen, naproxen, and dichlorvos;

[0565] - Tetrazolinones: fentrazamide;

[0566] - Other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, pyroxasulfone, pyroxasulfone, dimethoate and isoxazoline;

[0567] P11) Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, fluazifop, indazine fluazifop, isoxaben, triazine fluazifop;

[0568] P12) Decoupling herbicides: dinoseb, dinoterb and DNOC and their salts;

[0569] P13) Auxin herbicides:

[0570] 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, 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, 2,4-dichlorprop and its salts and esters, flopyrauxifen ), fluroxypyr, fluroxyisopropyl butoxyisopropyl, fluroxyisooctyl isooctyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl ester, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-squared and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA(2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, halauxifen ester and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid;

[0571] P14) Auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam, and naptalam-sodium;

[0572] P15) Other herbicides: bromobutyric acid chloranil, chloranil, chloranil, cyproconazole, benzylpyridinium, cyclopyrimorate and its salts and esters, dalapon, dazomethanil, diazepam, diazepam methyl sulfate, thiamethoxam, DSMA, cypermethrin, cypermethrin and its salts, ethoxybenzone, cypermethrin, cypermethrin butyl ester, furazolidone, cypermethrin, cypermethrin ammonium, indole, maleic hydrazide, fluazifop, methamphetamine, methacrylic acid sulfonate, methyl azide, methyl bromide, methyl-cypermethrin, methyl iodide, MSMA, oleic acid, oxazolidinone, nonanoic acid, chlorpyrifos, quinazolin, tetrafluanid, and cypermethrin.

[0573] Q) Safener

[0574] (Quinolin-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oximinophenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalene dicarboxylic anhydride, 2-halo-4-(haloalkyl)-5-thiazolecarboxylic acid, thiophosphates and N-alkyl-O-phenylcarbamates and agriculturally acceptable salts thereof and agriculturally acceptable derivatives thereof, such as amides, esters and thioesters, provided that they have an acid group.

[0575] In a particularly preferred embodiment, the agrochemical active ingredient is selected from azoxystrobin, flupyraclonil, fludioxonil, thiophanate-methyl, atrazine, tetracycline, clofoconazole, prothioconazole, tebuconazole, terbuthylazine, difluanid, and metribuzin, preferably selected from azoxystrobin, flupyraclonil, fludioxonil, prothioconazole, thiophanate-methyl, difluanid, terbuthylazine and atrazine, and most preferably is azoxystrobin.

[0576] Suitable safeners include (quinolin-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oximinophenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazolecarboxylic acid, thiophosphates and N-alkyl-O-phenylcarbamates and agriculturally acceptable salts thereof and agriculturally acceptable derivatives thereof, such as amides, esters, and thioesters, provided that they have an acid group.

[0577] Suitable nitrification inhibitors are linoleic acid, α-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (chlorpyrifos or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole 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-thiadiazole (dimethicone, trimethoprim), 2-sulfonamidothiazole (ST), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazolethiourea (TU), N-(1H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide and N-(1H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazol-1-ylmethyl )-formamide, neem, products containing neem ingredients, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, zinc sulfate, 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA1") and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA2"), and / or derivatives thereof, and / or salts thereof; glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium glycolate, hereinafter referred to as "DMPG"), and / or isomers thereof, and / or derivatives thereof; citric acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium citrate, hereinafter referred to as "DMPC" ”), and / or its isomers, and / or its derivatives; a lactic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium lactate, hereinafter referred to as “DMPL”), and / or its isomers, and / or its derivatives; a mandelic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium mandelate, hereinafter referred to as “DMPM”), and / or its isomers, and / or its derivatives; 1,2,4-triazole (hereinafter referred to as “TZ”), and / or its derivatives, and / or its salts; 4-chloro-3-methylpyrazole (hereinafter referred to as “ClMP”), and / or its isomers, and / or its derivatives, and / or its salts; a reaction adduct of dicyandiamide, urea and formaldehyde, or a triazone-formaldehyde-dicyandiamide adduct;2-Cyano-1-((4-oxo-1,3,5-triazin-1-yl)methyl)guanidine, 1-((2-cyanoguanidino)methyl)urea; 2-Cyano-1-((2-cyanoguanidino)methyl)guanidine; 3,4-dimethylpyrazole phosphate; allylthiourea, and chlorate.

[0578] Examples of urease inhibitors include N-(n-butyl)thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric acid triamide (NPPT), 2-nitrophenylphosphoric acid triamide (2-NPT), other NXPTs known to the skilled person, phenylphosphorodiamidates (PPD / PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see, for example, US Pat. No. 8,075,659). Such mixtures of NBPT and NPPT may contain NBPT in an amount of 40 to 95% wt.-%, and preferably 60 to 80% wt.-%, based on the total amount of active substances. This mixture is sold as LIMUS, which is a composition containing about 16.9 wt.-% NBPT, about 5.6 wt.-% NPPT, and about 77.5 wt.-% other ingredients (including solvents and adjuvants).

[0579] Suitable plant growth regulators are auxins, growth hormones, cytokinins, defoliants, ethylene regulators, ethylene releasers, gibberellins, growth inhibitors, orthopedics, growth retardants, growth stimulants and further unclassified plant growth regulators.

[0580] Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine and molybdenum.

[0581] Agrochemical compositions typically contain a biologically effective amount, e.g., a pesticidally effective amount, of an agrochemical active ingredient. The term "effective amount" refers to an amount of a composition or agrochemical active ingredient that is sufficient, for example, to control harmful fungi on cultivated plants or to protect materials, and that does not cause substantial damage to the treated plants. Such an amount can vary widely and depends on various factors, such as the fungal species to be controlled, the cultivated plants or materials to be treated, climatic conditions, and the specific agrochemical active ingredient used.

[0582] The agrochemical composition typically comprises an agrochemical active ingredient in a concentration of 1% to 70% by weight (% ws) on a solid weight basis, preferably 1 to 60% ws, more preferably 10 to 50% ws, and most preferably 20 to 45% ws, based on the total weight of the agrochemical composition. The agrochemical composition typically contains at least 5% ws of the agrochemical active ingredient, preferably at least 15% ws, more preferably at least 25% ws, and most preferably at least 35% ws of the agrochemical active ingredient, based on the total weight of the agrochemical composition. The agrochemical composition typically contains up to 95% ws of the agrochemical active ingredient, preferably up to 65% ws, more preferably up to at least 45% ws of the agrochemical active ingredient, based on the total weight of the agrochemical composition. The active substance is used in a purity of 90% to 100%, preferably 95% to 100%, as determined by nuclear magnetic resonance (NMR) spectroscopy.

[0583] The agrochemical composition typically comprises the grafted polymer in a concentration of 0.5 to 20% ws, preferably 0.5 to 10% ws, more preferably 1 to 8% ws, based on the total weight of the agrochemical composition. The concentration of the grafted polymer is typically up to 15% ws, more preferably up to 9% ws, most preferably up to 7% ws, based on the total weight of the agrochemical composition. The concentration of the grafted polymer is usually at least 2% ws, preferably at least 2.5% ws, based on the total weight of the agrochemical composition.

[0584] The graft polymer according to the present invention is typically present in dissolved form in the agrochemical composition, particularly if the agrochemical composition is an aqueous agrochemical composition. Typical solvents include those discussed below as adjuvants.

[0585] The grafted 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 having a continuous organic phase.

[0586] The weight ratio of active agrochemical ingredient to grafted 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.

[0587] Agrochemical compositions can be any conventional type of agrochemical compositions, including solutions, emulsions, suspensions, pulvis, powders, pastes, granules, compressed formulations, capsules, and mixtures thereof. Examples of composition types include suspensions (e.g., SC, OD, FS, SE, DC), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, pastilles, wettable powders or pulvis (e.g., WP, SP, WS, DP, DS), compressed formulations (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticide preparations (e.g., LN), and gel compositions (e.g., GF) for processing plant propagation materials such as seeds. These and other composition types are defined in " Catalogue of pesticide formulation types and international coding system [pesticide formulation types and international coding system catalogue] ", Technical Monograph [technical monograph] the 2nd phase, the 6th edition May, 2008, in CropLife International.

[0588] Preferred composition types are suspensions, emulsifiable concentrates (EC), wettable powders or wettable powders, and granules, particularly suspensions. Preferred suspensions include suspension concentrates (SC), suspoemulsions (SE), and dispersible concentrates (DC). Most preferred are suspension concentrates (SC).

[0589] These 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. Agrochemical compositions are typically prepared by contacting the grafted polymer and the active agrochemical ingredient. If the agrochemical composition is a suspension, the process typically involves contacting the active agrochemical ingredient with water to form a mill base. The premix is then typically subjected to grinding or milling to form the final suspension. The grafted polymer can be added to the mill base or the final suspension, in particular the mill base.

[0590] In case the agrochemical composition is a granule, it is typically obtained by preparing a premix containing the agrochemical active ingredient, the grafted polymer, a filler and typically up to 5 wt.-% of water and then extruding the premix. The extrudate is then dried and converted into granules.

[0591] Suitable auxiliaries that can be added to the agrochemical compositions are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, wetting agents, insect repellents, attractants, feeding stimulants, extenders, bactericides, antifreeze agents, defoamers, colorants, crystal growth inhibitors, tackifiers and binders.

[0592] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, for example kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example toluene, paraffin, tetralin, alkylated naphthalenes; alcohols, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, for example lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, for example N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

[0593] Suitable solid carriers or fillers are mineral earths, for example silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, for example cellulose, starch; fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, for example cereal flour, bark flour, wood flour, nut shell flour and mixtures thereof.

[0594] 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 emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants. Examples of surfactants are listed in McCutcheon's, Volume 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International or North American Edition).

[0595] Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. The example of sulfonates is alkyl aryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, fatty acids and oily sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodecyl- and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinates or sulfosuccinamates. The example of sulfate is the sulfate of the sulfate of fatty acids and oily sulfate, ethoxylated alkylphenol sulfate, alcohol sulfate, ethoxylated alcohol sulfate or the sulfate of fatty acid ester. The example of phosphate is phosphate ester. The example of carboxylates is alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylate.

[0596] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

[0597] Suitable cationic surfactants are quaternary ammonium surfactants, for example, quaternary ammonium compounds with one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are AB or ABA type block polymers comprising a block of polyethylene oxide and polypropylene oxide, or ABC type block polymers comprising an alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polyalkalis. The example of polyacids is an alkali metal salt of polyacrylic acid or a polyacid comb-like polymer. The example of polyalkalis is polyvinylamine or polyvinylamine.

[0598] Suitable adjuvants are compounds that themselves have negligible or even no pesticidal activity and that improve the biological performance of Compound I against the target organism. Examples are surfactants, mineral or vegetable oils, and other adjuvants. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0599] Suitable thickening agents are polysaccharides (e.g., xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinone and benzisothiazolinone. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerol. Suitable defoamers are salts of silicone, long-chain alcohols, and fatty acids. Suitable colorants (e.g., red, blue, or green) are low-water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, hexacyanoferrate) and organic colorants (e.g., alizarin colorants, azo colorants, and phthalocyanine colorants). Suitable tackifiers or adhesives are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0600] Examples of composition types and their preparation include:

[0601] i) Water-soluble concentrates (SL, LS)

[0602] 10 to 60 wt.-% of the agrochemical active substance, 5 to 15 wt.-% of a wetting agent (e.g., alcohol alkoxylate) and 1 to 15 wt.-% of the graft polymer are dissolved in water and / or a water-miscible solvent (e.g., alcohol) (total 100 wt.-%). The active substance dissolves upon dilution with water.

