Biodegradable Graft Polymers

Abstract

A graft polymer, its preparation and use in cleaning compositions, agrochemical compositions and the like, and compositions thereof, the graft polymer comprising a polymer backbone (A) which is a polyalkylene oxide ester polymer having a weight average molecular weight Mw of 500-50,000 g / mol, a polydispersity PD of 2-6, containing 10-560 ether groups and 2-51 ester groups bonded to each other with alkylene groups, and having significantly better biodegradability than conventional polyalkylene oxide polymers, and polymer side chains grafted onto said polymer backbone A, said polymer side chains (B) being obtainable by polymerizing i) at least one monomer (B1) selected from at least one vinyl ester monomer, and ii) optionally at least one further olefinically unsaturated monomer (B2) polymerizable with monomer B1.

Description

[Technical field]

[0001] The present invention relates to novel graft polymers comprising a polymeric backbone (A) as a graft substrate having polymeric side chains (B) grafted thereon.

[0002] The polymer backbone (A) is a polyalkylene oxide ester polymer ("PAG") comprising as building blocks: i) a polyalkylene oxide diol ("PAG"), ii) a PAG dicarbonate and / or iii) a PAG monocarbonate-monol (all hydroxyl and carboxyl groups mentioned for compounds i), ii) and iii) above are end groups of the PAG); if only i) and iii) are present, there are at least two internal ester groups within the PAG-ester polymer; such polymer backbone preferably has a weight average molecular weight Mw of 500-50000 g / mol, a polydispersity PD of 2-6, and comprises 10-560 ether groups and 2-51 ester groups bonded to each other with alkylene groups; and optionally further low molecular weight dicarbonates in addition to compound iii).

[0003] The polymer backbone (A) may also be described as a polyalkylene oxide ester polymer ("PAG") comprising the building blocks i) a polyalkylene oxide diol ("PAG"), ii) a PAG dicarbonate, and / or iii) a PAG monocarbonate-monol (all of the hydroxyl and carboxyl groups referred to in compounds i), ii) and iii) above are end groups of the PAG), whereby when only compounds i) and iii) are present, there are at least two internal ester groups within the PAG-ester polymer, and further low molecular weight dicarbonates may be included in addition to compound ii).

[0004] The polymer side chains (B) attached to the polymer backbone (A) may be obtained by polymerizing i) at least one monomer selected from vinyl ester monomers (B1) and further monomers (B2).

[0005] The graft polymers of the present invention based on such PAG-ester polymers exhibit significantly higher biodegradability than conventional graft polymers based on conventional polyalkylene oxide polymers.

[0006] The invention furthermore relates to a process for obtaining such graft polymers, which process is preferably carried out by free-radical polymerization.

[0007] The invention further relates to the use of such graft polymers in formulations of, for example, fabric and home care products and perfumes.

[0008] The present invention also relates to fabric care and home care products per se and to formulations of at least one perfume per se comprising such grafted polymers. [Background technology]

[0009] Polyalkylene oxides are important polymers with a wide range of applications, among which they are used as solvents, viscosity improvers, emulsifiers, dispersants, protective colloids, plasticizers, release agents, as well as components or raw materials in the manufacture of a wide variety of polymers, such as adhesives and graft polymers. Besides various technical applications, they are also used in a wide variety of consumer products, such as cosmetics or washing and cleaning agents.

[0010] They are also widely used as base components for the preparation of further graft polymers, exemplified below.

[0011] However, after use, a certain amount of these consumer products are washed away, and if they are not biodegradable or removed in sewage treatment plants, they may end up as microplastics in rivers and oceans. In the course of the present invention, it was recognized that polyalkylene oxides have a reduced biodegradability when their molecular weights are in the range of several hundred g / mol to several thousand g / mol at most. However, the polymers described in the present invention are preferably produced by radical graft polymerization and have improved biodegradability compared to the prior art.

[0012] Efforts have already been made in various countries to ban microplastics, especially in cosmetics. Beyond the ban of these insoluble microplastics, there is an intense exchange of ideas regarding future requirements for soluble polymers used in consumer products. It is therefore highly desirable to identify more biodegradable ingredients for this type of application. Even radically generated graft polymers with a polyethylene glycol backbone show only limited biodegradability in wastewater when the polyethylene glycol backbone has a molecular weight within the ranges mentioned above, especially when the molecular weight exceeds several thousand g / mol.

[0013] M w Low molecular weight polyethylene oxide with a molecular weight of 600 g / mol is easily biodegradable, whereas M w Polyethylene oxide with a molecular weight of 6000 g / mol shows poor biodegradability. The Safety Data Sheet for Pluriol E600 from BASF, revision 2.0, dated January 5, 2021, states that M w The DOC value (dissolved organic carbon) of polyethylene glycol with a molecular weight of 600 g / mol, measured according to OECD 301A, is found to be greater than 70%. w= 6000 g / mol, the Safety Data Sheet for BASF Pluriol® E6000 Pellet, Revision 2.0, dated 10 August 2018, states that it is only insufficiently biodegradable and that it is CO2 resistant according to OECD 301B. 2 The amount of produced is only 10-20% of the theoretical value (60d).

[0014] Classical polyalkylene oxides contain a polymer chain of oxyalkylene groups with OH groups at both ends, but the prior art also knows polyalkylene oxides with functionalized end groups that exhibit specific properties and can be used for specific applications.

[0015] Such conventional polyalkylene oxide-based graft polymers have been found to have surprisingly low biodegradability, which is often significantly lower than would be expected based on the biodegradability of the pure polyalkylene oxide.

[0016] The biodegradability of such conventional polyalkylene oxide-based graft polymers generally decreases with increasing degree of modification (i.e., increasing number of side chains on the backbone) of the polyalkylene oxide (often a polyalkylene oxide having two hydroxyl end groups is used, and thus such hydroxyl-containing polyalkylene oxides are generally referred to as "polyalkylene glycols") by radical grafting of polymerizable monomers onto such backbone, as compared to unmodified polyalkylene oxides and unmodified polyalkylene glycols. This is in part because the degradation of the polyalkylene oxide / glycol appears to start at the respective end groups and then continue along the polymer chain, thus inhibiting the biodegradation mechanism. That is, the degradation is hindered and may be stopped completely when the polymer side chains are grafted onto the backbone, thus adding branches onto the carbon atoms of the backbone. As a result, it is believed that the higher the degree of grafting (i.e., the more side chains attached to the backbone), the lower the biodegradability of such graft polymers. Unfortunately, it is also generally accepted that a higher degree of branching will result in better performance in a desired application, since the amount of side chains alone is enough to alter the chemical structure of the backbone to give the newly formed grafted polymer certain properties compared to the separate properties of the unmodified backbone and the simple mixture of (unbound / ungrafted) homopolymers that will constitute the side chains of the grafted polymer.

[0017] Thus, the challenge of combining the opposing properties of suitable graft polymers with good application performance and the biodegradability of the unmodified backbone (ie, unmodified polyalkylene oxide / glycol) remains unsolved at present.

[0018] There was therefore a need to improve the biodegradation of such polyalkylene oxide-based grafted polymers by improving the biodegradability of the grafted substrate while maintaining the overall structure of the grafted polymer, i.e., maintaining or even improving application performance.

[0019] The present invention is therefore directed to improving the biodegradability of graft substrates and to providing graft polymers based on such improved graft substrates which themselves have improved biodegradability over similar graft polymers based on "standard" polyalkylene oxide polymers, while still providing comparable or even improved performance in a variety of targeted applications.

[0020] Prior Art Regarding Polyalkylene Oxide Esters CN110498915A discloses the preparation of omega hydroxy alpha carboxy polyethylene oxide by polymerizing hydroxy compounds functionalized with ester groups, such as methyl 2,2-dimethyl-3-hydroxypropionate, with ethylene oxide to give omega hydroxy polyethylene oxide alpha ester intermediates, which are then hydrolyzed to the corresponding omega hydroxy alpha carboxy polyethylene oxide.The COOH end groups are said to serve as reaction sites with other molecules in forming modified polyethylene oxides, for example for their use in the biological or medical fields.

[0021] U.S. Patent No. 2,585,448 describes polyethylene oxide in which one or both of the OH end groups are esterified with aromatic or aliphatic carboxylic acids. The mono- and diesters are said to be useful as plasticizers.

[0022] Other documents relate to cyclic polyetheresters, usually called oxocrown ethers, which are cyclic polyalkylene oxides with at least one ester group in the ring.

[0023] JP 55-143981 A discloses the preparation of cyclic polyether esters, usually called oxocrown ethers. The oxocrown ethers described therein are cyclic esters having 2-9 ether groups and 1-2 ester groups. They are synthesized by a multi-step synthesis, starting with polyethylene oxide, which is converted to a monosodium salt of polyethylene oxide using metallic sodium, sodium bromide is eliminated while adding sodium bromoacetate, and p-toluenesulfonyl chloride (also called tosyl chloride) is added as a leaving group to the resulting carboxylate group, and the ω-hydroxy-α-tosyl ester is intramolecularly cyclized while eliminating the tosyl group in the presence of a template metal ion to obtain the corresponding oxocrown ether. Oxocrown ethers are described as being used, for example, as complexing agents for alkali metal and alkaline earth metal cations in organic synthesis, separation, analysis, biochemistry and pharmaceuticals.

[0024] Y. Nakatsuji et al., Synthesis (1981) 42-44, also describes the preparation of oxo crown ethers with 3-5 ether groups and one ester group. Polyethylene oxide is reacted with metallic sodium and bromoacetic acid to give polyethylene oxide with terminal methanecarboxylate groups, which are then esterified with methanol. The resulting ω-hydroxy-α-methyl esters are then either directly cyclized by intramolecular transesterification to the corresponding oxo crown ethers, or saponified to polyethylene oxide with terminal carboxylic acid and OH groups, which are then intramolecularly cyclized by dehydration.

[0025] L. van der Mee et al., J. Polymer Sci. Part A, Polymer Chem. 44(7) (2006) 2166-2176, disclose the preparation of 2-oxa-12-crown-4-ether by conversion of triethylene glycol with tert-butyl bromoacetate with elimination of sodium bromide and cyclization of the resulting tert-butyl ester in the presence of cobalt dichloride. Furthermore, the authors report the ring-opening polymerization of the resulting 2-oxa-12-crown-4-ether and the copolymerization of 2-oxa-12-crown-4-ether and ω-pentadecanolactone in the presence of Novozym 435 as catalyst and benzyl alcohol, [ka] Units or [ka] It is disclosed that the oxocrown ethers are linear polymers containing either a mixture of units. It is stated that oxocrown ethers are very interesting monomers for the synthesis of hydrophilic polyesters.

[0026] Besides the end-group functionalized polyalkylene oxides and oxocrown ethers, linear polyalkylene oxides having functionalized groups within the oxyalkylene chain are also known in the prior art.

[0027] US 2011 / 0,207,634 discloses the preparation of polyalkylene oxides with carboxylate end groups, where the polyalkylene oxide chain can contain exactly one ester group. Polyalkylene oxides with carboxylate end groups and one ester group in the polymer chain are prepared by reacting the corresponding polyalkylene oxide starting material with OH end groups with a base in the presence of a transition metal catalyst, eliminating hydrogen. Ether carboxylates are said to be useful for mild anionic surfactants.

[0028] WO 2001 / 012,203 relates to a new class of surgical polymers useful as sterile anti-adhesion barriers for use between animal tissues, which have a first repeat unit: [ka] (In the formula, R 1 and R 2 are independently hydrogen or C 1~8 is an alkyl group, R 3 is C 2~12 an alkylene group or an oxyalkylene group having up to 2000 repeating units; and an oxyalkylene group or a divalent unit having up to 2000 repeating units: [ka] (In the formula, R 5 is a specific alkylene group having up to 17 carbon atoms, a specific oxyalkylene group having 3 carbon atoms and 1 oxygen atom, a specific alkoxy group having 3 to 7 CH 2 A specific keto unit having a group and one keto group or 2 to 6 CH 2 and a second repeat unit which is either a -O-CO- group or a specific alkyl ester group having one -O-CO- group.

[0029] US 6,147,168, US 6,224,894, EP 0,771,832 and EP 0,771,849 contain repeat units as defined in WO 2001 / 012,203 and additional third repeat units, in particular divalent units: [ka] (In the formula, R 30 is a divalent alkylene, arylene, or arylalkylene group) or a divalent unit: [ka] (In the formula, R13 is a specific alkylene group having up to 17 carbon atoms, a specific oxyalkylene group having 3 carbon atoms and 1 oxygen atom, a specific alkoxy group having 3 to 7 CH 2 A specific keto group having one keto group or 2 to 6 CH 2 and a third repeat unit which is described as being a specific alkyl ester group having a -O-CO- group and one -O-CO- group, where P is an integer such that the number average molecular weight of the polymer is ensured to be less than 1,000,000.

[0030] The documents cited herein relating to linear polyalkylene oxides with functionalized groups in the oxyalkylene chain mention specific applications of such types of functionalized polyalkylene oxides, such as their use as mild anionic surfactants or for the manufacture of surgical instruments, but do not mention environmental issues, particularly the biodegradability of this type of polymer.Moreover, their synthesis requires at least two isolated components, such as dicarboxylic acids and diols, which must be prepared, isolated and purified in advance, which complicates the production.