[0603] ii) Dispersible Concentrate (DC)

[0604] 5 to 25 wt.% of the agrochemical active ingredient, 1 to 10 wt.% of the graft polymer and optionally a further dispersant (eg polyvinylpyrrolidone) are dissolved in an organic solvent (eg cyclohexanone) (total 100 wt.%). Dilution with water gives a dispersion.

[0605] iii) Emulsifiable concentrates (EC)

[0606] 15 to 70 wt.% of an agrochemical active ingredient, 1 to 15 wt.% of a graft polymer, and 5 to 10 wt.% of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., an aromatic hydrocarbon) (total 100 wt.%) and diluted with water to obtain an emulsion.

[0607] iv) Emulsion (EW, EO, ES)

[0608] 5 to 40 wt.% of the agrochemical active ingredient, 1 to 15 wt.% of the graft polymer, and 1 to 10 wt.% of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20 to 40 wt.% of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon). This mixture can be added to water (totaling 100 wt.%) using an emulsifier and made into a homogeneous emulsion.

[0609] v) Suspension (SC, OD, FS)

[0610] In an agitated ball mill, 20 to 60 wt.% of the agrochemical active ingredient are comminuted, 1 to 10 wt.% of the graft polymer and optionally further dispersants and wetting agents (e.g. sodium lignin sulfonate and alcohol ethoxylate), 0.1 to 2 wt.% of a thickener (e.g. xanthan gum) and water (total 100 wt.%) are added to give a fine suspension of the active ingredient. Dilution with water gives a stable suspension of the active ingredient. For FS compositions, up to 40 wt.% of a binder (e.g. polyvinyl alcohol) is added. Suspoemulsions (SE) can be obtained by mixing the suspension with an emulsifiable concentrate or with an emulsion, such as an oil-in-water emulsion (EW).

[0611] vi) Water-dispersible granules and water-soluble granules (WG, SG)

[0612] 50 to 80 wt.-% of the agrochemical active ingredient are finely ground, a graft polymer, optionally a further dispersant, and a wetting agent (e.g. sodium lignin sulfonate and alcohol ethoxylate) are added (total 100 wt.-%), and water-dispersible or water-soluble granules are prepared by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

[0613] vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

[0614] 50 to 80 wt.% of the agrochemical active ingredient are ground in a rotor-stator mill, 1 to 5 wt.% of the graft polymer and optionally a further dispersant (e.g. sodium ligninsulfonate), 1 to 3 wt.% of a wetting agent (e.g. alcohol ethoxylate) and a solid carrier (e.g. silica gel) are added (total 100 wt.%). Dilution with water gives a stable dispersion or solution of the active substance.

[0615] viii) Gel (GW, GF)

[0616] In an agitated ball mill, 5 to 25 wt.% of the agrochemical active ingredient are comminuted, 3 to 10 wt.% of the graft polymer and optionally a further dispersant (e.g. sodium ligninsulfonate), 1 to 5 wt.% of a thickener (e.g. carboxymethylcellulose) and water (total 100 wt.%) are added to give a fine suspension of the active substance. Dilution with water gives a stable gel of the active substance.

[0617] ix) Microemulsion (ME)

[0618] 5 to 20 wt.% of the agrochemical active ingredient is added to 5 to 30 wt.% of an organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10 to 25 wt.% of a surfactant blend (e.g., alkanol ethoxylates and arylphenol ethoxylates), 1 to 25 wt.% of a grafted polymer, and water (totaling 100%). This mixture is stirred for 1 hour to spontaneously generate a thermodynamically stable microemulsion.

[0619] x) Microcapsules (CS)

[0620] An oil phase containing 5 to 50 wt.% of an agrochemical active ingredient, 0 to 40 wt.% of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon), and 2 to 15 wt.% of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and a di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Free radical polymerization initiated by a free radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase containing 5 to 50 wt.% of an agrochemical active ingredient, 0 to 40 wt.% of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethylene-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol).

[0621] The addition of a polyamine (e.g., hexamethylenediamine) results in the formation of polyurea microcapsules. The monomer amount is 1 to 10 wt.%. The wt.% is related to the total CS composition. The microcapsules can then be dispersed in an aqueous composition. To this end, 1 to 40 wt.% of the microcapsules are mixed with 2 to 10 wt.% of the grafted polymer and, optionally, an additional dispersant, as well as a wetting agent (e.g., sodium lignin sulfonate and alcohol ethoxylate), 0.1 to 2 wt.% of a thickener (e.g., xanthan gum), and water (totaling 100 wt.%) to produce the CS composition.

[0622] xi) Dustable powders (DP, DS)

[0623] 1 to 10 wt.-% of the agrochemical active ingredient are finely ground and intimately mixed with 1 to 20 wt.-% of the graft polymer and a solid carrier (eg finely divided kaolin) (total 100 wt.-%).

[0624] xii) Granules (GR, FG)

[0625] 0.5 to 30 wt.-% of the agrochemical active ingredient are finely ground and combined with 1 to 20 wt.-% of a graft polymer and a solid carrier (eg silicate) (total 100 wt.-%). Granulation is achieved by extrusion, spray drying or fluidized bed.

[0626] xiii) Ultra Low Volume Liquids (UL)

[0627] 1 to 50 wt.-% of the agrochemical active ingredient and 1 to 30 wt.-% of the graft polymer are dissolved in an organic solvent (eg an aromatic hydrocarbon) (total 100 wt.%).

[0628] Composition types i) to xi) may optionally comprise further adjuvants such as those discussed above, for example 0.1 to 1 wt.-% bactericides, 5 to 15 wt.-% antifreeze agents, 0.1 to 1 wt.-% antifoaming agents and 0.1 to 1 wt.-% colorants.

[0629] In one embodiment, 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.

[0630] The agrochemical suspension contains at least a portion of the agrochemical active ingredient as solid particles suspended in a continuous phase, which is preferably an aqueous continuous phase. Thus, the agrochemical suspension is preferably an aqueous agrochemical suspension containing at least 5 wt.%, preferably at least 10 wt.%, more preferably at least 15 wt.%, most preferably at least 20 wt.%, particularly preferably at least 25 wt.%, such as at least 30 wt.%, and in particular at least 40 wt.%, of water, 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.%, such as up to 50 wt.% of water, based on the total weight of the suspension.

[0631] Agrochemical active ingredients typically exhibit low water solubility. The agrochemical active may have a water-solubility at 20°C and a 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.

[0632] Agrochemical active ingredients are present in agrochemical suspensions in the form of suspended particles. These particles can be characterized by their size distribution, which can be determined using dynamic light scattering techniques. A suitable dynamic light scattering measurement device is manufactured, among others, under the trade name Malvern Mastersizer 3000.

[0633] Particles of agrochemical active ingredients can be characterized by their median diameter, often abbreviated as the D50 value. The D50 value refers to the specific particle size at which half of the particle population, by volume, is smaller than this diameter. The D50 value is typically determined according to ISO 13320:2009. These particles may have a D50 value in the range of 0.05 to 25 μm, preferably in the range of 0.1 to 20 μm, more preferably in the range of 0.5 to less than 20 μm, most preferably in the range of 0.5 to 15 μm, and particularly preferably in the range of 0.5 to 10 μm. These particles typically have a D50 value of at least 0.75 μm, preferably at least 1 μm, and as an upper limit, preferably at most 3 μm or at most 2 μm.

[0634] Particles of the agrochemical active ingredient can be further characterized by their D90 value. The D90 value refers to the specific particle size at which 90% of the particle population by volume is smaller than this diameter. The D90 value is typically determined according to ISO 13320:2009. These particles can have a D90 value of less than 30 to 3 μm, particularly less than 20 μm or less than 15 μm, especially less than 10 μm, less than 8 μm, less than 6 μm, or less than 5 μm.

[0635] Particles of the agrochemical active ingredient can also be characterized by their D10 value. The D10 value refers to the specific particle size at which 10% of the particle population by volume is smaller than this diameter. The D10 value is typically determined according to ISO 13320:2009. These particles can typically have a D10 value of less than 2 μm, for example, in the range of 0.05 to <2 μm, particularly in the range of 0.1 to 1.5 μm, or in the range of 0.1 to 1 μm.

[0636] Preferably, these particles have a D50 value in the range from 0.5 to 10 μm, in particular in the range from 0.5 to 3 μm or in the range from 0.75 to 2 μm, and a D90 value of 3 to less than 10 μm.

[0637] These suspended particles may be in the form of crystalline or amorphous particles that are solid at 20°C.

[0638] Typically, at least 50 wt.-%, preferably at least 70 wt.-%, more preferably at least 90 wt.-% of the agrochemical active ingredient may be present as solid particles in the agrochemical suspension, based on the total weight of the agrochemical active ingredient.

[0639] The agrochemical suspension may contain additional active ingredients, which may be selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biocides, nitrification inhibitors, urease inhibitors, and / or growth regulators. The additional active ingredients may be present in the agrochemical suspension in dissolved form or as suspended particles. The concentration of the additional active ingredients is typically 1 to 50 wt.-%, preferably 10 to 25 wt.-%, based on the total weight of the agrochemical suspension.

[0640] The agrochemical suspension can be prepared at any pH value. Preferably, the agrochemical suspension according to the present invention has a pH below 9, more preferably between 4 and 8.

[0641] Agrochemical suspensions typically contain a thickener. The term "thickener" generally refers to inorganic clays (organically modified or unmodified), such as bentonite, attapulgite, hectorite and montmorillonite clays, and silicates (e.g., colloidal hydrated magnesium silicate, colloidal hydrated aluminum silicate, colloidal hydrated magnesium aluminum silicate, hydrated amorphous silica); and organoclays, such as polycarboxylates (e.g., poly(meth)acrylates and modified poly(meth)acrylates), polysaccharides (e.g., xanthan gum, agarose, rhamnose, pullulan, tragacanth gum, locust bean gum, guar gum, tara gum, welan gum, casein, dextrin, diutangum, cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose), polyvinyl ethers, polyvinyl pyrrolidone, polypropylene oxide-polyethylene oxide condensates, polyvinyl acetate, maleic anhydride, polypropylene glycol, polyacrylonitrile block copolymers, proteins and carbohydrates.

[0642] The present invention also relates to the use of the graft polymers according to the invention as dispersants for agrochemically active ingredients in agrochemical compositions, such as suspensions. It should be understood that all examples herein relating to agrochemical compositions relate both to the agrochemical composition according to the invention and to the use of the graft polymers according to the invention as dispersants for agrochemically active ingredients in agrochemical compositions.

[0643] Seed treatment solutions (LS), suspoemulsions (SE), flowable concentrates (FS), dry treatment powders (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually used for the purpose of treating plant propagation materials, in particular seeds. These compositions give active substance concentrations of 0.01 to 60 wt.-%, preferably 0.1 to 40 wt.-%, in ready-to-use formulations after two to ten times dilution. Application can be carried out before or during sowing. Methods for applying agrochemical compositions to plant propagation materials, in particular seeds, include dressing, coating, granulation, dusting, soaking and in-furrow application methods of the propagation materials. Preferably, the agrochemical compositions are applied to the plant propagation materials, for example by seed dressing, granulation, coating and dusting, so that germination is not induced.

[0644] The invention also relates to a method for controlling phytopathogenic fungi and / or unwanted plant growth and / or unwanted infestation by insects or mites and / or for regulating the growth of plants, wherein an agrochemical composition is allowed to act on the phytopathogenic fungi, the unwanted plant growth or the unwanted insects or mites; and / or on the habitat of the phytopathogenic fungi, the unwanted plant growth or the unwanted 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 useful plants and / or their habitat.

[0645] In one embodiment, the method is used to control phytopathogenic fungi. In another embodiment, the method is used to control unwanted plant growth. In another embodiment, the method is used to control unwanted infestation by insects or mites. These methods typically involve treating the plant to be protected, its habitat, phytopathogenic fungi and / or unwanted plant growth and / or unwanted infestation by insects or mites with an agrochemical composition.

[0646] Suitable treatment methods include, among others, soil treatment, seed treatment, in-furrow application, and foliar application. Soil treatment methods include irrigating the soil, drip irrigation (drip irrigation is applied to 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. In in-furrow application, the steps of digging furrows in the arable land, sowing the furrows with seeds, applying the pesticidal active compound to the furrows, and closing the furrows are typically included.

[0647] When used in plant protection, the amount of agrochemical active applied is, depending on the desired type of effect, 0.001 to 2 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha and in particular 0.1 to 0.75 kg / ha.

[0648] When used for the protection of materials or stored products, the amount of active substance applied depends on the type of application and the desired effect. The amount usually applied for the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic meter of treated material.

[0649] In the treatment of plant propagation material, such as seeds, for example by dusting, coating or soaking, amounts of active substance of 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g and most preferably 5 to 100 g per 100 kg of plant propagation material, preferably seeds, are generally required.

[0650] The present invention also relates to seeds comprising the agrochemical composition of the present invention in an amount of 0.1 g to 10 kg per 100 kg of seeds.

[0651] Various types of oils, wetting agents, adjuvants, fertilizers, or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the agrochemical composition as premixes or, if appropriate, not until just before use (tank mix). These agents can be admixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0652] The user typically applies the agrochemical composition according to the present invention using a pre-dosing device, a knapsack sprayer, a spray tank, a spray aircraft or drone, or an irrigation system. Typically, the agrochemical composition is prepared with water, a buffer, and / or additional adjuvants to the desired application concentration, thereby obtaining a ready-to-use spray liquid or agrochemical composition according to the present invention. Typically, 20 to 2,000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquid are applied per hectare of agriculturally usable area.

[0653] The present invention also relates to a method for combating or controlling invertebrate pests, comprising contacting the invertebrate pests, or their food supply, habitat, or breeding grounds, with a pesticidally effective amount of an agrochemical composition. Furthermore, the present invention relates to a method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting the plants, or the soil or water in which the plants are growing, with a pesticidally effective amount of an agrochemical composition. Furthermore, the present invention relates to a method for treating or protecting animals from infestation or infection by invertebrate pests, comprising contacting the animals with a pesticidally effective amount of an agrochemical composition.

[0654] Invertebrate pests according to the present invention are typically arachnids, molluscs, or insects, in particular insects.

[0655] According to one embodiment, the individual components of the composition according to the invention, such as the parts of a kit or the parts of a binary or ternary mixture, can be mixed by the user himself in a spray tank and, if appropriate, further auxiliaries can be added.

[0656] In a further embodiment, the individual components or partially premixed components of the composition according to the invention can be mixed by the user in a spray tank and, if appropriate, further auxiliaries and additives can be added.

[0657] In further embodiments, the individual components or partially premixed components of the composition according to the present invention may be applied jointly (eg, after tank mixing) or applied sequentially.

[0658] Other Uses

[0659] Another subject of the present invention is the use of the grafted polymers according to the invention and / or obtained or obtainable by the process according to the invention and / or as previously detailed in certain compositions for other uses:

[0660] Therefore, another subject matter of the present invention is the use of the graft polymers of the invention and / or obtained or obtainable by the process of the invention and / or as described in detail above in any of the aforementioned applications in this chapter: such as in cosmetic and personal care formulations, as crude oil demulsifiers, in technical applications (including in pigment dispersions for inkjet inks), in formulations for electroplating, in cementitious compositions, in agrochemical formulations as, for example, dispersants, crystal growth inhibitors and / or solubilizers, in paint and colorant formulations, for textile and leather treatment products used during or after production, formulations containing inorganic salts such as, in particular, silver salts, in mining, metal production and processing (including metal refining and metal quenching), purification of liquids such as wastewater from industry, production or consumers, preferably in cleaning compositions, in particular in cleaning compositions for improved removal of oily and fatty stains, removal of solid soils such as clay, anti-fouling agents, and / or as dye transfer inhibitors.

[0661] Therefore, another subject of the present invention is also a cleaning composition, an industrial and institutional cleaning product, or a formulation or product for any of the previously mentioned applications and fields of application, each comprising at least one grafted polymer as defined above or obtained or obtainable by the process of the invention and / or as described in detail herein.

[0662] Such inventive uses and inventive compositions / products encompass the use of grafted polymers as detailed herein and / or as obtainable or obtained by the process of the invention, such grafted polymers being similar to the grafted polymers as detailed above describing the polymer structure in any embodiment thereof disclosed herein before (including any variants mentioned, and more particularly any preferred, more preferred etc. embodiments).

[0663] The grafted polymers can also support the removal of various hydrophobic and hydrophilic soils, such as body soils, food and grease soils, particulate soils such as clay or carbon black, grass soils, makeup, motor oil, etc., from surfaces such as hard surfaces by surfactants and thus improve the washing and cleaning performance of the formulation.

[0664] In one embodiment, it is also preferred in the present invention that the cleaning composition additionally comprises (in addition to at least one grafted polymer as described above) at least one enzyme, which is preferably selected from one or more optionally further comprises at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersases, mannanases and peroxidases, and a combination of at least two of the aforementioned types, preferably at least one enzyme is selected from lipases.

[0665] Another subject of the present invention is therefore a cleaning composition, such as an industrial and institutional (I&I) cleaning product, comprising at least one graft polymer as defined above, and in particular for use in improved cleaning compositions as dye transfer inhibiting.

[0666] At least one grafted polymer as described herein is present in the cleaning composition of the present invention in an amount ranging from about 0.01% to about 20%, preferably from 0.05 to 10%, more preferably from about 0.1% to 8%, even more preferably from about 0.2% to about 6% and further more preferably from about 0.2% to about 4%, and most preferably in an amount of up to 2%, each as a % by weight relative to the total weight of such composition or product; such cleaning compositions may - and preferably do - further comprise from about 1% to about 70% by weight of a surfactant system.

[0667] Even more preferably, comprising at least one grafted polymer of the present invention and optionally further comprising at least one surfactant or surfactant system, and may additionally comprise at least one enzyme selected from the list consisting of: optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispases, mannanases and peroxidases and a combination of at least two of the aforementioned types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and a combination of at least two of the aforementioned types, more preferably at least one enzyme selected from lipases.

[0668] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, which can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, glass.

[0669] In one embodiment, the grafted polymers of the present invention can be used in a cleaning composition comprising a surfactant system comprising C10-C15 alkylbenzene sulfonate (LAS) as the primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0670] In another embodiment, the grafted polymers of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contain a C8-C18 linear or branched alkyl ether sulfate having 1-5 ethoxy units as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0671] In another embodiment, the graft polymers of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contains a C12-C18 alkyl ethoxylate surfactant having 5-10 ethoxy units as the main surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0672] In one embodiment of the present invention, the grafted polymers are components of cleaning compositions which each additionally comprise at least one surfactant, preferably at least one anionic surfactant.

[0673] The cleaning compositions of the present invention can be in any form, i.e., in the form of "liquid" compositions, including compositions containing liquids such as pastes, gels, emulsions, foams and mousses; in the form of solid compositions such as powders, granules, microcapsules, beads, noodles, pearlescent balls, agglomerates, tablets, granule compositions, sheets, pastilles, beads, fibrous articles, strips, flakes; or mixtures thereof; types delivered in single-, dual- or multi-compartment bags or containers; single-phase or multi-phase unit doses; spray or foam detergents; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in U.S. Pat. No. 6,121,165, Mackey et al.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in U.S. Pat. No. 5,980,931, Fowler et al.), which are activated by the user or consumer with water; and other homogeneous, non-homogeneous or single-phase or multi-phase cleaning product forms.

[0674] The composition can be encapsulated in a single or multi-compartment bag. The multi-compartment bag can have at least two, at least three, or at least four compartments. The multi-compartment bag can include compartments that are arranged side by side and / or overlapped. The composition contained in the bag or its compartments can be a liquid, a solid (such as a powder), or a combination thereof.

[0675] Non-limiting examples of "liquids" / "liquid compositions" include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels typically used for laundry, bleach and laundry additives. Liquids may contain gases, such as suspended air bubbles, or solids, such as particles.

[0676] Cleaning compositions, such as textile and household care products and formulations for industrial and institutional cleaning, more particularly laundry detergents and hand dishwashing detergents, are known to those skilled in the art. Any composition known to those skilled in the art, etc. (in connection with the respective use), can be used within the context of the present invention by comprising at least one polymer according to the invention, preferably at least one polymer in an amount suitable for exhibiting certain properties in such a composition, especially when such a composition is used in its field of use.

[0677] All such cleaning compositions, their ingredients (including (auxiliary) cleaning additives), their general compositions and more specific compositions are known, as shown, for example, in publications 800542 and 800500, as published by Liechtenstein Protegas, and also from WO 2022 / 136409 and WO 2022 / 136408, wherein in any of the aforementioned prior art documents, the graft polymers disclosed in the general compositions and also in each individual specific cleaning composition can be partially or completely replaced by the graft polymers of the present invention having the same function. In those aforementioned documents, various types of formulations for cleaning compositions are also disclosed; all such composition types - general compositions and also each individual specific cleaning composition - can also be used in the same manner for the cleaning compositions envisaged herein.

[0678] Therefore, in addition to or as an alternative to any already existing such prior art compositions containing a polymer or any such compound (which can be replaced by such an inventive graft polymer) - such alternatives being known to those skilled in the art - the present invention also encompasses any and all such disclosed compositions of the previously mentioned prior art disclosures but further comprising at least one of the inventive graft polymers, wherein the content of the inventive graft polymer is typically present in the formulation in a concentration of 0.05 wt.% to 20 wt.%, preferably up to 15 wt.%, more preferably 0.1 wt.% to 10 wt.%, even more preferably 0.5 wt.% to 5 wt.% and between 0.1 wt.% and 0.5 wt.% and including any lower value of 1, 1.5, 2, 2.5 or even 3 and any upper value between 5 wt.% and 10 wt.%, and any range consisting of any lower value and any upper value is also encompassed.