[0031] Prior art regarding graft polymers onto polylakylene oxide. WO 2007 / 138053 discloses amphiphilic graft polymers based on a water-soluble polyalkylene oxide (A) as graft substrate and side chains formed by polymerizing a vinyl ester component (B), said polymers having an average of less than one graft site per 50 alkylene oxide units and an average molar mass M of 3000 to 100000. However, WO 2007 / 138053 does not describe backbone materials based on block copolymers. Furthermore, WO 2007 / 138053 does not contain any disclosure regarding the biodegradability (also called "biodegradation") of the respective graft polymers disclosed therein.

[0032] Y.Zhang et al.J.Coll.Inter.Sci 2005,285,80 Pluronic TM This paper relates to the synthesis and characterization of certain graft polymers based on the main chain of the type. Poly(vinylpyrrolidone) is grafted onto Pluronic, a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer, by free radical polymerization of vinylpyrrolidone in dioxane with simultaneous chain transfer to the Pluronic. However, Y. Zhang does not disclose that the polymer side chains of each graft polymer are based on vinyl ester monomers. Furthermore, Y. Zhang does not disclose any biodegradability of the graft polymers disclosed therein. Y. Zhang also does not include any disclosure of the use of such graft polymers in fabric care and home care products.

[0033] WO 03 / 042262 relates to a graft polymer comprising (A) a polymeric graft backbone containing no monoethylenically unsaturated units and (B) polymeric side chains formed from a copolymer of two different monoethylenically unsaturated monomers (B1) and (B2), each containing a nitrogen-containing heterocycle, the proportion of the amount of side chains (B) being 35-55% by weight of the total polymer. However, the graft polymer according to WO 03 / 042262 is not based on a vinyl ester monomer in each of the polymeric side chains grafted onto the backbone. Besides, WO 03 / 042262 does not disclose the biodegradability of the graft polymers disclosed therein.

[0034] US Patent No. 5,318,719A relates to a new class of biodegradable water-soluble graft copolymers having building properties, anti-filming properties, dispersing properties and threshold crystal inhibiting properties, comprising (a) an acid functional monomer and, optionally, (b) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a) grafted to a biodegradable substrate comprising a polyalkylene oxide and / or a polyalkoxylated material. However, US Patent No. 5,318,719A does not disclose the use of a block copolymer backbone in each graft polymer. Furthermore, each side chain of the graft polymer must contain a large amount of an acid functional monomer such as acrylic acid or methacrylic acid. This type of acid monomer is not useful in the context of the present invention.

[0035] Other graft polymers on polyethylene glycol and polyalkylene glycols are also known from WO 00-18375, which uses PEG modified by radical polymerization with vinyl acetate, but also claims the use of further monomers such as vinylpyrrolidone, vinylimidazole, vinylcaprolactam and (meth)acrylic acid. In a preferred embodiment, PEG grafted with vinyl acetate is also exemplified, which is then hydrolyzed to give "polyvinyl alcohol modified" PEG, the main application of which is as a pharmaceutical coating agent, pharmaceutical binder polymer or film former to obtain dosage forms.

[0036] From US 2019-0390142 A1 the use in detergents of this type of graft polymer is known, which is similar to that of WO 00-18375, except that it is composed of polyalkylene glycol as the backbone and vinylpyrrolidone and vinyl acetate as grafted monomers (without hydrolysis of the vinyl acetate after polymerization).

[0037] US Patent No. 6,867,262 B1 discloses a graft polymer for use in preventing the formation of gas hydrate in oil field pipelines, the graft polymer comprising at least a vinyl lactam, preferably vinyl caprolactam, grafted onto a polyalkylene glycol, a polyether or a polymer having at least one heteroatom in the backbone, and further comprising a vinyl ester as an optional grafting monomer.

[0038] WO2007051742A1 discloses a process for preparing a graft polymer of vinyl lactam and to a lesser extent vinyl acetate grafted onto polyethylene glycol, which may be biodegradable and has a variety of uses, including as a gas hydrate inhibitor in oil field applications and as a detergent additive. Biodegradation is said to have been achieved, but no figures are disclosed.

[0039] From WO 91 / 19778 it is known to use graft polymers in detergents, which are obtainable by grafting monoethylenic carboxylic acids as grafted monomers onto a main chain, for example alkylene glycols, polyalkylene glycols, polytetrahydrofurans, glycerin, polyglycerin or reaction products of the abovementioned compounds with polyvalent carboxylic acids or polyvalent isocyanates.

[0040] WO2007138054A1 discloses vinyl acetate grafted PEG polymers for use in detergents.

[0041] Detergent compositions are generally well known in the art and can be formulated in many different ways to address many different problems. One of the problems that occurs during the process of washing laundry is the common occurrence of re-soiling, resulting in the darkening of fabrics, which is sought to be avoided, for example as described in EP 3266858 A1.

[0042] Traditional polyalkylene oxide based graft polymers have also been used in automatic dishwashing applications, for example to facilitate drying of hard surfaces, for example in EP 2788467; hand dishwashing formulations have likewise incorporated such graft polymers. Summary of the Invention [Problem to be solved by the invention]

[0043] the purpose The aim of the present invention was to find a new class of compounds which can replace polyalkylene oxides, in particular polyethylene oxide, polypropylene oxide, poly-1,2-butylene oxide and polytetrahydrofuran, in order to prepare graft polymers for use in typical applications such as home care and laundry applications, cleaning applications in general, agrochemical formulations and other typical applications in which the use of graft polymers grafted onto conventional polyalkylene oxide polymers has been tested or assumed to be used, and which have the same or at least very similar application properties as conventional polyalkylene oxide-based products, but which are more biodegradable.

[0044] Concurrently filed European Patent Application No. 21180239.2 describes the preparation of polyalkylene oxide ester polymers by selective oxidation of polyalkylene oxides followed by esterification, which serve as graft substrates for the graft polymers of the present invention.

[0045] It was also an object of the present invention to produce graft polymers based on such novel polyalkylene oxide ester polymers, preferably having improved biodegradability compared to graft polymers based on known polyalkylene oxide type polymers.

[0046] It was an object of the present invention to provide new graft polymers based on such new polyalkylene oxide ester polymers by grafting polymeric side chains, such as polymers obtained by polymerizing vinyl ester monomers and optionally other vinyl monomers, onto the polyalkylene oxide ester polymers.

[0047] It was also an object of the present invention to demonstrate that the novel compounds are useful in various applications, in particular in the field of detergent applications.

[0048] Furthermore, in addition to possessing beneficial properties with regard to biodegradability, these novel grafted polymers should preferably also exhibit beneficial properties with regard to their cleaning behavior, their dispersing properties and / or stabilizing properties when used in compositions such as cleaning compositions, fabric care and home care compositions, perfume formulations, pigment dispersions and the like.

[0049] A typical desired property is that the grafted polymer exhibits dark stain inhibition properties so that when applied in liquid and bar laundry formulations, dark staining of washed fabrics is reduced.

[0050] As mentioned elsewhere in this disclosure, the preparation of the building block "dicarbonate of PAG" used herein is known.

[0051] However, the preparation of mono-ol mono-carbonate PAGs, i.e., polyalkylene oxide polymers having a hydroxyl group at one end and a carbonate group at the other end, is not known. Such a process and such compounds are the subject of another co-filed application, European Patent Application No. 21180239.2, already mentioned, and since this application utilizes this novel compound, such structures and preparation processes are incorporated herein by reference in their entirety.

[0052] The PAG-ester polymer backbone used herein as the graft substrate itself is not yet known to those skilled in the art, but the process for producing this type of product and the product itself are the subject of the previously mentioned co-filed patent application European Patent Application No. 21180239.2, and as this application utilizes this novel compound, such structure and manufacturing process is incorporated herein by reference in its entirety.

[0053] As used herein, the articles "a" and "an," when used in a claim or an embodiment, are understood to mean one or more of the claimed or described subject matter. As used herein, the terms "include" and "including" are meant to be open-ended and thus encompass more than the specific items set forth after these words.

[0054] The compositions of the present disclosure can "comprise" the components of the present disclosure (i.e., contain other ingredients), "consist essentially of" (contains primarily or almost only the recited ingredients, with only minor amounts of other ingredients, primarily limited to impurities), or "consist of" (i.e., contains only the recited ingredients, and in addition may contain only impurities that are unavoidable in the technical circumstances, and preferably contains only the recited ingredients).

[0055] Similarly, the terms "substantially free of..." or "substantially free from..." or "containing / comprising essentially no..." may be used herein; this means that the specified substance is, at a minimum, not intentionally added thereto to form part of the composition, or preferably is not present at analytically detectable levels. This is meant to encompass compositions in which the specified substance is present only as an impurity in one of the other intentionally included substances. The specified material, if present at all, may be present at a level of less than 1% by weight of the composition, and may be less than 0.1%, less than 0.01%, or even 0%.

[0056] The term "about" as used herein, for example when written as "about X%", encompasses the exact numerical value "X" as well as small deviations of X, including deviations of minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, and even more preferably minus 0.5 to plus 0.5% from X (in this calculation, X is set to 100%) and smaller deviations. Needless to say, when the given numerical value X itself is already "100%" (e.g., purity), the term "about" can clearly mean deviations smaller than "100", and therefore only deviations smaller than "100".

[0057] Unless otherwise specified, all component or composition levels refer to the active portion of that component or composition and are exclusive of impurities, such as residual solvents or by-products that may be present in commercial sources of such component or composition.

[0058] All temperatures herein are in degrees Celsius (°C) unless otherwise specified. All measurements herein are made at atmospheric pressure at 20°C unless otherwise specified. In all embodiments of this disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless otherwise specified. [Means for solving the problem]

[0059] solution The object of the present invention is to provide a graft polymer comprising (A) a polymer backbone as a graft substrate and (B) polymer side chains grafted to the polymer backbone, The polymer main chain (A) is i) polyalkylene oxide (PAG) diols, ii) dicarboxylic acid of PAG and / or iii) PAG monocarbonate monool and optional other non-polymeric dicarboxylic acid compounds which may be present in addition to compound ii). can be obtained by condensation comprising Either at least a compound selected from iii) is present, or, if only i) and ii) are present, at least two internal ester groups are present; The PAG is obtained by polymerizing at least one monomer selected from 1,2-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; by polymerizing at least one monomer selected from 1,4-diols or their cyclic or oligomeric analogues, or the PAG is based on polymeric ethers of such 1,4-diols; by polymerizing at least one monomer selected from 1,6-diols or their cyclic or oligomeric analogues. or the PAG is based on polymeric ethers of 1,6-diols of this type; or any mixture of these, polymerized in any ratio, either as blocks of specific polymer units, or as statistical polymer structures, or as polymers containing one or more homoblocks of a specific monomer and one or more statistical blocks containing more than one monomer, as well as any combination of these, such as polymers having several different blocks of different monomers, or polymers having blocks of two different monomers, polymers having blocks of a statistical mixture of two or more monomers, etc. Said polymeric side chain (B) is obtainable by polymerizing i) at least one monomer selected from vinyl ester monomers (B1) and ii) optionally further monomers (B2), This is achieved by means of a graft polymer.

[0060] In an alternative embodiment, the PAG-ester based graft polymer is a graft polymer comprising (A) a polymer backbone as a graft substrate and (B) polymer side chains grafted to the polymer backbone, The polymer main chain (A) has a weight average molecular weight M w has a molecular weight of 500 to 50,000 g / mol, a polydispersity PD of 2 to 6, and contains 10 to 560 ether groups and 2 to 51 ester groups bonded to an alkylene group, and has 1 to 51 general formula (I): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 represents an alkyl group, a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in a direct chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 alkyl group, is a polyalkylene oxide ester polymer, Said polymeric side chain (B) is obtainable by polymerizing i) at least one monomer selected from vinyl ester monomers (B1) and ii) optionally further monomers (B2), It is a graft polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0061] The grafted polymers according to the invention can be used, for example, in cleaning compositions and / or fabric and home care products and / or agrochemical formulations. Their use in such compositions or products, for example, in terms of anti-resoiling and cleaning performance with respect to the removal of resoiling and stains, avoidance or reduction of resoiling or dark stains or solids, dispersion of active substances in agrochemical compositions, suppression of crystal growth, etc., is at least comparable and preferably even improved compared to the corresponding polymers or grafted polymers according to the prior art. They can also be advantageously used to suppress gas hydrate formation, improve the stability of pigment dispersions, hydrophobize surfaces, reduce microbial growth and / or suppress odors on such surfaces, although this depends to some extent on the monomer B used for grafting, and therefore the performances are adjusted according to the specific requirements of a particular application; the substitution pattern of such monomers can also be derived from similar grafted polymers based on simple PEG and polyalkylene glycols of the prior art.

[0062] The grafted polymers according to the invention not only exhibit performance characteristics for certain types of applications, but also exhibit improved biodegradability when used in such compositions or products as compared to known grafted polymers.

[0063] The grafted polymers with improved biodegradability according to the invention can be advantageously used in washing and cleaning compositions, where they aid the surfactants in removing hydrophobic soils from textiles or hard surfaces, thus improving the washing and cleaning performance of the formulations.Furthermore, they allow the removed soils to be better dispersed in the washing or cleaning liquid, preventing recontamination of the surface of the material to be washed or cleaned.