[0679] definition

[0680] As used herein, the articles "a" and "an" when used in the claims or examples should be understood to mean one or more of what is claimed or described. As used herein, the terms "include" and "including" are intended to be non-limiting and, thus, encompass more than the specific items mentioned after these words.

[0681] As used herein, the term "about" encompasses the exact numerical value "X" mentioned, for example, "about X%", etc., as well as small variations in X, including deviations from X of -5% to +5% (for this calculation, X is set to 100%), preferably -2% to +2%, more preferably -1% to +1%, even more preferably -0.5% to +0.5% and smaller variations. Of course, if the given value X itself is already "100%" (such as for purity, etc.), the term "about" can clearly and therefore does only mean its deviation from "100".

[0682] The term "free of water" means that the composition contains no more than 5 wt.-% water, based on the total amount of solvent, in another embodiment no more than 1 wt.-% water, based on the total amount of solvent, and in yet another embodiment the solvent contains no water at all.

[0683] The compositions of the present disclosure may "comprise" the components of the present disclosure (i.e. contain other ingredients), "essentially consist of the components of the present disclosure" (comprise mainly or almost only the mentioned ingredients and only very small amounts of other ingredients mainly only as impurities) or "consist of the components of the present disclosure" (i.e. contain only the mentioned ingredients and may additionally contain only impurities that are unavoidable in the technical environment, preferably contain only these ingredients).

[0684] Similarly, the term "substantially free of" or "substantially free from" or "substantially does not contain..." may be used herein; this means that the indicated material is in a very small amount not intentionally added to the composition to form a part thereof, or, preferably, is not present at an analytically detectable level. It is meant to include compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. If present at all, the indicated material may be present at a level of less than 1%, or even less than 0.1%, or even much less than 0.01%, or even 0%, by weight of the composition.

[0685] Generally, as used herein, the term "obtainable by" means that the corresponding product does not necessarily have to be produced (i.e., obtained) by the corresponding method or process described in the corresponding specific context, but includes products that exhibit all the characteristics of a product produced (obtained) by the corresponding method or process, wherein the product is not actually produced (obtained) by such a method or process. However, the term "obtainable by" also includes the more restrictive term "obtained by", i.e., a product that is actually produced (obtained) by the method or process described in the corresponding specific context.

[0686] Unless otherwise noted, all component or composition levels refer to the active moiety of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, that may be present in commercially available sources of such components or compositions.

[0687] Unless otherwise indicated, all temperatures herein are in degrees Celsius (° C.). Unless otherwise specified, all measurements herein are at 20° C. and under atmospheric pressure. In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specifically stated. All ratios are by weight unless otherwise specifically stated.

[0688] Throughout the present specification, the term "inventive compound" may be used instead of "inventive (graft) polymer(s)" and "(graft) polymer(s) of this (present) invention" to mean that these compounds are disclosed herein as the present invention, defined by their structure and / or their method of production or obtainable by a method defined herein.

[0689] The definitions given in the "Definitions"-section and their preferences are included as part of the invention as described herein.

[0690] The present invention encompasses the specific embodiments as described throughout this disclosure as part of the present invention; various additional options are disclosed in the present specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" (or "preferably", etc.), and the options of the specific embodiments can be selected individually and independently (unless such independent selection is not possible due to the nature of the feature or if such independent selection is expressly excluded) and then combined with any other embodiments (where other such options and preferences can also be selected individually and independently, unless such independent selection is not possible due to the nature of the feature or if such independent selection is expressly excluded), where each and any and all such possible combinations are included as part of the present invention as separate embodiments.

[0691] As used herein, the phrase " Cleaning composition " includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include those designed for cleaning any kind of soiled material or surface.

[0692] For Industrial and Institutional Cleaning "Compositions" include those designed for industrial and institutional cleaning, such as those for cleaning any kind of soiled material or surface, such as hard surface cleaners for any kind of surface, including tile, carpet, PVC surfaces, wooden surfaces, metal surfaces, painted surfaces.

[0693] phrase" Fabric care compositions" is meant to include compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry prewashes, laundry pretreaters, laundry additives, spray products, dry detergents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein and are detailed below when describing the compositions. Such compositions can be used as a pre-wash treatment, a post-wash treatment, or can be added during the rinse or wash cycle of a laundry operation.

[0694] phrase" Compositions for fabric and home care " includes cleaning compositions, which include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry prewashes, laundry pretreaters, laundry additives, spray products, dry detergents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, light-duty liquid detergent compositions, heavy-duty liquid detergent compositions, detergent gels typically used for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used as a pre-wash treatment, a post-wash treatment, or can be added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation. Typically, such compositions contain a cleaning additive.

[0695] The present invention encompasses as part of the present invention specific embodiments as described throughout this disclosure; various additional options disclosed in this specification as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" options for specific embodiments may be individually and independently selected (unless such independent selection is not possible due to the nature of the feature or if such independent selection is expressly excluded) and then combined within any other embodiment (where other such options and preferences may also be individually and independently selected), with each and any and all such possible combinations being included as part of the present invention as separate embodiments.

[0696] The following examples shall further illustrate the present invention without limiting the scope of the present invention.

[0697] Instance section

[0698] The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity Mw / Mn of the grafted polymer of the present invention can be determined by gel permeation chromatography in dimethylacetamide. The mobile phase (eluent) to be used is dimethylacetamide containing 0.5wt% LiBr. The concentration of the grafted polymer in tetrahydrofuran is 4.0 mg / mL. After filtration (pore size 0.2 μm), 100 μL of this solution is injected into the GPC system. Four columns (heated to 60°C) can be used for separation (PLgel pre-column, 3 PLgelMIXED-E columns). The GPC system is operated at a flow rate of 1 mL / min. A DRIAgilent1100 can be used as a detection system. Poly(ethylene glycol) (PEG) standards (PL) with a molecular weight Mn of 106 to 1 378 000 g / mol can be used for calibration.

[0699] Unless "Mw" or "Mn" is specified, the molecular weights given are calculated molecular weights based on the total molar amounts of the ingredients used to make the reaction. Since those reactions proceed essentially to completion, this is an acceptable way to calculate molecular weights.

[0700] Synthesis of the backbone and polymers of the present invention

[0701] The following main chains were prepared as the main chains of the graft polymers used in the present invention.

[0702] A: 35EO+3CL+9EO+3CL+35EO

[0703] B:3CL+34EO+3CL

[0704] C:51EO+3CL+9EO+3CL+51EO

[0705] D: 3CL+78EO+3CL

[0706] E: 1.5CL+34EO+1.5CL

[0707] F:5CL+61EO+5CL

[0708] G:1.5CL+611EO+1.5CL

[0709] H: 23EO+4CL+neopentyl glycol+4CL+23EO

[0710] I: (20EO+2PO) 无规 +4CL+neopentyl glycol+4CL+(20EO+2PO) 无规

[0711] J: 20EO+1CL+neopentyl glycol+1CL+20EO

[0712] K: (35EO+3CL) 无规 +9EO+(3CL+35EO) 无规

[0713] General synthesis of backbones A, C, H, I and J:

[0714] Caprolactone is oligomerized prior to alkylene oxide polymerization to give a mixed random / block structure, and the backbone is obtained by alkoxylation of polycaprolactone.

[0715] General synthesis of backbones B, D, E, F and G:

[0716] Add caprolactone after alkylene oxide polymerization to obtain a block structure of polycaprolactone-polyalkylene oxide-polycaprolactone

[0717] General synthetic concept of main chain K:

[0718] A suitable starter is reacted with a premixed combination of alkylene oxide and caprolactone.

[0719] Synthesis of graft polymer 1-21 of the present invention:

[0720] Table 1: Graft polymers 1-21 of the present invention were synthesized based on backbones AJ.

[0721]

[0722]

[0723] Notes:

[0724] VAc = vinyl acetate; VL = vinyl laurate; VP = vinyl pyrrolidone;

[0725] *Partially hydrolyzed: 40 mol% hydrolyzed based on the total amount of VAc.

[0726] Example 1 (present invention 1)

[0727] Example 1a: Polyethylene glycol modified with 6 mol of caprolactone (molecular weight 400 g / mol)

[0728] In a 4-necked container equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, 240.0 g of polyethylene glycol (molecular weight 400 g / mol) and 0.75 g of tin(II) ethylhexanoate were placed and heated to 100°C.

[0729] 415.0 g of ε-caprolactone were added within 15 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 14 hours. After cooling to room temperature, 645.0 g of an orange oil were obtained. 1 H-NMR indicated 99.5% conversion of caprolactone.

[0730] Example 1b (backbone A): polyethylene glycol (molecular weight 400 g / mol) modified with 6 mol of caprolactone and ethoxylated with 70 mol of ethylene oxide

[0731] In a 21 autoclave, 271.2g of polyethylene glycol (molecular weight 400g / mol) (Example 1a) modified with 6 moles of caprolactone and 2.1g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. 770.9g of ethylene oxide was added over 14 hours. In order to complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtering, 1041.0g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0732] Example 1c (grafted polymer)

[0733] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone A (455.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (245.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 40.8 g / h). After feeds 1 and 2 were complete, feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of polymer solution.

[0734] Example 2 (Present invention 2)

[0735] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone A (450.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (10.08 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 36.89 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (450.50 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 15.7 g / h and 00:10 h to 06:10 h: 7.39 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 75.0 g / h). After feeds 1 and 2 were complete, feed 3 (3.19 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 11.66 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 961 g of polymer solution.

[0736] Example 3 (Present invention 3)

[0737] Example 3a (backbone C): polyethylene glycol (molecular weight 400 g / mol) modified with 6 mol of caprolactone and ethoxylated with 102.2 mol of ethylene oxide

[0738] In a 21 autoclave, 192.9g of polyethylene glycol (molecular weight 400g / mol) (Example 1a) modified with 6 moles of caprolactone and 2.0g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. 801.8g of ethylene oxide was added over 14 hours. In order to complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtering, 990.0g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0739] Example 3b (grafted polymer):

[0740] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone C (455.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (245.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 40.8 g / h). After feeds 1 and 2 were complete, feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of polymer solution.

[0741] Example 4 (Present invention 4)

[0742] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone C (400.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (7.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 31.90 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (600.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 13.1 g / h and 00:10 h to 06:10 h: 5.13 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 83.4 g / h). After feeds 1 and 2 were complete, feed 3 (4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.12 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1065 g of polymer solution.

[0743] Example 5 (Present invention 5)

[0744] Example 5a: Polyethylene glycol ethoxylated with 44 mol of ethylene oxide (molecular weight 1500 g / mol)

[0745] In a 2L autoclave, 599.9g of polyethylene glycol (molecular weight 1500g / mol) and 2.7g of potassium tert-butoxide were placed and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. 754.2g of ethylene oxide was added over 14 hours. To complete the reaction, the mixture was allowed to post-react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. After filtration, 1350.0g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0746] Example 5b (backbone D): polyethylene glycol (molecular weight 1500 g / mol) ethoxylated with 44 mol of ethylene oxide and modified with 6 mol of caprolactone

[0747] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 1044.1 g of polyethylene glycol ethoxylated with 44 mol of ethylene oxide (molecular weight 1500 g / mol) (Example 5a) and 1.25 g of tin(II) ethylhexanoate were placed and heated to 90°C.

[0748] 205.5 g of ε-caprolactone were added within 15 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 10 hours. After cooling to room temperature, 1236.0 g of an orange oil were obtained. 1 H-NMR indicated 98.8% conversion of caprolactone.

[0749] Example 5c (grafted polymer)

[0750] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone D (455.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (245.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 40.8 g / h). After feeds 1 and 2 were complete, feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of polymer solution.

[0751] Example 6 (Present invention 6)

[0752] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone D (679.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (10.87 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 39.76 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (a mixture of 242.50 g of vinyl acetate and 48.50 g of vinyl laurate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 16.9 g / h and 00:10 h to 06:10 h: 7.97 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 48.5 g / h). After feeds 1 and 2 were complete, feed 3 (3.43 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.56 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1036 g of polymer solution.

[0753] Example 7 (Present invention 7)

[0754] Example 7a (backbone E): polyethylene glycol modified with 3 mol of caprolactone (molecular weight 1500 g / mol)

[0755] In a 4-necked container equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, 480.0 g of polyethylene glycol (molecular weight 1500 g / mol) and 0.6 g of tin(II) ethylhexanoate were placed and heated to 80°C.

[0756] 109.6 g of ε-caprolactone were added within 5 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 10 hours. After cooling to room temperature, 580.0 g of an orange oil were obtained. 1 H-NMR indicated a 96.7% conversion of caprolactone

[0757] Example 7b (grafted polymer)

[0758] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone E (540.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (7.56 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.67 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (135.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 11.8 g / h and 00:10 h to 06:10 h: 5.55 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 22.5 g / h). After feeds 1 and 2 were complete, feed 3 (2.39 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 8.74 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 721 g of polymer solution.

[0759] Example 8 (Present invention 8)

[0760] Example 8a: Polyethylene glycol ethoxylated with 47.2 mol of ethylene oxide (molecular weight 600 g / mol)

[0761] In a 2L autoclave, 222.5g of polyethylene glycol (molecular weight 600g / mol) and 2.0g of potassium tert-butoxide were placed and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 130°C. 770.0g of ethylene oxide was added over 10 hours. To complete the reaction, the mixture was allowed to react at 140°C for another 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80°C. After filtration, 990.0g of a light brown solid (hydroxyl value: 45.8mg KOH / g) was obtained.

[0762] Example 8b (backbone F): polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 mol of ethylene oxide and modified with 10 mol of caprolactone

[0763] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 617.9 g of polyethylene glycol ethoxylated with 47.2 mol of ethylene oxide (molecular weight 600 g / mol) (Example 8a) and 0.9 g of tin(II) ethylhexanoate were placed and heated to 80°C.

[0764] 288.8 g of ε-caprolactone were added within 15 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 12 hours. After cooling to room temperature, 900.0 g of an orange oil were obtained. 1 H-NMR indicated 99.0% conversion of caprolactone.

[0765] Example 8c (grafted polymer)

[0766] A polymerization vessel equipped with a stirrer and a reflux condenser was first charged with Backbone F (397.29 g) under a nitrogen atmosphere and heated to 90°C. Feed 1 (3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.56 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (238.37 g of vinyl acetate) and feed 3 (158.92 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate of feed 1 (0:00 h to 00:10 h: 12.9 g / h and 00:10 h to 06:10 h: 6.09 g / h) and a constant feed rate of feed 2 (00:10 h to 06:10 h: 39.7 g / h) and feed 3 (00:10 h to 06:10 h: 26.5 g / h). After feeds 1, 2, and 3 were completed, feed 4 (2.03 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.80 g of propane-1,2-diol) was metered in at a constant feed rate over 0.56 hours at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 721 g of polymer solution.

[0767] Example 9 (Present invention 9)

[0768] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone F (50.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (1.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.10 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (50.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 1.74 g / h and 00:10 h to 06:10 h: 0.82 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 8.33 g / h). After feeds 1 and 2 were complete, feed 3 (0.35 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.30 g of tripropylene glycol) was metered in over 0.56 h at 90 ° C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90 ° C for 1.00 h. The polymerization mixture was heated to 95 ° C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 107 g of polymer solution.

[0769] Example 10 (Present invention 10)

[0770] Example 10a:

[0771] Polyethylene glycol ethoxylated with 47.2 mol of ethylene oxide and modified with 3 mol of caprolactone (molecular weight 600 g / mol) (main chain G) In a 4-necked container equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, 669.8 g of polyethylene glycol ethoxylated with 47.2 mol of ethylene oxide (molecular weight 600 g / mol) (Example 8a) and 0.8 g of tin(II) ethylhexanoate were placed and heated to 80°C.

[0772] 85.6 g of ε-caprolactone were added within 15 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 12 hours. After cooling to room temperature, 746.0 g of an orange solid were obtained. 1 H-NMR indicated 98.0% conversion of caprolactone.

[0773] Example 10b (grafted polymer)

[0774] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone G (75.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (1.68 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (75.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 2.61 g / h and 00:10 h to 06:10 h: 1.23 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 12.50 g / h). After feeds 1 and 2 were complete, feed 3 (0.53 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.94 g of tripropylene glycol) was metered in over 0.56 h at 90 ° C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90 ° C for 1.00 h. The polymerization mixture was heated to 95 ° C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 160 g of polymer solution.

[0775] Example 11 (Present invention 11)

[0776] A polymerization vessel equipped with a stirrer and a reflux condenser was first charged with Backbone G (97.50 g) under a nitrogen atmosphere and heated to 90°C. Feed 1 (0.60 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.92 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (30.00 g of vinyl acetate) and feed 3 (22.50 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate of feed 1 (0:00 h to 00:10 h: 2.51 g / h and 00:10 h to 06:10 h: 3.75 g / h) and a constant feed rate of feed 2 (00:10 h to 06:10 h: 5.00 g / h) and feed 3 (00:10 h to 06:10 h: 3.75 g / h). After feeds 1, 2, and 3 were completed, feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.44 g of propane-1,2-diol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 162 g of polymer solution.

[0777] Example 12 (Present invention 12)

[0778] Example 12a: Neopentyl glycol modified with 8 moles of caprolactone

[0779] In a 4-necked container equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 104.1 g of neopentyl glycol and 1.0 g of tin (II) ethylhexanoate were placed and heated to 140° C. 913.0 g of ε-caprolactone were added over 15 minutes. The reaction mixture was heated to 160° C. to 205° C. and stirred at 160° C. under nitrogen for 4 hours. After cooling to room temperature, 971.0 g of a light yellow oil was obtained. 1 H-NMR indicated 99.0% conversion of caprolactone.

[0780] Example 12b: Neopentyl glycol modified with 8 moles of caprolactone and ethoxylated with 46 moles of ethylene oxide) (Backbone H)

[0781] In a 2L autoclave, 356.1g of neopentyl glycol (Example 12a) modified with 8 mol of caprolactone and 2.01g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. 709.2g of ethylene oxide was added over 14 hours. In order to complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80°C. 1.1g of acetic acid was added. After filtration, 1060.0g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0782] Example 12c (grafted polymer)

[0783] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone H (79.80 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (1.49 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.17 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (53.20 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 4.89 g / h and 00:10 h to 06:10 h: 0.23 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 8.87 g / h). After feeds 1 and 2 were complete, feed 3 (0.34 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 2.99 g of tripropylene glycol) was metered in over 0.56 h at 90 ° C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90 ° C for 1.00 h. The polymerization mixture was heated to 95 ° C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 150 g of polymer solution.

[0784] Example 13 (Present invention 13)

[0785] Example 13a: Neopentyl glycol modified with 8 mol of caprolactone and alkoxylated with a mixture of 40 mol of ethylene oxide and 4 mol of propylene oxide (backbone 1)

[0786] In a 2L autoclave, 300.0g of neopentyl glycol (Example 12a) modified with 8 mol of caprolactone and 1.8g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. A mixture of 519.6g of ethylene oxide and 68.5g of propylene oxide was added over 14 hours. In order to complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. 0.9g of acetic acid was added. After filtration, 880.0g of light brown oil was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0787] Example 13b (grafted polymer)

[0788] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone I (78.00 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (1.35 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 11.88 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (42.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 4.41 g / h and 00:10 h to 06:10 h: 0.23 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 7.09 g / h). After feeds 1 and 2 were complete, feed 3 (0.31 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 2.70 g of tripropylene glycol) was metered in over 0.56 h at 90 ° C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90 ° C for 1.00 h. The polymerization mixture was heated to 95 ° C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 136 g of polymer solution.

[0789] Example 14 (Present invention 14)

[0790] A polymerization vessel equipped with a stirrer and a reflux condenser was first charged with Backbone I (97.50 g) under a nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (45.00 g of vinyl acetate) and feed 3 (7.50 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at variable feed rates of feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 1.25 g / h) and constant feed rates of feed 2 (00:10 h to 06:10 h: 7.50 g / h) and feed 3 (00:10 h to 06:10 h: 1.25 g / h). After feeds 1, 2, and 3 were completed, feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate over 0.56 hours at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 165 g of polymer solution.

[0791] Example 15 (Present invention 15)

[0792] A polymerization vessel equipped with a stirrer and a reflux condenser was first charged with Backbone I (97.50 g) under a nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (37.50 g of vinyl acetate) and feed 3 (15.00 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate of feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 2.12 g / h) and a constant feed rate of feed 2 (00:10 h to 06:10 h: 6.25 g / h) and feed 3 (00:10 h to 06:10 h: 2.50 g / h). After feeds 1, 2, and 3 were completed, feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate over 0.56 hours at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 167 g of polymer solution.

[0793] Example 16 (Present Invention 16)

[0794] A polymerization vessel equipped with a stirrer and a reflux condenser was first charged with Backbone I (97.50 g) under a nitrogen atmosphere and heated to 90°C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (30.00 g of vinyl acetate) and feed 3 (22.50 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate of feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 2.12 g / h) and a constant feed rate of feed 2 (00:10 h to 06:10 h: 5.00 g / h) and feed 3 (00:10 h to 06:10 h: 3.75 g / h). After feeds 1, 2, and 3 were completed, feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate over 0.56 hours at 90°C. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 165 g of polymer solution.

[0795] Example 17 (Present Invention 17)

[0796] Example 17a: Neopentyl glycol modified with 2 moles of caprolactone

[0797] In a 4-necked container equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 156.2 g of neopentyl glycol and 0.5 g of tin(II) ethylhexanoate were placed and heated to 140° C. 342.4 g of ε-caprolactone were added over 15 minutes. The reaction mixture was heated to 160° C. and stirred at 160° C. under nitrogen for 2 hours. After cooling to room temperature, 477.0 g of a light yellow oil was obtained. 1 H-NMR indicated 99.0% conversion of caprolactone.