[0064] In other embodiments, they can be used in agrochemical formulations comprising agrochemical active ingredients; in such agrochemical formulations the graft polymers serve, for example, to disperse, avoid sedimentation, emulsify and / or stabilize such formulations by acting on the agrochemical active substances, for example by avoiding or reducing crystal growth of (semi-)crystalline active substances and / or the formulation ingredients themselves, or by acting on the formulation itself.

[0065] The terms "polymer (backbone)", "graft substrate" and "PAG-ester" and "PAG-ester polymer" are used interchangeably herein and all refer to the polyalkylene oxide esters disclosed in parallel filed European Patent Application No. 21180239.2 and detailed herein, which serve as graft substrates for the graft polymers of the present invention.

[0066] Properties of PAG-esters The polyalkylene oxide ester (PAG-ester) used as the polymer backbone of the present invention has a weight average molecular weight M w , its polydispersity PD, its number of ether groups, its number of ester groups and the presence of at least one structural element (I).

[0067] The weight average molecular weight M of the polyalkylene oxide ester polymer used as the polymer backbone of the present invention w is 500 to 50,000 g / mol. w includes the mass of each individual chain that contributes to the overall molecular weight of the polymer, taking into account that larger molecules have a higher mass than smaller molecules. It is determined by liquid-solid size-exclusion chromatography (SEC) and detecting the differential refractive index against a reference cell, and the units are calibrated using polymers of known molecular weight. Calculations are then used to determine the M based on the change in the chromatogram curve. w This type of method is well known in the art. wis preferably ≧750 g / mol, more preferably ≧1000 g / mol, particularly preferably ≧2000 g / mol, very particularly preferably ≧3000 g / mol, most preferably ≧4000 g / mol, preferably ≦45000 g / mol, more preferably ≦40000 g / mol, particularly preferably ≦35000 g / mol, very particularly preferably ≦25000 g / mol, most preferably ≦15000 g / mol.

[0068] Weight average molecular weight M w Since M is only an average value of molecular weight and does not provide information on the distribution of the molecular weights of individual molecules, the polyalkylene oxide ester polymers used as the polymer backbone of the present invention are further defined by the polydispersity PD. w / M n is defined as M n is the usual arithmetic mean, i.e., number average molecular weight, which represents the average of the molecular weights of the individual molecules. The polydispersity PD of the polyalkylene oxide ester polymer of the present invention is 2 to 6, preferably ≧2.5, more preferably ≧3, and preferably ≦5.

[0069] Number average molecular weight M n is preferably 250 to 20000 g / mol, more preferably ≧500 g / mol, and particularly preferably ≧1000 g / mol, more preferably ≦15000 g / mol, and particularly preferably ≦10000 g / mol.

[0070] Biodegradability is the ability of organic substances to be broken down into simpler substances by the action of enzymes derived from microorganisms. During this decomposition process oxygen is consumed and carbon dioxide is evolved, both of which can be measured by defined tests. Tests that are accepted worldwide are published as OECD 301 Chemicals Testing Guidelines. Depending on the specific test method, dissolved organic carbon (DOC), carbon dioxide evolution or oxygen consumption are measured over time during decomposition under standardized conditions.

[0071] Based on OECD measurements, the polyalkylene oxide ester polymers used in the present invention as the inventive polymer backbone A can usually be biodegraded to 70-90% within one month, even if they have a weight average molecular weight Mw of 20,000 g / mol, whereas conventional polyalkylene oxide polymers only reach values ​​below 20% or even below 10%.

[0072] Detailed structure of PAG-ester The polymer backbone (A) of the graft polymer of the present invention is a polyalkylene oxide ester polymer ("PAG") comprising as building blocks: i) a polyalkylene oxide diol ("PAG"), ii) a PAG dicarbonate and / or iii) a PAG monocarbonate-monol (all hydroxyl and carboxyl groups mentioned for compounds i), ii) and iii) above are end groups of the PAG), and when only i) and iii) are present, there are at least two internal ester groups within the PAG-ester polymer, such polymer backbone preferably having a weight average molecular weight Mw of 500-50000 g / mol, a polydispersity PD of 2-6, and comprising 10-560 ether groups and 2-51 ester groups bonded to each other with alkylene groups, and optionally further low molecular weight dicarbonates in addition to compound iii).

[0073] The polymer backbone (A) may also be described as a polyalkylene oxide ester polymer ("PAG") comprising the building blocks i) a polyalkylene oxide diol ("PAG"), ii) a PAG dicarbonate, and / or iii) a PAG monocarbonate-monol (all of the hydroxyl and carboxyl groups referred to in compounds i), ii) and iii) above are end groups of the PAG), whereby when only compounds i) and iii) are present, there are at least two internal ester groups within the PAG-ester polymer, and further low molecular weight dicarbonates may be included in addition to compound ii).

[0074] PAG-esters comprise at least one, preferably at least two, and more preferably a minimum of three different polymer subunits linked by covalent ester bonds, the structure being formed according to one of the three options below: In one embodiment, the two compounds that form an ester bond are: i) Mono-ol mono-carbonate of polyalkylene oxide (PAG) ii) each with itself; Condensation, In another embodiment, the two compounds that form the ester bond are: i) a polyalkylene oxide (PAG) diol; ii) PAG containing two carbonates as end groups, i.e., carbonate groups at both ends of the PEG (or PAG, respectively); is condensed, In a third embodiment, a mixture of both the above embodiments is used, i.e. i) a mono-ol monocarbonate of polyalkylene oxide (PAG); ii) polyalkylene oxide (PAG) diols and iii) PAGs containing two carbonates as end groups, i.e., carbonate groups at both ends of the PEG (or PAG, respectively); is condensed.

[0075] This third embodiment can be exemplified by the use of a mixture containing all three required compounds, i.e. polyalkylene oxide (PAG) monol monocarbonate, polyalkylene oxide (PAG) diol and PAG-dicarbonate. Such a mixture can be prepared in one step, for example by partial oxidation of the PAG-diol, by incomplete oxidation, i.e. by stopping the oxidation after a few hours, directly obtaining a mixture containing these three components.

[0076] On the other hand, it is of course also possible to obtain the PAG-ester from a mixture having a specific composition by adding the required starting materials.

[0077] Preferably, the preferred choice for obtaining the PAG-esters used as backbones for obtaining the grafted polymers of the present invention is the synthetic route of the third embodiment.

[0078] Moreover, it is of course possible and encompassed by the present invention to use more than one specific PAG-polymer in the reactions of the three embodiments described above. Thus, in all three embodiments defined above, it is possible to use, for example, PEG and other PAGs as the "PAG" portion, for example, to combine a diol of PEG with a diacid of a PAG other than PEG, or a mono-ol-mono acid of PEG with a mono-ol-mono acid of a PAG other than PEG, or a mixture of a mono-ol-mono acid of PEG with a mono-ol-mono acid of a PAG other than PEG and a diacid of a PAG other than PEG and / or a diacid of PEG, etc. It is of course meant that all possible combinations are possible and encompassed by the concept of the present invention, and thus the hydrophilicity / hydrophobicity of the resulting polymer backbone can be tailored, thus providing further variability for tailoring the properties of the desired grafted polymer using such PAG-ester polymer backbones.

[0079] As used herein, "PAG" is any form of polyalkylene oxide polymer as defined herein; however, only when "PAG" is used in direct contrast to "PEG" (i.e., PAG prepared exclusively from ethylene oxide, commonly known as "PEG," which refers to a pure ethylene oxide homopolymer), is "PAG" intended to mean other PAGs other than PEG.

[0080] Such non-PEG PAGs can be derived from propylene oxide, butylene oxide or higher alkylene oxides up to C10, or from mixtures of two or more C2-C10 alkylene oxides, such as a mixture of ethylene oxide and propylene oxide.

[0081] The PAG can be composed of alkylene oxide in the form of only one monomer, or of alkylene oxide in the form of two, three, four or more monomers; thus it can be, for example, a block copolymer of two or more alkylene oxides, e.g., a polymer that is either a block or random polymer of ethylene oxide and propylene oxide, or a polymer that contains a mixture of block units (each block being either a homoblock or itself a random block) and statistical / random portions.

[0082] A "diblock" PAG has two different blocks (polymer subunits), a "triblock" PAG has three different blocks (polymer subunits), and so on. The number of individual blocks in this type of block copolymer is not limited, thus an "n-block copolymer" contains n different blocks (polymer subunits). The size / length of such blocks within each block (polymer subunit) can vary. The minimum length / size of a block is based on two individual monomers (as the smallest unit).

[0083] In the case of the PAGs used in the oxidation to produce PAG-esters, the polymers used as grafting substrates are composed of more than one different monomer (single type of monomer unit), in which case the polymer chains of the PAG can be in the form of blocks in which a block of a first single type of monomer unit is bonded to a block of a second single type of monomer unit different from the first; such polymer chains can contain more than two blocks, for example, three, four, five or more blocks, and all such blocks and block structures can be obtained by standard means. Instead of blocks of a single type of monomer unit, each block may be composed of more than one type of monomer unit, the monomers being statistically distributed within such a particular block; it goes without saying that combinations of blocks composed of a single type of monomer unit with blocks composed of more than one single type of monomer unit are also possible by standard means; all such combinations conceivable from the possibilities mentioned above are in principle possible and can be obtained by standard means; the preferred structures, because they are easily obtainable, are PAGs composed of a single type of monomer unit or PAGs prepared from a statistical mixture of more than one type of monomer unit or PAGs prepared from two or three or more blocks (preferably up to three blocks, more preferably up to two blocks), preferably each of two or more blocks composed of only one single type of monomer unit per block.

[0084] For example, even if one intends to produce a PAG consisting of a diblock structure with two different single monomer units, each block being a homopolymer block of a different single monomer unit, such blocks may still contain "dirty structure": the boundary between the two blocks may be blurred due to the presence of unreacted monomers used in the polymerization of the first block, and the beginning of the second block may contain "dirty" structure, i.e., some of the monomer units used in the first block that did not react during the polymerization of the first block may only react when the second monomer unit is added to the reaction zone to be polymerized. Such a dirty structure can be obtained if the reaction of the first monomer unit that will become the shell of the first block is not stopped, the unreacted first monomer units are not removed from the reaction vessel, and the reaction is continued by adding the second monomer unit after the polymerization of the first block is "completed" (only nearly completed), without interruption or cleaning in between. For commercial reasons, it is preferred to continue the polymerization without interruption / cleaning, and therefore the preferred structure will include such impurity structures, while in other embodiments it is preferred to not include impurity structures.

[0085] Overall, the PAG used for oxidation is HO-CH 2 It is important that only those which have a - end group or can be oxidized to a carboxylic acid group.

[0086] A preferred embodiment of the present invention is a graft polymer comprising (A) a PAG-ester polymer backbone as a graft substrate and (B) polymer side chains grafted to the PAG-ester polymer backbone, The PAG-ester polymer backbone (A) is i) a polyalkylene oxide diol (PAG-diol or PAG-DO), ii) can be obtained by condensation with a PAG containing dicarbonic acid as an end group (PAG-DC); The PAG can be obtained by polymerizing at least one monomer selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, 2,3-pentene oxide or C5-C10-alkylene oxides, preferably C2-C4, more preferably C2 and C3, most preferably only C2 alkylene oxides; Said polymeric side chain (B) may be obtained by polymerizing at least one monomer selected from i) vinyl ester monomers (B1) and ii) further monomers (B2); Concerning graft polymers.

[0087] Another preferred embodiment of the present invention is a graft polymer comprising (A) a PAG-ester polymer backbone as a graft substrate and (B) polymer side chains grafted to the PAG-ester polymer backbone, The PAG-ester polymer backbone (A) is i) Polyalkylene oxide mono-monocarbonate (PAG-MC), ii) polyalkylene oxide diol (PAG-DO) and iii) a PAG containing dicarbonic acid as a terminal group (PAG-DC); each PAG can be obtained by polymerizing at least one monomer selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, 2,3-pentene oxide or C5-C10-alkylene oxides, preferably C2-C4, more preferably C2 and C3, most preferably exclusively C2 alkylene oxides; Said polymeric side chain (B) may be obtained by polymerizing at least one monomer selected from i) vinyl ester monomers (B1) and ii) further monomers (B2); Concerning graft polymers.

[0088] Another preferred embodiment of the present invention is a graft polymer comprising (A) a PAG-ester polymer backbone as a graft substrate and (B) polymer side chains grafted to the PAG-ester polymer backbone, The PAG-ester polymer backbone (A) is i) Polyalkylene oxide mono-ol monocarbonate (PAG-MC); can be obtained by condensing The PAG can be obtained by polymerizing at least one monomer selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, 2,3-pentene oxide or C5-C10-alkylene oxides, preferably C2-C4, more preferably C2 and C3, most preferably only C2 alkylene oxides; Said polymeric side chain (B) may be obtained by polymerizing at least one monomer selected from i) a vinyl ester monomer (B1), preferably vinyl acetate, and ii) a further monomer (B2); Concerning graft polymers.

[0089] In the three preferred embodiments mentioned above, it is also possible to obtain the structure of the polymer backbone by selecting among the following starting materials: PAG(1)-diol, PAG(2)-dicarbonate, PAG(3)-monol-monocarbonate, and these are therefore encompassed by the present invention, where PAG(1), PAG(2) and PAG(3) are different polyalkylene oxides; for example, PAG(1) can be pure PEG, PAG(2) can be an EO-PO-polymer, and PAG(3) can be an EO-butylene oxide-polymer. Of course, each PAG can be individually selected to be composed of any amount and any ratio (if more than one alkylene oxide is selected to obtain the PAG) of C2-C12-alkylene oxide.

[0090] With respect to the three preferred embodiments defined above, in general and specifically, the ratio of polymer backbone (A) to polymer side chains (B) in the graft polymer according to the invention is not limited to a specific value. Any ratio known to the skilled person can be used. However, it is understood that the graft polymer comprises more than 0.2% by weight (relative to the total weight of the graft polymer) of polymer side chains (B). Preferably, the graft polymer comprises more than 1% by weight of polymer side chains (B) (relative to the total weight of the graft polymer). More preferably, the graft polymer comprises 20-95% by weight of block copolymer backbone (A) and 5-80% by weight of polymer side chains (B) (relative to the total weight of the graft polymer).

[0091] With regard to the three preferred embodiments defined above, preferably and specifically the graft polymer comprises 40-85 wt. %, more preferably 50-80 wt. %, even more preferably 55-75 wt. % of a PAG-polymer backbone, preferably a PEG-polymer (A), and preferably 15-60 wt. %, more preferably 20-50 wt. %, even more preferably 20-50 wt. %, even more preferably 25-45 wt. % of a polymer side chain (B) (based on the total weight of the graft polymer).

[0092] In a preferred embodiment, the PAG used is essentially ethylene oxide based, such as PEG. In a more preferred embodiment, the PAG used in the preparation of the PAG-ester polymer (via the three compounds PAG monol-monocarbonate, PAG-dicarbonate and PAG-diol) is greater than 70 weight percent, more preferably greater than 90 weight percent, based on ethylene oxide, and most preferably is homopolyethylene oxide, i.e., "PEG", such that the PAG-ester polymer used in the preparation of the graft polymer of the present invention is purely PEG based with no other alkylene oxides in the PAG.

[0093] The graft polymer according to the present invention can have any molecular weight known to those skilled in the art. However, the preferred graft polymer has a weight average molecular weight M w is preferably 1000 to 500000 g / mol, preferably 2000 to 200000 g / mol, more preferably 5000 to 100000 g / mol, and even more preferably 7500 to 50000 g / mol. Needless to say, it is possible to combine various lower limit values ​​with various upper limit values, for example, 1000 to 50000 g / mol, 5000 to 50000 g / mol, 2000 to 50000 g / mol, and all such combinations are encompassed by the present invention.

[0094] The graft polymer according to the present invention preferably has a low polydispersity, which is less than or equal to 6. Preferably, the polydispersity M of the graft polymer is w / M n is <4, preferably <3.5, more preferably <3, and most preferably in the range of 1.2 to 2.5 (M w = weight average molecular weight, M n = number average molecular weight; polydispersity is unitless. g / mol / g / mol ]). M w and / or M n The respective values ​​of can be determined as described below in the experimental section.

[0095] The polymer backbone (A) contained in the graft polymer according to the present invention may be end-capped or not end-capped (uncapped) at each end group of the backbone. Thus, in the present invention, it is possible to optionally end-cap one or both end groups of the polymer backbone (A), and preferably the polymer backbone (A) is end-capped at both end groups or, if the polymer backbone (A) is end-capped, the end-caps are preferably C 1 ~C 25-alkyl groups, which are attached to the backbone as ether groups or in ester groups, depending on the actual end groups pf of the PAG employed. Such endcapping can be carried out by known means and is usually carried out before carrying out the graft polymerization.

[0096] PAG-polymers can contain varying amounts of hydrophilic ethylene glycol units which affect the overall properties of the grafted polymer, especially its water solubility.

[0097] It is generally accepted that a higher EO content results in a more hydrophilic and therefore more water soluble polymer.

[0098] In addition, a higher EO content also leads to higher biodegradability.

[0099] Therefore, in the present invention, when high hydrophilicity is desired, it is preferable to have a medium to high EO content, and it is more preferable to have a high EO content.

[0100] In another embodiment, the structure of the PAG-ester for use as a graft substrate for the graft polymer of the present invention is The weight average molecular weight Mw is 500 to 50,000 g / mol, the polydispersity PD is 2 to 6, and the alkylene group is bonded to each other and the ether group is bonded to each other, and the alkylene group is bonded to each other. [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C1~12 represents an alkyl group, a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 alkyl group, It is a polyalkylene oxide ester polymer.

[0101] The critical feature of the polyalkylene oxide ester polymers used in the present invention, which allows for surprisingly high biodegradability, is the presence of ester groups in the polyalkylene oxide polymer chain. The polyalkylene oxide units, which are themselves at least appreciably biodegradable, are linked together with ester groups. Since the polyalkylene oxide units themselves contain alternating ether and alkylene groups, the polyalkylene oxide ester polymers can also be described as polymers containing ether and ester groups linked together with alkylene groups. For the sake of completeness, it is noted that the term "polyalkylene oxide" does not include acetal or ketal units in which one carbon atom is linked to two ether groups, such as -O-CH2-O-. This is consistent with the common usage of the term polyalkylene oxide and is known to those skilled in the art.

[0102] The term "ether group" in the context of this document defines an -O- unit, both of which are bonded to carbon atoms which, independently of one another, have the oxidation number -2, -1 or 0 and which are further bonded to a hydrogen atom or to another carbon atom, e.g. -2 for a methyl group, -1 for an unsubstituted alkylene group and 0 for an alpha-alkyl substituted alkylene group. Similarly, the term "ester group" defines a -CO- unit bonded on one side to a carbon atom having an oxidation number of -3, -2, -1 or 0, e.g., -3 for a methyl group, -2 for an unsubstituted alkylene group which is further bonded to another carbon atom in the polymer chain, -1 for an alpha alkyl substituted alkylene group which is further bonded to another carbon atom in the polymer chain or which is further bonded to an -O- group, and 0 for an alpha alkyl substituted alkylene group which is bonded to an -O- group, and bonded on the other side to an -O- unit, the other side of which is in turn bonded to a carbon atom having an oxidation number of -2, -1 or 0.

[0103] Specifically, the polyalkylene oxide ester polymer used in the present invention contains 10 to 560 ether groups and 2 to 51 ester groups bonded to each other with an alkylene group, which is represented by 1 to 51 general formula (I): [ka] (In the formula, The -O- unit on the left is linked to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 represents an alkyl group, a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 The structural elements of the compound include any of the alkyl groups.

[0104] The number of ether groups specified above as 10 to 560 and the number of ester groups specified above as 2 to 51 refer to individual polyalkylene oxide ester polymer molecules. w The number of ether and ester groups in a particular polyalkylene oxide ester polymer molecule, which is composed of a polyalkylene oxide ester polymer having a molecular weight of 500 to 50,000 g / mol and a polydispersity index PD of 2 to 6, shows an individual distribution depending on the polydispersity index PD. Thus, a polyalkylene oxide ester polymer usually contains polyalkylene oxide ester polymer molecules having different numbers of ester and ether groups.

[0105] The weight average molecular weight M can be determined analytically using the knowledge of a person skilled in the art. w Based on the polydispersity PD of the polyalkylene oxide ester polymer and the ratio of ether groups to ester groups, the average number of ether groups and ester groups of the polyalkylene oxide ester polymer can be determined.

[0106] Adjacent units of the polymer which are attached to the -O- unit on the left side of formula (I) and to the -CO- unit on the right side contain further alkylene groups, ether groups and ester groups or form a number of ester groups together with the mentioned -O- and -CO- units, respectively, such that a polyalkylene oxide ester polymer is formed containing a total number of ether and ester groups within the specified ranges.

[0107] The end group of the polyalkylene oxide ester polymer can be essentially any end group suitable for forming the end of such a polymer. Examples of suitable end groups are -OH, -COOH, primary, secondary or tertiary amine groups, branched or linear alkyl groups, aralkyl groups, aromatic groups, hydroxyalkyl groups, carbonyl groups, carboxyl groups, carboxylic acid ester groups, amide groups, urethane groups, carbamide groups, xanthic acid groups, dithiocarbamate groups or carbamate groups. However, -OH, -COOH, carboxyl groups, hydroxyalkyl groups and alkyl groups are usually preferred, especially -OH and -COOH.

[0108] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 2 , R 3 , R 4 and R 5 represents a hydrogen atom, R 1 is a hydrogen atom or C 1~12 More preferably, R 1 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0109] The subscripts a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5. Preferably, a, b, and c are 1, and d and e are 0. More preferably, a is 1, and b, c, d, and e are 0.

[0110] Particularly preferred structural elements according to formula (I) have the general formula (Ia): [ka] (In the formula, R 1 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, b and c represent integers of 0 or 1, and the sum of b to c is 0 or 2.

[0111] Further particularly preferred structural elements according to formula (Ia) are of the general formula (Ib): [ka] (In the formula, R 1 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0112] The unit X in (I) represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units each independently contain, in a chain directly bonded between two -O- units, a C 2~6 The carbon atoms in the chain, which may also be represented as alkylene units, containing 2 to 6 carbon atoms and directly bonded between two -O- units, are each independently two hydrogen atoms or one hydrogen atom and one C 1~12 Preferred units X include any of the alkyl groups represented by the general formula (Ic): [ka] (In the formula, α is a subscript from 1 to Xn that defines the running count of each repeat unit, R 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα are each independently a hydrogen atom or C, taking into consideration that α is the sequence number of each repeating unit. 1~12 represents an alkyl group, a xα , b xα , c xα , d xα , e xα , f xα each independently represents an integer of 0 or 1, taking into consideration that α is the sequence number of each repeating unit; xα ~f xα The sum of is 2 to 6, Xn represents an integer between 4 and 100.

[0113] For example, R 1 xα and groups such as, for example, a xαThe lower case x in the subscripts of the formulas R indicates that they are related to the unit X. The capital X in the formula Xn, which is the number of repeating units, also indicates the same. 1 xα and groups such as, for example, a xα The lower case α in the subscripts such as ##STR1## indicates that the groups and subscripts each have their own sub-number and indicates that within a polyalkylene oxide unit X, the groups and subscripts can vary from one alkylene oxide unit to another. For example, R 1 x1 The R group can be a hydrogen atom, while the R 1 x2 can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript c of the alkylene oxide unit with sequence number 1 x1 can be 0, while the c of the alkylene oxide unit with sequence number 2 x2 can be 1, and so on.

[0114] R in formula (Ic) 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα C in the group 1~12 The alkyl group may be linear, 3~12 In the case of alkyl, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 2 xα , R 3 xα , R 4 xα , R 5xα and R 6 xα represents a hydrogen atom, R 1 xα is a hydrogen atom or C 1~12 More preferably, R 1 xα stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0115] Subscript a xα , b xα , c xα , d xα , e xα , f xα each independently represents an integer of 0 or 1; xα ~f xα The sum of a is 2 to 6. Preferably, a xα , b xα , c xα , f xα is 1, and d xα , e xα is 0. More preferably, a xα , f xα is 1, and b xα , c xα , d xα , e xα is 0.

[0116] Particularly preferred units X have the general formula (Id): [ka] (In the formula, R 1 xα is a hydrogen atom or C 1~12an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, b xα , c xα represents an integer of 0 or 1, and the sum of b to c is 0 or 2; Xn is an integer between 4 and 100.

[0117] Further particularly preferred units X based on formula (Id) have the general formula (Ie): [ka] (In the formula, R 1 xα is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Xn is an integer between 4 and 100.

[0118] The number of repeating units Xn in formula (Ic) is an integer from 4 to 100. It is preferably ≧5, more preferably ≧8, particularly preferably ≧10, and is also preferably ≦75, more preferably ≦50.

[0119] The alkylene oxide units in the unit X are each independently selected from different groups R 1 xα ~R 6 xα In that sense, and with different subscripts axα ~f xα It is emphasized that the repeating units may be identical to the units X or may be different from each other in this respect. In this regard, in formula (Ic), the subscript xα is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 1 xα Specify the child number of each subscript as, for example, a xα As already mentioned, the following specification is used:

[0120] It is further emphasized that each structural element (I) in the polyalkylene oxide ester polymer, when more than one element (I) is present, may be the same as or different from the other(s).

[0121] The different moieties of the structural element (I), such as the radicals, subscripts and units X, including their general and preferred values, are as already described above. The following paragraphs relate to particular preferred combinations of these moieties.

[0122] Particularly preferred polyalkylene oxide ester polymers are R 1 represents a hydrogen atom or a methyl group; R 2 , R 3 represents a hydrogen atom, d, e are 0, a is 1, b and c each represent an integer of 0 or 1, and the sum of b to c is 0 or 2; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, 2 or 4 carbon atoms in the chain directly bonded between two ether groups, and each alkylene oxide unit has, independently of one another, one of the carbon atoms located α to the -O- unit either containing 2 hydrogen atoms or containing 1 hydrogen atom and 1 methyl group, and the remaining 1 or 3 carbon atoms each containing 2 hydrogen atoms, and the number of methyl groups bonded to the α carbon atom of each -O- unit does not exceed 1, Contains a structural element (I).

[0123] This is especially true when the structural element (I) is C 2 -units only or C 4 Each C 2 -Units and C 4 The - unit can be bonded to either hydrogen atoms alone or to a hydrogen atom and one methyl group. 2 -Unit or C 4 If a methyl group is present in the -unit, it is attached to the carbon atom alpha to the -O-unit, and the number of methyl groups attached to the alpha carbon atom of each -O-unit does not exceed one.