[0798] Example 17b: Neopentyl glycol modified with 2 moles of caprolactone and ethoxylated with 40 moles of ethylene oxide (backbone J)

[0799] In a 2L autoclave, 149.6g of neopentyl glycol (Example 17a) modified with 2 mol of caprolactone and 1.9g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. 792.0g of ethylene oxide was added over 14 hours. In order to complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. 1.0g of acetic acid was added. After filtering, 940.0g of light brown oil was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0800] Example 17c (grafted polymer)

[0801] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone J (97.50 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (1.68 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and, 10 minutes after the start of feed 1, feed 2 (37.50 g of vinyl acetate) and feed 3 (15.00 g of vinyl laurate) were simultaneously started and metered into the stirred vessel at variable feed rates for feed 1 (0:00 h to 00:10 h: 2.61 g / h and 00:10 h to 06:10 h: 1.23 g / h) and constant feed rates for feed 2 (00:10 h to 06:10 h: 6.25 g / h) and feed 3 (00:10 h to 06:10 h: 2.50 g / h). After feeds 1, 2, and 3 were completed, feed 4 (0.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.96 g of tripropylene glycol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1.00 hours. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 159 g of polymer solution.

[0802] Example 18 (Present Invention 18)

[0803] First, Example 8c (110.00 g) was charged to a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and heated to 80° C. Water (49.86 g) was added, and Feed 1 (50% aqueous sodium hydroxide solution, 11.50 g) was started at a constant feed rate over 1:00 h. After the addition was complete, the mixture was stirred at 80° C. for 1 h to obtain 250 g of a polymer solution.

[0804] Example 19 (Present Invention 19)

[0805] Example 19a: Polyethylene glycol (molecular weight 1500 g / mol) modified with 6 mol of caprolactone (main chain B):

[0806] In a 4-necked container equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, 750.0 g of polyethylene glycol (molecular weight 1500 g / mol) and 1.1 g of tin(II) ethylhexanoate were placed and heated to 90°C.

[0807] 342.4 g of ε-caprolactone were added within 15 minutes. The reaction mixture was heated to 155° C. and stirred at 155° C. under nitrogen for 11 hours. After cooling to room temperature, 1100.0 g of an orange oil were obtained. 1 H-NMR indicated 97.5% conversion of caprolactone

[0808] Example 19b (grafted polymer)

[0809] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone B (480.0 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (2.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.1 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (258.5 g of vinyl acetate) were simultaneously started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 9.70 g / h and 00:10 h to 06:10 h: 4.58 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 43.08 g / h). After feeds 1 and 2 were complete, feed 3 (1.88 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.6 g of propane-1,2-diol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 781 g of polymer solution.

[0810] Example 20 (Present invention 20)

[0811] Example 20a: Polyethylene glycol (molecular weight 400 g / mol) modified with 6 mol of caprolactone and 70 mol of ethylene oxide (main chain K):

[0812] In a 2L autoclave, 150g of polyethylene glycol (molecular weight 400g / mol) and 2.7g of potassium tert-butoxide were placed, and the mixture was heated to 80°C. The container was purged three times with nitrogen and the mixture was heated to 140°C. A mixture of 977.5g of ethylene oxide and 217.1g of caprolactone was added over 15 hours. To complete the reaction, the mixture was allowed to react for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80°C. After filtration, 1340.0g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0813] Example 20b (grafted polymer)

[0814] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone K (350.0 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.0 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (650.0 g of vinyl acetate) were simultaneously started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 12.4 g / h and 00:10 h to 06:10 h: 5.83 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 108.3 g / h). After feeds 1 and 2 were complete, feed 3 (2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1,2-diol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1059 g of polymer solution.

[0815] Example 21 (Present invention 21)

[0816] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with backbone K (550.0 g) under a nitrogen atmosphere and heated to 90° C. Feed 1 (3.40 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.0 g of propane-1,2-diol) and, 10 minutes after the start of feed 1, feed 2 (296.2 g of vinyl acetate) were simultaneously started and metered into the stirred vessel at a variable feed rate for feed 1 (0:00 h to 00:10 h: 11.1 g / h and 00:10 h to 06:10 h: 5.25 g / h) and a constant feed rate for feed 2 (00:10 h to 06:10 h: 49.4 g / h). After feeds 1 and 2 were complete, feed 3 (2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1,2-diol) was metered in over 0.56 hours at 90°C at a constant feed rate. After complete addition of the feeds, the mixture was stirred at 90°C for 1 hour. The polymerization mixture was heated to 95°C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 899 g of polymer solution.

[0817] Synthesis of comparative examples

[0818] Synthesis of Comparative Example 1:

[0819] The polymer was prepared as described in WO 2021 / 160795 following “Procedure for comparative example 1: graft polymerization of vinyl acetate on polyethylene glycol)-(Comp.Ex.1)” but adjusting the amount of PEG (60 instead of 40) relative to VAc (40% instead of 60).

[0820] Synthesis of Comparative Example II:

[0821] The polymer was prepared as described in US 2019 / 0390142 A1 Example 1K.

[0822] Synthesis of Comparative Example III:

[0823] The polymer was prepared as described in Example 44 of the unpublished patent application PCT / EP 2022 / 072416.

[0824] Synthesis of Comparative Example IV:

[0825] The polymer was prepared as described in Example 13 of the unpublished patent application PCT / EP 2022 / 072402.

[0826] Synthesis of Comparative Example V:

[0827] The polymer was prepared as described in Example 12 of the unpublished patent application PCT / EP 2022 / 072402.

[0828] Synthesis of Comparative Example VI:

[0829] The polymer was prepared as described in Example 18 of the unpublished patent application PCT / EP 2022 / 072416.

[0830] Synthesis of Comparative Example VII:

[0831] The polymer was prepared as described in the unpublished patent application PCT / EP 2022 / 072416, Example 19. To reduce the viscosity of the polymer, 15 wt% Lutensol XL 100 (alcohol ethoxylate, product of BASF) and 10 wt% demineralized water were added after the polymerization.

[0832] Synthesis of Comparative Example VIII: (following the disclosure of unpublished patent application PCT / EP 2022 / 065983 (now published as WO 2022 / 263354))

[0833] Comparative Example VIII based on a PEG ester backbone was synthesized via the following steps.

[0834] Step 1: Oxidation of PEG

[0835] A polyalkylene oxide having two primary OH terminal groups (referred to as a "diol") is oxidized to form a mixture containing at least a polyalkylene oxide having two COOH terminal groups (referred to as a "diacid") and a polyalkylene oxide having one primary OH and one COOH terminal group (referred to as a "monoacid"), and optionally also a polyalkylene oxide having two primary OH terminal groups. The mixture is prepared as follows.

[0836] Platinum / charcoal (5.0 wt.-% Pt / C, water content: 59.7 wt.-%, 283 g, 29.2 mmol Pt) was suspended in a mixture of polyalkylene oxide containing two primary OH end groups (see Table 1 for details) and water (see Table 2 for details), heated to 52° C. and stirred at 800 rpm. Oxygen was passed through the stirred mixture (20 nL / h) via a glass tube equipped with a glass frit and the temperature was allowed to rise to 60° C. The oxygen dosage and temperature were maintained for the time periods mentioned in Table 1, after which the oxygen dosage was stopped and the mixture was allowed to cool to room temperature. The solid was separated from the liquid phase by filtration, and the filter cake was washed with 500 mL of warm water. The washing water was mixed with the filtrate. Water was removed from the liquid mixture by distillation using a wiped film evaporator (total height: 87.2 cm, diameter: 3.54 cm, wiped film height: 43 cm, feed: 4.0 mL / min, 44° C., 1.8 kPa absolute, 600 rpm).

[0837] Polymer Backbone - Table 2 - Oxidation of PEG

[0838]

[0839]

[0840] Notes to Table 2:

[0841] #1 EO = polyethylene oxide

[0842] #2 Calculation of acid value based on reaction solution

[0843] Step 2: Esterification

[0844] A mixture of polyalkylene oxides obtained by oxidation of diols (see Table 1) (see Table 2) and an esterification catalyst (see Table 2) were mixed and heated at a temperature of 135° C. under vacuum at a pressure of 1 kPa absolute for the period mentioned in Table 3.

[0845] Table 3 - Esterification to PEG-esters

[0846] Polymer backbone descriptors B1 educts A1(76.0g)+A2(1100g) <![CDATA[Esterification catalyst #1 > <![CDATA[0.83wt.-%;TIB Kat 620 #2 ]]> Reaction time [h] 72 <![CDATA[K-value #2 > 20.2

[0847] Notes to polymer backbone - Table 3:

[0848] #1 Catalyst = Zinc Octoate

[0849] #2The K-value measures the relative viscosity of a dilute polymer solution and is a relative measure of the average molecular weight. As the average molecular weight of a particular polymer increases, the K-value also tends to increase. The K-value is determined in a 3% by weight NaCl solution at 23°C and a polymer concentration of 1% polymer according to the method of H. Fikentscher in "Cellulosechemie," 1932, 13, 58.

[0850] Step 3: Synthesis of comparative grafted polymer Comparative Example VIII

[0851] The polymer backbone B1 (350.0 g) was metered into a vessel equipped with a stainless steel anchor stirrer (and two further necks) and heated to 95° C. 1.00 g of a 14 wt % solution of tert-butyl peroxy-2-ethylhexanoate in tripropylene glycol was added over 1 min. Thereafter, the dosage of vinyl acetate (350.0 g) was started and continued at a constant feed rate over 7.5 h. Simultaneously, an initiator solution (50.0 g) of tert-butyl peroxy-2-ethylhexanoate as a 14 wt % solution in tripropylene glycol was metered in over 8.5 h at a constant feed rate. To complete the reaction, the mixture was stirred for a further 180 min. Finally, the volatile components were stripped at 120° C. for 90 min with nitrogen at a feed rate of 6 L N2 / h.

[0852] Polymer biodegradability

[0853] Use OECD 301F manometric respirometry, the polymer biodegradation in the test wastewater is tested in triplicate. 30mg / mL test substance is inoculated into the wastewater extracted from the Mannheim wastewater treatment plant, and at 25 ℃, incubated 28 days in sealed flasks. During this time, oxygen consumption is measured as the change of pressure in the flask using OxiTop C (WTW). Use NaOH solution to absorb the CO 2 that escapes. After using blank correction, the amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as % of ThOD (theoretical oxygen demand).

[0854] Table 4: Biodegradation data of comparative polymers and polymers according to the invention at day 28 of OECD 30 IF.

[0855]

[0856] Table 4 - continued

[0857]

[0858]

[0859] (Dates of inventions 1 to 21: repeated from Table 1 for better comparison)

[0860] As shown in Table 4, the graft polymers of the present invention showed at least comparable percentage biodegradation at day 28 of the OECD 30 IF test.

[0861] Stability of Inventive Graft Polymer 5 (Inventive 5) relative to Comparative Example VIII

[0862] Aqueous solutions of the inventive graft polymer 5 (Inventive 5) and comparative polymer 1 (9 wt %) were prepared, and the mixture was stored at 54° C. for two weeks.

[0863] During storage of Comparative Example VIII, a brown precipitate formed. The reported precipitate and solution 1 H NMR (298K, D2O, 400MHz) spectra showed no difference. 1 Comparison of H NMR spectra shows 1 Significant rearrangement of the H NMR shifts in the region of 4.0 to 4.35 ppm (typical for PEG-ester bonds) and 1.8 to 2.2 ppm (typical for bound / unbound acetate), as shown in Figure 1 As shown in .