[0124] Such elements are typically based on ethylene oxide, propylene oxide, tetrahydrofuran monomers or mixtures thereof. The -CHCH based on propylene oxide in formula (I) 3 -CH 2 -O- units and -CH based on tetrahydrofuran 2 -CH 2 -CH 2 -CH 2 In the -O- unit, the structural element (I) has one or more C groups not having a methyl group in the border region of the element (I). 2This can be advantageous when the copolymer contains units based on C-. This can be achieved by first polymerizing propylene oxide or tetrahydrofuran, then stopping the addition of propylene oxide and tetrahydrofuran, respectively, and feeding ethylene oxide to complete the polymerization. 2 This can be readily achieved by obtaining -based units. The resulting polyalkylene oxide can then be further treated as described below to form structural units (I) in the polyalkylene oxide ester polymer. Using the preparation process described herein, ethylene oxide is copolymerized with propylene oxide and tetrahydrofuran, respectively, to form -CHCH 3 -CH 2 -O- units and -CH 2 -CH 2 -CH 2 -CH 2 The -O- unit is -CH 2 -CH 2 This results in a disordered structure with alternating -O- units, resulting in -CHCH 3 -CH 2 -O- units and -CH 2 -CH 2 -CH 2 -CH 2 -O-unit to -CH 2 -CH 2 The transition to the -O- unit may become unclear. Such effects are well known in the art, and the corresponding alternating structures are sometimes called "impurity structures".

[0125] Other particularly preferred polyalkylene oxide ester polymers are R 1 represents a hydrogen atom or a methyl group; b, c, d, e are 0, a is 1, X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, two carbon atoms in the chain which are directly bonded between two ether groups, and each alkylene oxide unit has, independently of one another, one of the carbon atoms which is in the α-position to the -O-unit either contains two hydrogen atoms or one hydrogen atom and one methyl group, and the other carbon atom contains two hydrogen atoms, and the number of methyl groups bonded to the α-carbon atom of each -O-unit does not exceed one, Contains a structural element (I).

[0126] This is especially true for C olefins in which the structural element (I) is based on ethylene oxide and propylene oxide. 2 -units, respectively.

[0127] In particular, the weight average molecular weight M w In the case of polyalkylene oxide ester polymers with lower molecular weights, such as less than 1000 g / mol, the polymer may alternatively have cyclic structures, but overall has a non-cyclic structure.

[0128] Particularly preferred are the acyclic polyalkylene oxide ester polymers shown below, where the groups and subscripts relate to formulae (I) and (Ic):

[0129] [Table 1]

[0130] [Table 2]

[0131] [Table 3]

[0132] [Table 4]

[0133] For the polyalkylene oxide ester polymers described above as B), R 1 xα The group is preferably H, while the remaining R 1 xα The group is preferably methyl. This is typically based on the preparation of this type of element starting from the polymerization of propylene oxide, copolymerizing ethylene oxide onto the end.

[0134] For the polyalkylene oxide ester polymers described above as C), the subscript b at or near the boundary between two X units xα and c xα is preferably 0, while the remaining b xα and c xα is preferably 1. This is typically based on the preparation of this type of element starting from the polymerization of 1,2-butylene oxide, copolymerized at the end with ethylene oxide.

[0135] As already mentioned above, the polyalkylene oxide ester polymer of the invention comprises 10 to 560 ether groups and 2 to 51 ester groups, in which case it comprises 1 to 51 structural elements of formula (I). For the avoidance of doubt, it is emphasized that the amount of ether and ester groups mentioned above relates to the entire polyalkylene oxide ester polymer, including each group present in the structural element of formula (I). The polyalkylene oxide ester polymer preferably comprises ≧15, more preferably ≧20, particularly preferably ≧30 ether groups, and preferably ≦500, more preferably ≦400, particularly preferably ≦350 ether groups. It preferably comprises ≧3, more preferably ≧4, particularly preferably ≧5 ester groups, and preferably ≦41, more preferably ≦31, particularly preferably ≦21, very particularly preferably ≦15 ester groups.

[0136] The ratio of the number of ether groups to the number of ester groups is preferably 4 to 100, more preferably ≧5, particularly preferably ≧10, very particularly preferably ≧15, and preferably ≦75, more preferably ≦50, particularly preferably ≦40, very particularly preferably ≦35.

[0137] The number of structural elements (I) in the polyalkylene oxide ester polymer is 1 to 51, preferably ≧2, more preferably ≧3, particularly preferably ≧4, very particularly preferably ≧5, and preferably ≦41, more preferably ≦31, particularly preferably ≦21, very particularly preferably ≦15, most preferably ≦9.

[0138] The polyalkylene oxide ester polymer may be formed entirely by the structural element (I) and, at both ends, each end group containing one or more further alkylene oxide elements or one or more other structural elements. Preferably, the polyalkylene oxide ester polymer contains at the end of the element a further alkylene oxide element having -O- and -CO- units, which together with the -CO- and -O- units of the other elements form an ester group.

[0139] The structural element that forms an ester group together with the structural element (I) or with other structural elements comprises at least one -O- or at least one -CO- unit at one end of such structural element. In that case, the -O- and -CO- units formally form an ester unit. Such structural elements of further alkylene oxide units preferably comprise either two -CO- or two -O- units at the end of such structural element. Since an ester group formally requires one -O- and one -CO- unit, the number of structural elements with one -O- and one -CO- units at their ends should advantageously be balanced.

[0140] As already mentioned above, the polyalkylene oxide ester polymer further comprises such a further structural element in addition to the structural element (I). Specifically, in addition to the structural element (I), the polyalkylene oxide ester polymer further comprises 1 to 25 structural elements represented by the general formula (II): [ka] (In the formula, The -CO- unit on the left is bonded to the -O- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently a hydrogen atom or C 1~12 represents an alkyl group, g, h, i, j, k, m, n, o, p, and q are each independently an integer of 0 or 1, the sum of g through k is 1 to 5, and the sum of m through q is 1 to 5; Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, the alkylene oxide units each independently containing 2 to 6 carbon atoms in a chain directly bonded between two ether groups, the carbon atoms in the chain directly bonded between two ether groups each independently containing 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a structural element, A number of -CO- units of the structural elements of formulae (I) and (II) of general formula (III): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -O- unit on the right is bonded to a -CO- unit of an adjacent unit of the polymer to form an additional ester unit, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 are each independently a hydrogen atom or C 1~12 represents an alkyl group, s, t, u, v, w, and x are each independently an integer of 0 or 1, and the sum of s to x is 2 to 6; Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between the two ether groups, and the carbon atoms in the chain directly bonded between the two ether groups each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a polyalkylene oxide ester polymer comprising polyalkylene oxide units of any one of the following alkyl groups: However, the total number of ester groups, taken together with the structural elements of formula (I), does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer.

[0141] Each end of the structural element (II) can be bonded, for example, to the side containing the -O- unit of the structural element (I), the structural element (III), the side containing the -O- unit of any other polyalkylene oxide, or to another structural element of the polymer that is not represented by any of the structural elements (I), (II), or (III). Needless to say, it is also possible for one end of (II) to be bonded to an end group of the polyalkylene oxide ester polymer. Similarly, each end of the structural element (III) can be bonded, for example, to the side containing the -CO- unit of the structural element (I), the structural element (II), the side containing the -CO- unit of any other polyalkylene oxide, or to another structural element of the polymer that is not represented by any of the structural elements (I), (II), or (III). Needless to say, it is also possible for one end of (III) to be bonded to an end group of the polyalkylene oxide ester polymer.

[0142] R in formula (II) 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 The groups are each independently a hydrogen atom or a C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 7 , R 8 , R 9 , R 10 , R 11 , R 14 , R 15 , R 16 , R 17 represents a hydrogen atom, R 13 is a hydrogen atom or C 1~12 More preferably, R13 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0143] In formula (II), the subscripts g, h, i, j, k, m, n, o, p, and q each independently represent an integer of 0 or 1, and the sum of g to k is 1 to 5, and the sum of m to q is 1 to 5. Preferably, i, j, k, m, n, and o are 1, and g, h, p, and q are 0. More preferably, k and m are 1, and g, h, i, j, n, o, p, and q are 0.

[0144] Particularly preferred structural elements according to formula (II) are of the general formula (IIa): [ka] (In the formula, R 13 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, i, j, n, and o are integers of 0 or 1, the sum of i through j is 0 or 2, and the sum of n through o is 0 or 2.

[0145] Further particularly preferred structural elements according to formula (IIa) are those of the general formula (IIb): [ka] (In the formula, R13 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0146] The unit Y in formula (II) represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, which alkylene oxide units each independently contain, in a chain directly bonded between two -O- units, 2~6 The carbon atoms in the chain, which may also be represented as alkylene units, containing 2 to 6 carbon atoms and directly bonded between two -O- units, are each independently two hydrogen atoms or one hydrogen atom and one C 1~12 The alkyl group may be any of the alkyl groups.

[0147] Preferred units Y are of the general formula (IIc): [ka] (In the formula, β represents a subscript from 1 to Yn that defines the sequence number of each repeat unit, R 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ are each independently a hydrogen atom or C, taking into consideration that β is the sequence number of each repeating unit. 1~12 represents an alkyl group, g yβ , h yβ , i yβ , j yβ , k yβ, l yβ are each independently an integer of 0 or 1, taking into consideration that β is the sequence number of each repeat unit; g yβ ~l yβ The sum of is 2 to 6, Yn represents an integer from 0 to 99.

[0148] For example, R 7 yβ Groups such as, for example, g yβ The lower case y in the subscripts of the formulas R indicates that they are related to the unit Y. The same is true for the number of repeating units, Yn, as well as the capital Y. 7 yβ Groups such as, for example, g yβ The lowercase β in the subscripts such as ##STR1## indicates that the group and subscript each have their own subnumber and indicates that within a polyalkylene oxide unit Y, the group and subscript can vary from one alkylene oxide unit to another. For example, R 7 y1 The R group can be a hydrogen atom, while the R 7 y2 can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript i of the alkylene oxide unit having sequence number 1 y1 can be 0, while the i of the alkylene oxide unit having the sequence number 2 y2 can be 1, and so on.

[0149] R in formula (IIc) 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ C in the group 1~12 The alkyl group may be linear and may be C 3~12In the case of C, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ represents a hydrogen atom, R 7 yβ is a hydrogen atom or C 1~12 More preferably, R 7 yβ stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0150] Subscript g in formula (IIc) yβ , h yβ , i yβ , j yβ , k yβ , l yβ each independently represents an integer of 0 or 1; g yβ ~l yβ The sum of g is 2 to 6. yβ , h yβ , i yβ , l yβ is 1, and j yβ , k yβ is 0. More preferably, g yβ , l yβ is 1, and h yβ , i yβ , j yβ , k yβ is 0.

[0151] Particularly preferred units Y are those of the general formula (IId): [ka] (In the formula, R 7 yβ is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, h yβ , i yβ represents an integer of 0 or 1, and h yβ ~i yβ is 0 or 2, Yn is a unit of measurement that represents an integer from 0 to 99.

[0152] Further particularly preferred units Y according to formula (IId) are those of the general formula (IIe): [ka] (In the formula, R 7 yβ is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Yn is a unit of measurement that represents an integer from 0 to 99.

[0153] The number of repeating units Yn in formula (IIc) is an integer from 0 to 99. It is preferably ≧1, more preferably ≧3, particularly preferably ≧7, very particularly preferably ≧9, and is preferably ≦74, more preferably ≦49.

[0154] The alkylene oxide units in the unit Y are each independently selected from different groups R 7 yβ ~R 12 yβ In terms of, and different subscript g yβ ~l yβ It is emphasized that the repeating units Y may be identical or different from each other in this respect. In this regard, in formula (IIc), the subscript yβ is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 7 yβ For example, the subscript number is g yβ As already mentioned, the following specification is used:

[0155] It is further emphasized that each structural element (II) in the polyalkylene oxide ester polymer, when more than one element (II) is present, may be the same as or different from the other one or more.

[0156] R in formula (III) 19 , R 20 , R 21 , R 22 , R 23 , R 24 are each independently a hydrogen atom or C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 19 , R 20 , R21 , R 22 , R 23 , R 24 represents a hydrogen atom, R 19 is a hydrogen atom or C 1~12 More preferably, R 19 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0157] In formula (III), the subscripts s, t, u, v, w, and x each independently represent an integer of 0 or 1, and the sum of x is 2 to 6. Preferably, s, t, u, and x are 1, and v and w are 0. More preferably, s and x are 1, and t, u, v, and w are 0.

[0158] Particularly preferred structural elements based on formula (III) have the general formula (IIIa): [ka] (In the formula, R 19 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, t and u are integers of 0 or 1, and the sum of t to u is 0 or 2.

[0159] Further particularly preferred structural elements based on formula (IIIa) are of the general formula (IIIb): [ka] (In the formula, R 19 is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0160] The unit Z in (III) represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, which alkylene oxide units each independently contain, in a chain directly bonded between two -O- units, a C 2~6 The carbon atoms in the chain, which may also be represented as alkylene units, containing 2 to 6 carbon atoms and directly bonded between two -O- units, are each independently two hydrogen atoms or one hydrogen atom and one C 1~12 The alkyl group may be any of the alkyl groups.

[0161] Preferred units Z are of the general formula (IIIc): [ka] (In the formula, γ represents a subscript from 1 to Zn that defines the sequence number of each repeat unit, R 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ are each independently a hydrogen atom or C, taking into consideration that γ is the sequence number of each repeating unit. 1~12 represents an alkyl group, · szγ , t zγ , u zγ , v zγ , w zγ , x zγ each independently represents an integer of 0 or 1, taking into consideration that γ is the sequence number of each repeat unit; s zγ ~x zγ The sum of is 2 to 6, Zn represents an integer from 0 to 100.

[0162] For example, R 19 zγ Groups such as, for example, s zγ The lower case z in the subscripts indicates that they are related to the unit Z. The capital Z in the number of repeating units, Zn, also indicates the same. 19 zγ Groups such as, for example, s zγ The lowercase γ in the subscripts such as ##STR1## indicates that the radicals and subscripts each have their own subnumber and indicates that within a polyalkylene oxide unit Z, the radicals and subscripts may vary from one alkylene oxide unit to another. For example, the R 19 z1 The R group can be a hydrogen atom, while the R 19 z2 can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript u of the alkylene oxide unit with sequence number 1 z1 can be 0, while u of the alkylene oxide unit with sequence number 2 can be z2 can be 1, and so on.

[0163] R in formula (IIIc) 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24zγ C in the group 1~12 The alkyl group may be linear, 3~12 In the case of alkyl, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ represents a hydrogen atom, and R 19 zγ is a hydrogen atom or C 1~12 More preferably, R 19 zγ stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0164] The subscript s in formula (IIIc) zγ , t zγ , u zγ , v zγ , w zγ , x zγ each independently represents an integer of 0 or 1; zγ ~x zγ The sum of is 2 to 6. Preferably, s zγ , t zγ , u zγ , x zγ is 1, and v zγ , w zγ is 0. More preferably, s zγ , x zγ is 1, and t zγ , uzγ , v zγ , w zγ is 0.

[0165] Particularly preferred units Z have the general formula (IIId): [ka] (In the formula, R 19 zγ is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, t zγ , u zγ represents an integer of 0 or 1; t zγ ~u zγ is 0 or 2, Zn is a unit of zinc (representing an integer from 0 to 100).

[0166] Further particularly preferred units Z according to formula (IIId) have the general formula (IIIe): [ka] (In the formula, R 19 zγ is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Zn is a unit of zinc (representing an integer from 0 to 100).

[0167] The number of repeating units Zn in formula (IIIc) is an integer from 0 to 100. It is preferably ≧2, more preferably ≧4, particularly preferably ≧8, very particularly preferably ≧10, and is preferably ≦75, more preferably ≦50.

[0168] The alkylene oxide units in the unit Z are each independently selected from different groups R 19 zγ ~R 24 zγ In terms of, and different subscripts s zγ ~x zγ It is emphasized that the repeating units Z may be identical or different from each other in this respect. In this regard, in formula (IIIc), the subscript zγ is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 19 zγ For example, the subscript number is s zγ As already mentioned, the following specification is used:

[0169] It is further emphasized that each structural element (III) in the polyalkylene oxide ester polymer, when more than one element (III) is present, may be the same as or different from the other one or more.

[0170] The different moieties of structural elements (II) and (III), such as the groups, subscripts and units X and Y, including their general and preferred values, are as already described above. The following paragraphs relate to particular preferred combinations of these moieties.

[0171] Particularly preferably, the polyalkylene oxide ester polymer comprising the structural elements (I), (II) and (III) is R 13 , R 19 each independently represents a hydrogen atom or a methyl group; R 9 , R10 , R 11 , R 14 , R 15 , R 20 , R 21 , R 24 represents a hydrogen atom, g, h, p, q, v, w are 0, k, m, s, and x are 1, i, j, n, o, t, and u each independently represent an integer of 0 or 1, the sum of i through j is 0 or 2, the sum of n through o is 0 or 2, and the sum of t through u is 0 or 2; Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, 2 or 4 carbon atoms in the chain directly bonded between two ether groups, and in which, independently of one another, one of the carbon atoms in the α-position to the -O- unit either contains 2 hydrogen atoms or contains 1 hydrogen atom and 1 methyl group, and the other remaining 1 or 3 carbon atoms each contain 2 hydrogen atoms, and the number of methyl groups bonded to the α-carbon atom of each -O- unit does not exceed 1.

[0172] This is especially true when the structural elements (II) and (III) are C 2 -units only or C 4 Each C 2 -Units and C 4 The - unit can be bonded to either hydrogen atoms alone or to a hydrogen atom and one methyl group. 2 -Unit or C 4 If a methyl group is present in the -unit, it is attached to the carbon atom alpha to the -O-unit, and the number of methyl groups attached to the alpha carbon atom of each -O-unit does not exceed one.

[0173] Such elements are typically based on ethylene oxide, propylene oxide, tetrahydrofuran monomers or mixtures thereof. The propylene oxide-based -CHCH 3 -CH 2 -O- units and -CH based on tetrahydrofuran 2 -CH 2 -CH 2 -CH 2 In the -O- unit, it may be advantageous if the structural elements (II) and (III) contain one or more C2-based units without methyl groups in the boundary region of each element. This can be achieved by first polymerizing propylene oxide or tetrahydrofuran, then stopping the addition of propylene oxide and tetrahydrofuran, respectively, and feeding ethylene oxide to complete the polymerization, thereby forming C2-based units at both ends. 2 This can be readily accomplished by obtaining -based units. The resulting polyalkylene oxide can then be further treated as described below to form structural units (II) and (III) in the polyalkylene oxide ester polymer. Using the preparation process described herein, ethylene oxide is copolymerized with propylene oxide and tetrahydrofuran, respectively, to form -CHCH 3 -CH 2 -O- units and -CH 2 -CH 2 -CH 2 -CH 2 The -O- unit is -CH 2 -CH 2 This results in a disordered structure with alternating -O- units, resulting in -CHCH 3 -CH 2 -O- units and -CH 2 -CH 2 -CH 2 -CH 2 -O-unit to -CH 2 -CH 2The transition to the -O- unit may become unclear. Such effects are well known in the art, and the corresponding alternating structures are sometimes called "impurity structures".

[0174] Other particularly preferred polyalkylene oxide ester polymers are R 13 , R 19 each independently represents a hydrogen atom or a methyl group; R 9 , R 10 , R 11 , R 14 , R 15 , R 20 , R 21 , R 24 represents a hydrogen atom, g, h, i, j, n, o, p, q, t, u, v, w are 0, k, m, s, and x are 1, Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, two carbon atoms in the chain directly bonded between two ether groups, and each alkylene oxide unit, independently of one another, has one of the carbon atoms in the α-position to the -O- unit either containing two hydrogen atoms or one hydrogen atom and one methyl group, and the other remaining carbon atom contains two hydrogen atoms, and the number of methyl groups bonded to the α-carbon atom of each -O- unit does not exceed 1.

[0175] This is especially true for C 2 , in which the structural elements (II) and (III) are based on ethylene oxide and propylene oxide. 2 -units, respectively.

[0176] The number of structural elements (II) in the polyalkylene oxide ester polymer is from 1 to 25, preferably ≧2, more preferably ≧3, particularly preferably ≧4, very particularly preferably ≧5, most preferably ≧6, and preferably ≦23, more preferably ≦22, particularly preferably ≦20, very particularly preferably ≦17. The total number of elements (I) and (II) is adapted so that the total number of ester groups does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer.

[0177] Since the formation of ester groups from elements (I), (II) and (III) requires an -O- unit at the end of one element and an -CO- unit at the end of another element, the total number of such -O- units and -CO- units in the elements forming the polyalkylene oxide ester polymer is preferably adjusted so that the intended amount of ester groups is formed. The potentially redundant -O- or -CO- units may be attached, for example, to the end group of the polymer or to other structural elements. Since the number of -O- and -CO- units in element (I) is already balanced, and element (II) provides only -CO- units, element (III) is preferably present in a number suitable for forming an ester bond with the -CO- units of the structural elements of formulae (I) and (II). More preferably, the ratio of the number of elements (II) to the number of elements (III) is 0.8 to 1.2, particularly preferably ≧0.9, very particularly preferably ≧0.95, and particularly preferably ≦1.1, very particularly preferably ≧1.05, most preferably 1. The extra -O- or -CO- units may, for example, be attached to end groups or other structural elements.

[0178] Since the polyalkylene oxide ester polymers used in the present invention are advantageously produced by esterification of monomers, it is preferable to use monomers that are readily available. Suitable monomers are in particular monomers that already contain structural element (I), for example, monomers of element (I) that contain a hydroxy group as a precursor of -O- units at one end and a carboxylic acid, carboxylic acid alkyl ester or carboxylate (e.g., -COONa, etc.) group as a precursor of -CO- units at the other end. Even if the monomers of element (I) can be prepared in large quantities with high purity, it is easier to obtain a mixture of monomers of elements (I), (II) and (III). Thus, polyalkylene oxide ester polymers based on such mixtures contain elements (I), (II) and (III). When based on a composition of such monomer mixtures, polyalkylene oxide ester polymers in which the ratio of the number of structural elements (I) to the number of structural elements (II) is 0.5 to 8 are preferred, a ratio of 0.7 to 6 is more preferred, and a ratio of 0.85 to 4.7 is particularly preferred.

[0179] As already mentioned above, the polyalkylene oxide ester polymers used in the present invention can also contain, apart from the end groups, further polyalkylene oxide elements other than (I), (II) and (III) or further different structural elements. Further polyalkylene oxide elements other than (I), (II) and (III) can be, for example, elements having an alkylene unit with more than 6 carbon atoms in the chain directly bonded between two ether groups. The other structural elements can be, for example, based on diols other than structural element (III), dicarboxylic acids other than structural element (II) or alpha-hydroxy-omega carboxylic acids other than structural element (I), for example sebacic acid or terephthalic acid. In general, structural elements (I), (II) and (III) are the number-average molecular weight M of the polyalkylene oxide ester polymer. nThe nature of the structural elements, and hence the composition of the polyalkylene oxide ester polymer, can be determined, for example, by hydrolysis of the ester bonds and the structural units using conventional analytical methods such as gas chromatography, HPLC, NMR and the like.

[0180] Due to the presence of end groups on both sides of the polymer, the amount of structural elements (I), (II) and (III) is usually at least equal to the number average molecular weight M of the polyalkylene oxide ester polymer, even if the polymer contains no other elements than (I), (II) and (III). n However, due to the quantitative effect that the molecular mass of the hydrogen atom is very small compared to the molecular weight of the polyalkylene oxide ester polymer, especially when -OH groups are present as end groups, a value of 100% can be achieved, taking into account the accuracy of the analytical measurement.

[0181] Although elements other than elements (I), (II) and (III) may be present in the polyalkylene oxide ester polymer, preferably only two end groups are included in addition to elements (I), (II) and (III).

[0182] Particularly preferred polyalkylene oxide ester polymers based on structural elements (I), (II) and (III) are the following polymers, where the groups and subscripts relate to formulae (I), (Ic), (II), (IIc), (III) and (IIIc):

[0183] [Table 5]

[0184] [Table 6]

[0185] [Table 7]

[0186] [Table 8]

[0187] For the polyalkylene oxide ester polymers described above as B), R 2 at or near the boundaries of two of the X, Y and Z units is 1 xα , R 7 yβ and R 19 zγ The group is preferably H, while the remaining R 1 xα , R 7 yβ and R 19 zγ is preferably methyl. This is typically based on the preparation of this type of element starting from the polymerization of propylene oxide, copolymerizing ethylene oxide at the end.

[0188] For the polyalkylene oxide ester polymers described above as C), R 2 is at or near the boundary between two of the X, Y and Z units. 1 xα , R 7 yβ and R 19 zγ The group is preferably H, while the remaining R 1 xα , R 7 yβ and R 19 zγ is preferably ethyl. This is typically based on the preparation of this type of element starting from the polymerization of 1,2-butylene oxide, copolymerized at the end with ethylene oxide.

[0189] Both definitions of the general structure of the PAG-ester / polyalkylene oxide ester polymers defined above as separate embodiments, used as the polymer backbone A to obtain the graft polymers of the present invention, are integral parts of the present invention; both definitions largely overlap, but it is particularly emphasized that the second structure definition is more comprehensive and is defined using organic chemistry terms, while the first structure definition is more narrow and uses polymer chemistry terminology. This latter polymer terminology is also intended to serve to clarify for readers who are more familiar with polymer chemistry terms than organic chemistry terms. Nevertheless, the graft polymers of the present invention include both structures and are in no way intended to limit the present invention to either one of the structure definitions; furthermore, both are embodiments of the polymer backbone (A) of the present invention.

[0190] The polyalkylene oxide ester polymers / PAG-ester polymers of the invention can be easily prepared by esterifying the blocks of each structural element that builds the polymer, while the block to be esterified contains at least one esterifiable end group in the block if it is intended to be a terminal group of the polyalkylene oxide ester polymer, or two esterifiable end groups in the block if it is intended to be an internal group of the polyalkylene oxide ester polymer. In principle, as esterifiable end groups, basically any group that is usually known as an esterifiable group can be used. However, the esterifiable end group that will later form the -O-part of the -COO-ester group is, for example, -OH, and the esterifiable end group that will later form the -CO-part of the -COO-ester group is, for example, -COOH, -COOR, such as, for example, the -COOCH3 group (R is a hydrocarbon group having 1 to 12 C atoms) or a carboxylate, the cation of which is preferably an alkali metal, such as sodium or potassium, preferably -COOH and -COONa.