[0864] Fresh and stored samples of the grafted polymer of the present invention (Invention 5) 1 Comparison of the H NMR spectra (298K, D2O, 400 MHz) showed no significant rearrangement in the spectra, as shown in FIG. Figure 2 As shown in .

[0865] These results clearly show the better hydrolytic instability of the polymers from the present invention.

[0866] Agrochemical formulations

[0867] All references to completely demineralized water refer to water that has been completely demineralized and additionally purified by ion exchange, having a pH of approximately 5.5.

[0868] preparation

[0869] A suspension concentrate was prepared by grinding 40 wt.% solid (ws) active ingredient, 5% ws dispersant, and 0.3% ws Agnique DFM 111S (silicon emulsion deaerator) with completely demineralized water in a Lau GmbH "DAS200" disperser with glass spheres (diameter: 2 or 3 mm) to obtain a particle size distribution of dispersed pesticide particles characterized by a D90 of ≤ 10 μm, a D50 of ≤ 3 μm, and a D10 of ≤ 1 μm. Particle analysis was performed according to method (I). Storage stability was assessed as described in method (II). Blooming and suspension efficiency were determined according to methods (III) and (IV). The specific components and experimental results are shown in the table below.

[0870] Method (I): Particle size analysis according to CIPAC MT 187

[0871] About 1.0mL of sample (suspension) is gently shaken into 9mL of complete demineralized water. The diluted sample is added dropwise to a Malvern Master Sizer dispersion unit (Hydro MV) until a laser shadow of 6% (+ / - 1.5%) is reached. In the dispersion unit, the sample is diluted in 120mL of complete demineralized water and pumped into the measurement cell of a Malvern Mastersizer 3000 (Malvern Panalytical GmbH, Germany) using a 632.8nm laser (4mW He-Ne) for analysis. The sample and the complete demineralized water for dilution are at room temperature. Particle size distribution is calculated using the Fraunhofer model as known in the art, including D10, D50 and D90 values. Referring to, for example, ISO 13320-1:1999 (E).

[0872] Method (II): Accelerated storage test according to CIPAC MT 46.3

[0873] Approximately 10 mL of the sample (suspension) was placed in a 40 mL penicillin glass bottle equipped with a screw cap and a polyethylene insert and kept at a specified temperature (+ / - 2°C) in a temperature-controlled cabinet for a defined period of time. In the swing test indicated below as "-10°C / +40°C", the temperature was switched between -10°C and 40°C every 12 h. After the defined period of time, the bottle was removed from the oven and allowed to reach room temperature before further analysis.

[0874] Method (III): Bloom

[0875] A 100 mL test cylinder was filled with 95 mL of CIPAC water D. 4 drops of suspension concentrate were then added and the distribution was evaluated: 1: uniform, 3: the cylinder was completely filled, but not completely uniform (<20%), 5: the SC was not distributed and remained at the top or at the bottom, 2 and 4 were in between, respectively.

[0876] Method (IV): Suspension rate according to CIPAC MT 161

[0877] Take the filled test cylinder from method III and add more suspension concentrate until the cylinder contains 5 g of suspension concentrate. Subsequently, homogenize the cylinder contents by inverting 180° ten times and allow to stand for 30 minutes. Next, remove the top nine-tenths of the contents and then dry the remaining tenth (approximately 50°C / 500 mbar), analyze gravimetrically, and calculate the suspension rate according to the following method:

[0878] Calculation 1:

[0879] 1-(wt. solid / wt. water in sample composition) = % wt.

[0880] Calculation 2:

[0881] [(Starting Sample Weight) x (Calculated Value of 1 as a decimal)] = Grams of Dispersible Solids

[0882] Calculation 3:

[0883]

[0884] Azoxystrobin

[0885] Comparative Examples:

[0886]

[0887]

[0888]

[0889]

[0890]

[0891]

[0892]

[0893]

[0894]

[0895]

[0896]

[0897]

[0898]

[0899]

[0900]

[0901]

[0902]

[0903]

[0904]

[0905]

[0906]

[0907]

[0908]

[0909]

[0910]

[0911]

[0912]

[0913]

[0914]

[0915]

Claims

1. A graft polymer, characterized in that: (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer backbone as grafting matrix, The polymer backbone comprises at least one subunit (a1) and at least one subunit (a2), wherein (a1) is a unit comprising, preferably consisting essentially of, a portion derived from at least one alkylene oxide monomer selected from the group of C2- to C10-alkylene oxides, preferably C2- to C5-alkylene oxides, and / or at least one polyalkylene oxide polymer having two hydroxyl end groups, (a2) is a unit comprising, preferably consisting of, a moiety derived from at least one lactone and / or at least one hydroxy acid, this seed unit (a2) being a moiety derived from a single lactone and / or hydroxy acid or being an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid, Wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein i) lactones, i.e. cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; as well as ii) hydroxy acids, which can be derived from any lactone by hydrolysis, in particular from any lactone within the preceding group i), in particular α-, β- or γ-hydroxy acids derived from the corresponding lactone by hydrolysis, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; Preferably lactic acid or caprolactone, more preferably caprolactone, The polymer main chain a) Obtained through the following means: (A1) copolymerization of at least one subunit (a1) and at least one subunit (a2), wherein optionally, at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and at least one subunit (a2); (A2) first oligomerizing / polymerizing subunit (a2) and then polymerizing the product with subunit (a1); (A3) first oligomerizing / polymerizing subunit (a1) and then copolymerizing the product with subunit (a2); or (A4) first providing an oligomeric or polymeric subunit (a1) carrying a capping group on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4, which - as a starter block - is thereafter reacted with at least one subunit (a2) and optionally at least one subunit (a1) - wherein the subunit (a1) may be different from the one / those in the starter block or may be arranged in a different order compared to those in the starter block - to attach a new block comprising parts from the subunits used for (co)polymerization to the uncapped side of the starter block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; Where more than one subunit (a1) and / or more than one subunit (a2) are already present in the oligomer or polymer employed, those subunits may be arranged in any order within such oligomer or polymer employed, and wherein in case more than one subunit (a1) and / or more than one subunit (a2) are present for polymerization, those subunits (and optional oligomers / polymers, if employed) may be arranged in any order within the resulting backbone; and wherein in the case of (A1), (A2) and (A3), the use of a starter molecule is optional; or b) selected from: (A1) a backbone consisting of a randomly arranged sequence of monomeric, oligomeric and / or polymeric (a1) subunits and monomeric, oligomeric and / or polymeric (a2) subunits, wherein more than one subunit (a1) and / or more than one subunit (a2) are present; (A2) a backbone consisting of oligomeric or polymeric subunits (a2) as inner blocks and two outer blocks of oligomeric and / or polymeric (a1)-subunits, which are defined as "-[block of (a1)]-[block of (a2)]-[block of (a1)]-", and may also comprise higher block polymers such as 5-blocks, 7-blocks and 9-blocks, etc., in which further blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as pentablocks "[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]", etc.; (A3) a backbone consisting of an inner block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunits (a2), at least in the form of a triblock polymer defined as "-[block of (a2)]-[block of (a1)]-[block of (a2)]-"; and (A4) A main chain consisting of: The first block has (i) a capping group on one end - such a capping group is a C1 to C18-, preferably C1-C4-alkyl group attached to the first block via an ether function; and (ii) oligomeric or polymeric subunit (a1); as well as a second block, which is attached to the first block via an ether or ester functionality at the opposite end of the first block ("opposite" with respect to the end-capping group on the first block), the second block consisting of at least one subunit (a2) and optionally at least one subunit (a1), wherein the optional subunit (a1) in the second block may be different from that / those in the first block or may be arranged in a different order compared to those in the first block, and the order of the subunits (A1) and (a2) may also be in any order, including a random structure, Such a diblock structure has the following as an idealized structure when only subunit (a2) is used for the second block: [capping group]-[subunit (a1)]-[subunit (a2)] Or in the case of using subunits (a1) and (a2) for the second block, the following is the idealized structure: [End-capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; and wherein in the case of (A1), (A2) and (A3), the use of a starter molecule is optional; as well as (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60%, most preferably 20 to 50%, of polymer side chains (B) grafted onto the polymer backbone (A), wherein said polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally nitrogen-containing monomers (B2) and optionally further monomers (B3) and optionally further monomers, All percentages are given as weight percentages relative to the total weight of the grafted polymer.

2. The graft polymer according to claim 1, wherein At least two different alkylene oxides are used to prepare the backbone / are present in the backbone.

3. The graft polymer according to claim 1, wherein These monomers are: (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate and any further vinyl esters known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and / or vinyl benzoate; Optionally (B2) at least one nitrogen-containing monomer selected from the group consisting of vinyllactams, vinylimidazoles, 1-vinyltriazole, 4-vinylpyridine, 4-vinylpyridine-N-oxide, 2-vinylpyridine, 1-vinyloxazolidinone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N′-dialkyl(meth)acrylamides; mono- and dialkylamino-alkyl(meth)acrylates, preferably vinyllactam monomers and / or vinylimidazole monomers, the vinyllactams more preferably being selected from N-vinyllactams such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam and most preferably N-vinylpyrrolidone, and the vinylimidazoles preferably being N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole; Optionally (B3) at least one additional monomer such as any one or more of 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amine if hydrolyzed after polymerization, N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl (meth)acrylates; and Optionally At least one additional monomer, different from the previous ones, this other monomer is only present in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chains (B) and is preferably only present as an impurity and not intentionally added for the polymerization.

4. The graft polymer according to any one of claims 1 to 3, wherein The amount of - if (B2) exists - (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%, based on the total weight of the graft polymer, wherein Measured in weight percent based on the total weight of the graft polymer, (B1) (vinyl ester) is 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%; Measured as a percentage by weight based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and every number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1). or -If (B2) does not exist- (B) is 5% to 60%, preferably up to 50% and preferably 20%; in (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3) expressed as a percentage by weight based on the total weight of the graft polymer. (B2) (nitrogen-containing monomer) is 0%, And further premise is that in all the previous cases (B3) (additional monomers) is from 0% to 10%, preferably up to 2%, more preferably up to 1%, even more preferably about 0%, but in any case up to 10% of the amount of (B1) and does not exceed the amount of (B2).

5. The graft polymer according to any one of claims 1 to 4, wherein At least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 80 weight percent, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as vinyl ester (weight percents based on the total weight of the vinyl ester monomers B1 employed).