[0191] For the sake of completeness, it is noted that in principle polyalkylene oxide ester polymers having weight-average molecular weights Mw of more than 50 000 g / mol, for example 100 000 g / mol or even more, can also be readily prepared by esterifying the corresponding blocks.

[0192] In this connection, a preferred process has been found for the preparation of the polyalkylene oxide ester polymers of the invention, in which a polyalkylene oxide comprising structural element (I) and having one primary OH and one COOH end group, or a mixture of such polyalkylene oxides, is esterified in the presence of an esterification catalyst at a temperature between 50 and 250° C. and a pressure between 0.1 kPa abs and 1 MPa abs.

[0193] Polyalkylene oxides containing structural element (I) and having one primary OH end group and one COOH end group can be synthesized in various ways. One of the possibilities is to partially oxidize the corresponding polyalkylene oxide having two primary OH end groups and separate the polyalkylene oxide component having one primary OH end group and one COOH end group (called "mono-acid" and also called "PAG-MC" for "PAG-monocarbonic acid") from the unconverted polyalkylene oxide having two OH end groups (called "diol" and also called "PAG-DO" for "PAG-diol") and the fully oxidized polyalkylene oxide having two COOH end groups (called "diacid" and also called "PAG-DC" for "PAG-dicarbonic acid"), for example by vacuum distillation. Another possibility is to synthesize a specific polyalkylene oxide with one primary OH and one COOH end group, for example by adding metallic sodium and bromoacetic acid to the polyalkylene oxide and treating the resulting sodium carboxylate end groups to the corresponding carboxylic acid end groups. However, both methods, although complex in terms of their process steps, due to vacuum distillation and complex synthesis steps, may be relevant if polyalkylene oxide ester polymers with a high content of structural unit (I) are desired.

[0194] Additionally, there is provided an alternative and more preferred process for preparing the polyalkylene oxide ester polymers of the present invention, comprising the steps of: a) a polyalkylene oxide or a mixture of such polyalkylene oxides comprising the structural element (I) and having one primary OH and one COOH end group, b) a polyalkylene oxide or a mixture of such polyalkylene oxides, which comprises the structural element (II) and has two COOH end groups, c) a polyalkylene oxide or a mixture of such polyalkylene oxides comprising structural element (III) and having two primary OH end groups, at a temperature of 50 to 250° C. and a pressure of 0.1 kPa abs to 1 MPa abs in the presence of an esterification catalyst.

[0195] It has further been found according to the invention that the mixture of components a) to c) can be easily produced by partial oxidation of the corresponding polyalkylene oxide having two primary OH end groups. Such partial oxidation is further described below. For the sake of completeness, it is mentioned that the mixture of components a) to c) can of course also be prepared by mixing the individual components.

[0196] The ester groups of the polyalkylene oxide ester polymer are usually formed by esterification of the polyalkylene oxide block having an esterifiable end group, and since one -O-containing end group such as an -OH group and one -CO-containing end group such as a -COOH group are required to obtain each ester group, it is preferable that these amounts are equal or approximately equal. However, if there is a slight excess of one type, this can be absorbed by an element other than (I), (II) and (III) that can be linked to the -O- or -CO- group. Furthermore, two end groups of the polyalkylene oxide ester polymer can also be linked to two of such groups. Based on this, the ratio of the number of OH end groups to the number of COOH end groups is preferably 0.9 to 1.1, more preferably ≧0.95, particularly preferably ≧0.98, even more particularly preferably ≧0.99, and more preferably ≦1.05, particularly preferably ≦1.02, even more particularly preferably ≦1.01.

[0197] The esterification of each polyalkylene oxide block can generally be carried out by a method known in the industry, for example, as described in U.S. Patent No. 6,310,235 or U.S. Patent No. 5,324,853. The educt is esterified in the presence of an esterification catalyst, preferably provided such that the number of OH end groups to the number of COOH end groups of the educt is within a target range.

[0198] Typically, various types of esterification catalysts can be used. These can be broadly divided into acidic catalysts, amphoteric catalysts and basic catalysts. Representatives of acidic catalysts include mineral acids, such as sulfuric acid and phosphoric acid, and organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid, trifluormethansulfonsaeure. Further acidic catalysts can also be acidic solids, such as zeolites, in particular Ti-zeolites, various oxides, mixed metal oxides, sulfated oxides, acidic ion exchange resins, protonic heteropolyoxoanions, salts of heteropolyoxoanions, acidic clays and phosphates. Representative basic catalysts include, for example, ZnO, La 2 O 3 , ThO 2 , ZrO 2 , hydrotalcite, hydroxyapatite, alkali metal oxides, alkaline earth metal oxides, basic zeolites and solid superbases such as Verkade bases or guanidine. Possible amphoteric catalysts include oxides of zinc (II), tin (II) and tin (IV). In addition, Lewis acid catalysts derived from metal cations of group 4 of the periodic table of the elements, such as Ti and Zr compounds, such as Ti (VI) and Zr (IV), Lewis acid catalysts derived from metal cations of group 3 of the periodic table of the elements, such as Sc (III) compounds or Lewis acid catalysts derived from metal cations of group 5 of the periodic table of the elements, such as Al (III) compounds, are also useful. However, catalysts containing metal cations of groups 12 and 15 of the periodic table of the elements, such as Sn (IV), Sn (II), Zn (II) and Bi (III), are also included. The corresponding anions can usually be selected from alkoxylates, e.g. isopropoxylates and isobutyrates, alkanoates, aralkylcarboxylates, halogens, sulfates, organic sulfonates such as p-toluenesulfonate or methanesulfonate, amidomethanesulfonates, trifluoromethanesulfonates or trifluoromethanesulfonimides.

[0199] The esterification catalyst is usually used in a conventional amount in the range of 0.02 to 10% by weight, preferably ≧0.05% by weight, more preferably ≧0.1% by weight, and preferably ≦5% by weight, more preferably ≦2% by weight, based on the total amount of the compound to be esterified.

[0200] The esterification can be carried out in the absence or presence of a solvent. When carried out in the presence of a solvent, it is preferred to use an organic solvent that is inert under the reaction conditions. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers. Preferably, the solvent is selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dibutyl ether, tetrahydrofuran, dioxane and mixtures thereof. Suitable solvents that form an azeotrope with water are aromatic hydrocarbons, such as benzene, alkyl aromatic compounds, toluene or xylene. Suitable halogenated compounds with high boiling points are also useful.

[0201] The esterification is carried out at a temperature of 50 to 250°C, preferably ≧70°C, more preferably ≧80°C, and preferably ≦220°C, more preferably ≦200°C. When the esterification catalyst is an organic acid or a mineral acid, the esterification is usually carried out at a temperature in the range of 50 to 160°C. When the esterification catalyst is a metal-containing catalyst, the esterification is usually carried out at a temperature in the range of 80 to 250°C. With regard to pressure, the esterification can be carried out in a wide pressure range from vacuum to pressures above atmospheric pressure, ranging from 0.1 kPa abs to 1 MPa abs. It is preferably carried out at ≦0.5 MPa abs, more preferably ≦0.2 MPa abs.

[0202] The esterification can be carried out in the absence or presence of an inert gas, which is generally understood to mean a gas which, under the reaction conditions defined, does not take part in any reaction with the starting materials, reagents, solvents or resulting products involved in the reaction.

[0203] Suitable reactors for carrying out the esterification process are in principle all reactors suitable for esterification reactions, examples of which include stirred tanks.

[0204] The esterification usually requires a reaction time of from 1 to 24 hours, more typically from 2 to 12 hours, which depends mainly on the nature of the inducer, the type and amount of catalyst and the reaction temperature.

[0205] The obtained polyalkylene oxide ester polymer is usually, but not necessarily, subjected to work-up depending on the intended purity. When work-up is performed, components other than the polyalkylene oxide ester polymer, especially esterification catalyst, are usually removed. The polyalkylene oxide ester polymer free of esterification catalyst is generally important for product quality. Heterogeneous catalysts can usually be removed by physical methods such as filtration or centrifugation. Homogeneous catalysts can usually be removed using fixed ion exchange equipment.

[0206] In a preferred embodiment, the catalyst is not removed but remains in the polyalkylene oxide polymer, this embodiment being preferred when the amount of catalyst used is near the lower to very low end of the ranges disclosed herein.

[0207] The molecular weight of the polyalkylene oxide ester polymer can be easily adjusted by the ratio of OH end groups to COOH end groups of the compound to be esterified. Simply put, the more this ratio deviates from exactly 1:1, the fewer ester groups are formed in the polyalkylene oxide ester polymer. In practice, this can be achieved, for example, by adding a diol component or a diacid component, ideally one of the sources, to the reaction mixture. However, the addition of other monools or monocarboxylic acids can also serve this purpose.

[0208] The end groups of the polyalkylene oxide compounds that are not esterified with other polyalkylene oxide compounds usually form the end groups of the polyalkylene oxide ester polymers of the invention. Thus, the unesterified -OH end groups of the polyalkylene oxide compounds become the -OH end groups of the polyalkylene oxide ester polymers, and the unesterified -COOH, -COOR or -COOM end groups of the polyalkylene oxide compounds become the -COOH, -COOR or -COOM end groups of the polyalkylene oxide ester polymers (R is usually a hydrocarbon group having 1 to 12 C atoms, for example a methyl group, and M is usually an alkali metal, for example sodium or potassium).

[0209] For the sake of completeness, it is mentioned that, apart from the block containing structural element (I) or the structural elements (I) to (III), other elements having esterifiable end groups can also be present, especially if it is intended to prepare a polyalkylene oxide ester polymer which must also contain such other elements. Examples of such other elements are polyalkylene oxide elements having alkylene units with more than 6 carbon atoms in the chain directly bonded between two ether groups.

[0210] As already mentioned above, mixtures of components a)-c) containing so-called "mono-acids", "di-acids" and "diols" can be easily prepared by partial oxidation of the corresponding polyalkylene oxides ("diols") having two primary OH end groups. This allows a high degree of freedom, therefore, in the case where a polyalkylene oxide ester polymer with a higher content of structural element (I) is required, by separating at least a portion of the other components (so-called "di-acids" and "diols") to obtain a polyalkylene oxide (so-called "mono-acid") or a mixture of such polyalkylene oxides with a higher content of structural element (I) and one primary OH and one COOH end group.

[0211] In a preferred process, the polyalkylene oxide or mixture of such polyalkylene oxides containing structural element (I) and having one primary OH and one COOH end group used for the esterification is prepared by partial oxidation of the corresponding polyalkylene oxide or mixture of such polyalkylene oxides having two primary OH end groups with oxygen at a temperature of 20-100°C and an oxygen partial pressure of 0.01-2 MPa abs in the presence of water and a heterogeneous catalyst comprising platinum, palladium or gold.

[0212] Depending on the composition and structure of the polyalkylene oxide ester polymer in question, the polyalkylene oxide comprising structural element (I) and having one primary OH and one COOH end group, or a mixture of such polyalkylene oxides, prepared by partial oxidation as described above, can of course be blended with other components, such as a polyalkylene oxide comprising structural element (II) and having two COOH end groups, a polyalkylene oxide comprising structural element (III) and having two OH end groups, any other polyalkylene oxide having OH and / or COOH groups or any other esterifiable structural element.

[0213] In a more preferred process, the mixture of components a)-c) used for the esterification is prepared by partial oxidation of the corresponding polyalkylene oxide having two primary OH end groups or a mixture of such polyalkylene oxides with oxygen in the presence of water and a heterogeneous catalyst comprising platinum, palladium or gold at a temperature of 20-100° C. and an oxygen partial pressure of 0.01-2 MPa abs, the oxidation reaction being stopped after the ratio of the number of OH end groups to the number of COOH end groups reaches a range of 0.9-1.1.

[0214] The corresponding polyalkylene oxides having two primary OH end groups used as starting materials for partial oxidation can be easily prepared by methods known in the art. The presence of primary OH groups is necessary for the oxidation of OH end groups to COOH end groups. For example, polyethylene oxide can be advantageously prepared by polymerizing ethylene oxide. Similarly, polypropylene oxide and poly-1,2-butylene oxide can be advantageously prepared by polymerizing propylene oxide and 1,2-butylene oxide, respectively, but due to the presence of a secondary OH group at one end, ethylene oxide units are usually formed in the outer region by copolymerizing ethylene oxide at the end at the end of the polymerization, while the inner region contains propylene oxide and 1,2-butylene oxide units, respectively. Furthermore, polytetrahydrofuran can be advantageously prepared by polymerizing tetrahydrofuran.

[0215] The partial oxidation process is carried out in the presence of water. Water promotes the oxidation of -OH end groups to -COOH end groups in various ways. For example, when a suspension catalyst is used, water improves its suspension in the reaction mixture and also reduces the viscosity of the reaction mixture. The content of water in the liquid phase is preferably maintained at 50-95 wt.%, preferably ≧60 wt.%, preferably ≦90 wt.%, more preferably ≦80 wt.%.

[0216] The catalyst used in the partial oxidation process is a heterogeneous catalyst containing platinum, palladium or gold as active component, preferably platinum. Usually, the active metal is fixed on a support. A variety of different materials can be used as the support. Examples include inorganic oxides, such as aluminum oxide, zirconium oxide, titanium dioxide, silicon oxide, inorganic silicates, such as aluminum silicate or charcoal. It is of course also possible to use a mixture of different supports. It is preferred to use charcoal as the support.