6. The graft polymer according to any one of claims 1 to 5, wherein (A) The polyalkoxylate-ester backbone comprises a moiety derived from: (i) an alkylene oxide (AO) comprising at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably at least one of EO and PO, wherein the amount of the AO is 40 wt% to 99 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any values and ranges therebetween, each based on the total weight of the backbone, The amount of EO is from 0 wt.% to 100 wt.%, preferably 10 wt.%, more preferably 20 wt.%, even more preferably 30 wt.%, even more preferably 40 wt.%, such as 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt.%, based on the total AO, The total amount of PO and / or BO is each from 0 wt.% to 100 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, even more preferably up to 70 wt.%, even more preferably up to 60 wt.% and most preferably up to 50 wt.%, and any value in between, such as up to 5 wt.%, 10 wt.%, 15 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 55 wt.% %, 65 wt.%, 75 wt.%, 85 wt.% or up to 95 wt.%, and more preferably 10 wt.%, even more preferably 20 wt.%, even further more preferably 30 wt.%, such as 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO adds up to 100 wt.%, wherein the total amount of AO adds up to 100 wt.%; (ii) lactone / hydroxy acid monomers in an amount of 1 wt.% and up to 60 wt.%, preferably up to 50 wt.%, more preferably up to 40 wt.%, most preferably up to 30 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the backbone, preferably caprolactone only; The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

7. The graft polymer according to claim 6, wherein (i) alkylene oxide (AO) selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, wherein the amount of the AO is 40 wt% to 99 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any values and ranges therebetween, each based on the total weight of the backbone, The amount of EO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt% based on the total AO, The total amount of PO and BO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt%, each based on the total weight of AO, wherein the total amount of PO and BO adds up to 100 wt.% for the sum of PO and BO, and The total amount of AO is 100 wt.%; (ii) the amount of lactone / hydroxy acid monomer is 1 wt.% and up to 60 wt.%, preferably up to 40 wt.%, more preferably up to 30 wt.%, even more preferably up to 25 wt.%, even further more preferably up to 20 wt.% and most preferably up to 15 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the backbone, preferably caprolactone only; The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

8. The graft polymer according to claim 6, wherein (i) Alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, more preferably only EO The amount of EO is 20 wt% to 100 wt% based on the total AO, The total amount of PO and BO is from 0 wt.% to 80 wt.%, preferably up to 50 wt.%, more preferably up to 30 wt.%, even more preferably up to 20 wt.% and even further preferably up to 10 wt.% and most preferably zero, such as 45 wt.%, 45 wt.%, 45 wt.%, 25 wt.%, 15 wt.%, 7 wt.% and 5 wt.%, and any values therebetween, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO adds up to 100 wt.%, The total amount of AO is 100 wt.%; (ii) the amount of lactone / hydroxy acid monomer is 5 wt% and up to 50 wt%, preferably up to 40 wt%, more preferably up to 35 wt% and even more preferably up to 30 wt%, and as a lower limit preferably 7 wt%, more preferably 10 wt%, even more preferably 12 wt% and most preferably 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt% and any values therebetween as lower limits and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any values therebetween as upper limits, preferably caprolactone only; The total weight of the subunits (a1) and (a2) in the main chain (A) is 100 wt%.

9. The graft polymer according to any one of claims 1 to 8, wherein (B) These monomers are: (B1) at least one vinyl ester chosen from vinyl acetate, vinyl propionate and / or vinyl laurate, in an amount ranging from 70% to 100% by weight of the total weight of the monomers grafted onto the backbone (A), preferably only vinyl acetate, and (B2) optionally at least one nitrogen-containing monomer in an amount of 0 to 30% by weight of the total amount of monomers grafted onto the backbone (A), which is preferably an N-vinyllactam such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone and / or N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, The vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after the polymerization.

10. The graft polymer according to any one of claims 1 to 9, wherein The other monomers (B2) and (B3) are basically not used.

11. The graft polymer according to any one of claims 1 to 10, wherein Monomers (B1) and (B2) are present and no other monomers are employed.

12. The graft polymer according to any one of claims 1 to 11, wherein After the polymerization reaction, the at least one vinyl ester-monomer (B1)-derived moiety is partially or fully hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mol% and preferably 20 mol%, more preferably 20 mol% to 50 mol%, even more preferably 30 mol% to 45 mol%, such as about 40 mol% hydrolyzed, based on the total moles of (B1) employed.

13. The graft polymer according to any one of claims 1 to 12, wherein Wherein at least one of the following i), ii) and iii) is satisfied: i) the polymer backbones (A1), (A2) and (A3) may carry two hydroxyl groups as terminal groups or may be terminated with C1 to C22-alkyl, preferably C1 to C4-alkyl groups; such terminal groups are attached using standard means after the final preparation of the backbone, while in the case of (A4) such terminations are carried out on the oligomeric / polymeric subunit (a1) before polycondensation with subunit (a2); ii) the graft polymer has a polydispersity (PDI) Mw / Mn (wherein Mw = weight average molecular weight and Mn = number average molecular weight [g / mol / g / mol]) of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, and any number a as an upper or lower limit and any range therebetween, such as 1.3 to 2.6, 1 to 3, etc.; iii) the biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, even further more preferably at least 50%, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75% etc. and any values in between and up to 100% within 28 days when tested according to OECD 301F.

14. A method for obtaining a graft polymer according to any one of claims 1 to 13, comprising the following steps: At least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), and optionally further monomers (B3) and further further monomers optionally comprised as impurities in (B1), (B2) and / or (B3) are polymerized in the presence of at least one polymer backbone (A), wherein the polymer side chains (B) are obtained by free radical polymerization, preferably using free radical-forming compounds to initiate the free radical polymerization.

15. The process according to claim 14 , which comprises polymerizing at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomers (B3) in the presence of at least one polymer backbone (A), preferably selected from the group consisting of main chains (A1), (A2), (A3) and (A4), a free-radical forming initiator (C) and optionally up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one solvent (D), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that the fraction of unconverted grafting monomers (B1), optionally (B2) and optionally (B3) and initiator (C) in the reaction mixture relative to the polymer backbone (A) remains constant. % or even 100 wt.%) of vinyl acetate is used as the vinyl ester (B1) and is continuously kept in a quantitative deficiency, wherein preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent and most preferably essentially only (i.e. about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (the weight percentages are based on the total weight of the vinyl ester monomers B1 employed), and - preferably - the amounts of the monomers are those as in any of the previous claims listing such amounts.

16. The method according to any one of claims 14 or 15, wherein Essentially no other monomers (B3) are used.

17. The method according to any one of claims 14 to 16, wherein The other monomers (B2) and (B3) are basically not used.

18. The method according to any one of claims 14 to 17, wherein After the polymerization reaction, the fraction derived from at least one vinyl ester monomer (B1), preferably originating from the use of only vinyl acetate as (B1), is partially or completely hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mol % and preferably 20 mol %, more preferably 20 mol % to 50 mol %, even more preferably 30 mol % to 45 mol %, such as about 40 mol %, based on the total moles of (B1) employed, and preferably no further monomer (B3) is employed, more preferably an N-vinyl lactam, preferably N-vinylpyrrolidone, is employed as (B2).

19. The method according to any one of claims 14 to 18, wherein The method comprises at least one further method step selected from i) to iv): i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

20. The method according to any one of claims 14 to 19, wherein The method comprises at least one further method step selected from the group consisting of: i) a post-polymerization process step, which is carried out after the main polymerization, wherein a further amount of initiator (optionally dissolved in the solvent) is added, preferably within a time period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, wherein the free-radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization; and wherein after the polymerization and before the post-polymerization, there is preferably a waiting period, during which the main polymerization is allowed to proceed, before the post-polymerization is started by starting the addition of the further free-radical initiator, such period being preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerization process step is - preferably - the same as in the main polymerization or increased, such increase preferably being about 5°C to 40°C, preferably 10°C to 20°C higher than the temperature of the main polymerization; ii) a step of subjecting the graft polymer as obtained from the main polymerization or, if carried out, the post-polymerization process step, to purification, concentration and / or drying means in order to remove a part or substantially all of the remaining solvents (as long as they are removable due to their boiling point) and / or volatiles such as residual monomers, wherein a. the concentration is carried out by removing a portion of the solvent and optionally also volatiles by preferably applying a distillation process such as heat or vacuum distillation, preferably vacuum distillation, and / or applying stripping with a gas such as steam or an inert gas such as nitrogen, preferably using steam from water - whereby this step additionally serves as a means for purification - to increase the solid polymer concentration - and optionally also for purification, allowing it to proceed until the desired solid content and optionally also purity is obtained, preferably allowing it to proceed until the desired part or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed; b. the drying is carried out by subjecting the graft polymer, which contains at least residual amounts of volatiles such as remaining solvent and / or unreacted monomers, etc., to means for removing the volatiles, such as drying using rollers, a spray dryer, vacuum drying or freeze drying, preferably - primarily for cost reasons - spray drying; and optionally combining this drying method step with means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such a process preferably being selected from spray-agglomeration, granulation or drying in a fluidized bed dryer, spray-granulation apparatus, etc.

21. The method according to any one of claims 14 to 20, wherein The amount of water during the polymerization is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on the total weight of graft polymer (at the end of the polymerization) or on the total weight of (A) and (B) (at the start of the polymerization).

22. An agrochemical composition comprising at least one graft polymer according to any one of claims 1 to 13 or a graft polymer obtained or obtainable according to any one of claims 14 to 21.

23. The composition according to claim 22, wherein The agrochemical active ingredients are selected from the group consisting of pesticides, in particular herbicides, fungicides and insecticides.

24. The agricultural chemical composition according to any one of claims 22 to 23, wherein The agrochemical active ingredient is selected from azoxystrobin, flupyraclonil, fludioxonil, prothioconazole, thiophanate-methyl, diflufenacil, tetracyclanil, clofosconazole, tebuconazole, atrazine, indazine fluazifop, saflufenacil, sulfamethoxam, glufosinate-ammonium, cyproconazole, terbuthylazine and metribuzin, preferably selected from azoxystrobin, flupyraclonil, fludioxonil, prothioconazole, diflufenacil, terbuthylazine, thiophanate-methyl and atrazine, in particular azoxystrobin.

25. The agricultural chemical composition according to any one of claims 22 to 24, wherein The weight ratio of the active agrochemical ingredient to the grafted polymer in the agrochemical composition is in the range of 1:1 to 30:

1.

26. The agricultural chemical composition according to any one of claims 22 to 25, wherein The agrochemical composition is a suspension, an emulsifiable concentrate, a wettable powder, a wettable powder, or a granule, in particular a suspension such as a suspension concentrate, a suspoemulsion or a dispersible concentrate, most preferably a suspension concentrate.

27. Use of at least one graft polymer according to any one of claims 1 to 13 or a graft polymer obtained or obtainable according to any one of claims 14 to 21 in an agrochemical composition according to any one of claims 23 to 26.

28. Use of at least one graft polymer according to any one of claims 1 to 13 or obtained or obtainable by the process according to any one of claims 14 to 21 in a composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, preferably a laundry detergent formulation or a dishwashing detergent formulation, Optionally further comprising at least one enzyme, the at least one enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispases, mannanases and peroxidases, and a combination of at least two of the foregoing types, preferably at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, relative to the total weight of such composition or product, and Such products or compositions further comprise from about 1% to about 70% by weight of a surfactant system.

29. A composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, preferably a laundry detergent, a dishwashing composition, a cleaning composition and / or a fabric and home care product, each containing at least one graft polymer according to any one of claims 1 to 13 or a graft polymer obtained or obtainable by the process according to any one of claims 14 to 21, The cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation, Optionally further comprising at least one enzyme, the at least one enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispases, mannanases and peroxidases, and a combination of at least two of the foregoing types, preferably at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, relative to the total weight of such composition or product, and Such products or compositions further comprise from about 1% to about 70% by weight of a surfactant system.

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