[0217] Preferred catalysts with platinum as active component generally contain 0.1% to 10% by weight of platinum, preferably ≧0.5% by weight, more preferably ≧1% by weight, even more preferably ≧4% by weight, and preferably ≦8% by weight, more preferably ≦6% by weight, based on the total mass of the heterogeneous catalyst in each case. More preferably, heterogeneous catalysts are used which contain 1 to 10% by weight, in particular 4 to 10% by weight, of platinum on charcoal.

[0218] The catalyst used may also contain further metals besides platinum, palladium or gold. The term "further metals" is understood to mean metals of periods 4 to 6 of groups 3 to 16 of the periodic table of the elements, starting with scandium (atomic number 21) and ending with polonium (atomic number 84). Preferably, the total content of further metals is 0 to 100% by weight, preferably 0 to 30% by weight, more preferably 0 to 10% by weight, even more preferably 0 to 1% by weight, in particular 0 to 0.1% by weight, based on the mass of platinum. In particular, the total content of cadmium, lead and bismuth is preferably 0 to 1% by weight, more preferably 0 to 0.5% by weight, particularly preferably 0 to 0.1% by weight, even more preferably 0 to 0.05% by weight, in particular 0 to 0.01% by weight, based on the mass of platinum. Thus, the catalyst is preferably prepared without the intentional addition of further metals.

[0219] The supported heterogeneous catalysts can be used in various geometric shapes and sizes, for example as powders or moldings. Powder catalysts can be operated, for example, in suspension mode. In the case of a fixed bed mode, it is preferred to use moldings, for example pellets, cylinders, hollow cylinders, spheres or extrudates or tablets. In that case, the moldings are usually fixed in the reactor by known methods. In the case of catalyst moldings, their average particle size is preferably 1 to 10 mm.

[0220] However, preferably, a catalyst in powder form is used, which is then suspended in the reactor. A filter is usually used here to hold the suspended catalyst so that it does not flow out of the reaction system. An example of a commonly used filter is the cross-flow filter.

[0221] Regardless of the geometric shape and size of the catalyst particles, the platinum is generally in the form of particles having an average diameter of 0.1 to 50 nm as measured by x-ray diffraction, although smaller or larger particles may also be present.

[0222] In the preparation of supported heterogeneous catalysts, platinum is generally applied to a support by a suitable method, such as that described in US 2020 / 017,745.

[0223] The supported heterogeneous catalyst generally has a BET surface area, measured according to DIN ISO 9277:2014-01, of ≧1 m2 / g and ≦10000 m2 / g. When carbon is used as the support, the BET surface area is preferably in the range of ≧500 m2 / g and ≦10000 m2 / g.

[0224] The preferred platinum-based catalyst is typically applied in an amount of 0.1 to 50 mg, preferably ≧1 mg and preferably ≦20 mg, of platinum per gram of polyalkylene oxide to be partially oxidized.

[0225] Since the aqueous solution of the polyalkylene oxide feedstock has a neutral pH, the pH at the start of the oxidation is usually at or near 7. As a result of the formation of COOH groups, the pH gradually decreases and thus generally reaches a value of 1 or 3 as the oxidation approaches its end.

[0226] However, the partial oxidation can also be carried out in the presence of a base such as sodium hydroxide or potassium hydroxide. The basic conditions increase the oxidation power and lead to the formation of carboxylates instead of carboxylic acids. As already mentioned above in the description of the esterification process, the carboxylates can also be used directly for the esterification.

[0227] In the absence of a basic compound, the carboxylic acid is formed directly, thereby avoiding (i) the use of additional chemicals (base and exogenous acid) and (ii) the disposal of salts formed from the base and exogenous acid.

[0228] The oxidation medium used in the partial oxidation process is molecular oxygen. The oxygen is added either in pure form or diluted with other gases, for example in the form of air or O2 / N2 mixtures. Preferably, a gaseous oxygen content of ≧90% by volume is used, more preferably ≧95% by volume, even more preferably ≧99% by volume, in particular ≧99.5% by volume. The use of very concentrated or pure oxygen makes it possible to keep the off-gas relatively small.

[0229] To facilitate the distribution of the oxygen in the reactor, it is advantageous to meter it in the form of fine bubbles, for example through a frit.

[0230] The oxygen partial pressure in the oxidation is 0.01 to 2 MPa, preferably ≧0.02 MPa, more preferably ≧0.05 MPa, and preferably ≦1 MPa, more preferably ≦0.3 MPa.

[0231] The oxidation is carried out at a temperature of 20-100°C, preferably ≧30°C, more preferably ≧40°C, and preferably ≦80°C, more preferably ≦70°C.

[0232] Reactors suitable for carrying out the partial oxidation process are in principle any reactor suitable for carrying out exothermic gas / liquid reactions. Examples include stirred tanks, trickle bed reactors and bubble column reactors. To remove the heat of reaction, the reactor is usually equipped with a cooling device. Depending on the type of reactor and the nature of the catalyst, the cooling device advantageously comprises a cooling element inside the reactor or a cooling element in an external circuit outside the reactor. For example, stirred tanks are preferably equipped with internal cooling elements, while bubble columns are more advantageously equipped with cooling elements, for example in the external circuit.

[0233] When the catalyst is in the form of moldings, it is usually fixed in the reactor in the form of a fixed bed.For this purpose, trickle bed reactors are a particularly useful option, in which case the catalyst can be introduced in the form of a bed.However, it is also possible to use catalyst moldings in stirred tank reactors.In that case, it is advantageous to fix the catalyst moldings in a partition, for example in a wire cage.

[0234] The preferred use of the powdered catalyst is in the form of a suspension in the reaction mixture. Reactors suitable for this purpose are, for example, stirred tanks or bubble columns. In order to prevent the powdered catalyst from settling, it is necessary to carry out a corresponding mixing of the liquid reaction mixture. In stirred tanks, this is usually achieved by using a stirrer. In the case of bubble columns, mixing is usually achieved via an external circuit with a transport pump. In principle, the bubble column can be operated in either the upward or downward direction with respect to the liquid circuit, but the downward direction is usually more advantageous.

[0235] The partial oxidation process can be operated semi-continuously or continuously, in either case oxygen is fed to the reactor continuously or at least intermittently to ensure the desired partial pressure, preferably continuously.

[0236] In semi-continuous operation, the reactor is initially charged with the entire aqueous reactant mixture along with the catalyst prior to starting the reaction, and no fresh reactants are added or liquid reaction mixture is withdrawn during the oxidation reaction. The reactor is not emptied until after the oxidation reaction is complete.

[0237] In continuous operation, the liquid reaction mixture is likewise present in the reactor together with the catalyst, but small amounts of liquid reactant are constantly withdrawn and a corresponding amount of aqueous reactant is provided, where if a suspended catalyst is used, the liquid reaction mixture is advantageously removed from the reactor by means of a filtering device, for example a cross-flow filter.

[0238] Since the partially oxidized polyalkylene oxide is in any event destined to contain polyalkylene oxides with one primary OH and one COOH end group, the oxidation reaction must be carried out in such a way that some primary OH groups remain unoxidized and others are already oxidized to COOH groups. This can be easily achieved by stopping the oxidation reaction when the desired amount of partially oxidized polyalkylene oxide is present. Except for low molecular weight polyalkylene oxides with molecular weights of only a few hundred g / mol, the probability of a primary OH group being oxidized to a COOH group is independent of whether the other end group of the polyalkylene oxide is already oxidized or not. At the beginning of the oxidation, polyalkylene oxides with one primary OH and one COOH end group (called "mono-acids") are mainly produced. As their amount increases, the probability of the other OH group also being oxidized also increases, so polyalkylene oxides with two COOH end groups (called "di-acids") are also formed.

[0239] In the case of semi-continuous operation, the simplest way to stop further oxidation is to stop the supply of oxygen in a timely manner. At the very least, the oxygen present in the reactor will be consumed. Additional operations that can be combined with such stopping of the oxygen supply are, for example, supplying additional inert gas to replace part of the oxygen in the reactor, reducing the total pressure in the reactor so that the oxygen partial pressure naturally decreases, or cooling the reaction liquid, for example by withdrawing it from the reactor through a cooling device. However, the most effective measure is to stop the oxygen supply.

[0240] The oxidation reaction takes many hours to proceed, and the time range in which a high content of "mono acids" is present is long enough that the interruption of the progression of such an oxidation reaction can be controlled very easily. The time range in which the partial oxidation reaction should be stopped can be determined in various ways. Firstly, the time required for partial oxidation under defined conditions such as temperature, oxygen partial pressure, nature and amount of catalyst can be determined by preliminary tests in which the oxidation is stopped at different times and the composition of the reaction product is analyzed. The oxidation time required to obtain the desired composition can then be estimated. Another possibility for controlling the partial oxidation is to measure the amount of oxygen fed to the reactor as an indicator of the oxygen absorbed by the oxidation. The degree of oxidation can then be calculated by the amount of OH groups present in the polyalkylene oxide derivative and the stoichiometric amount of oxidation of them to COOH groups. Another method is to take samples over time and analyze them, for example by titration and by measuring the acid number as an indicator of the COOH groups already formed. Last but not least, physical measurements such as electrical conductivity, dielectric constant or impedance measurements can also be carried out in situ, which of course require prior calibration.

[0241] In the case of continuous operation, the degree of oxidation can be easily controlled by the residence time of the mixture in the reactor under reaction conditions.

[0242] As already mentioned above, the oxidation reaction requires a long time. The usual reaction time for partially oxidizing about 50% of OH groups is about 3 to 20 hours, preferably ≧4 hours, more preferably ≧5 hours, preferably ≦18 hours, more preferably ≦15 hours.

[0243] For the sake of completeness, it should be mentioned that in addition to the main reaction of oxidation of OH groups to COOH groups, oxidative decomposition also occurs to a lesser extent. In such oxidative decomposition, a small number of alkylene oxide units may be completely oxidized. As a result, the inner chain length of the partially oxidized alkylene oxide is inevitably slightly shorter than that of the alkylene oxide from which it was derived before the partial oxidation.

[0244] After the reaction is completed, the reaction mixture is usually removed from the reactor and separated from the catalyst. If a suspended catalyst is used, it is advisable to remove it by filtration. Alternatively, it is possible to allow the suspended catalyst to settle to the bottom of the reactor after the reaction is completed and remove the supernatant. It is also possible to separate the catalyst using centrifugation. The removed catalyst can generally be reused without further workup. The water or at least a large part of the water is usually removed by distillation, for example by a thin film evaporator. The partially oxidized polyalkylene oxide can then be used in the esterification step.

[0245] The polyalkylene oxide ester polymers of the present invention can replace conventional polyalkylene oxide polymers in a wide range of applications.

[0246] Products containing or made with such polyalkylene oxide ester polymers are significantly more biodegradable than similar products containing or made with conventional polyalkylene oxide polymers.

[0247] The polyalkylene oxide ester polymers used as the polymer backbone A of the present invention are a new type of polymer that can replace the usual applications of polyalkylene oxides, especially polyethylene oxide, polypropylene oxide, poly-1,2-butylene oxide and polytetrahydrofuran, such as in the encapsulation of perfumes and in the preparation of graft polymers for use in home care and laundry applications. Some of the application properties of the polyalkylene oxide ester polymers are even improved over those of conventional polyalkylene oxides. The greatest advantage of this new type of polymer is the greatly improved biodegradability, which can be important in contributing to environmental protection, because, in particular, the polyalkylene oxide ester polymers can easily replace conventional polyalkylene oxides in home care and laundry applications. The polyalkylene oxide ester polymers are safe and durable in their applications.

[0248] Moreover, the polyalkylene oxide ester polymers of the present invention can be easily prepared in high yields in a two-step process from readily available starting materials.

[0249] This also applies to graft polymers based on polyalkylene oxide ester polymers, which are described in more detail below.

[0250] Graft Polymer The graft polymers of the present invention comprise a polymeric backbone (A) as defined above using the two structural definitions of the PAG-ester / polyalkylene oxide ester polymers, and a polymeric side chain (B) attached to the polymeric backbone, the polymeric side chain (B) comprising at least one vinyl ester monomer (B1) and optionally at least one olefinically unsaturated monomer (B2) different from monomer (B1), preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, and the remaining amount of vinyl ester can be any other known vinyl ester, but most preferably no such other vinyl esters are present.

[0251] As regards the polymeric side chain (B) contained in the graft polymer according to the invention, it is preferred that the polymeric side chain (B) is obtained by radical polymerization of at least one vinyl ester monomer (B1) and, optionally, at least one olefinically unsaturated monomer (B2) different from the monomer (B1), preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) being selected from vinyl acetate and vinyl propionate, more preferably vinyl acetate, the remaining amounts of vinyl esters being any other known vinyl esters.

[0252] Preferably, only vinyl acetate and / or vinyl propionate are used as vinyl esters, more preferably at least 80 weight percent, even more preferably at least 90 weight percent of the vinyl esters used are vinyl acetate, and most preferably essentially only vinyl acetate (i.e., about 100 weight % or even 100 weight %) is used.

[0253] As vinyl ester monomer (B1), besides vinyl acetate or vinyl propionate, any other vinyl ester known to the skilled artisan can be used, such as vinyl valerate, vinyl pivalate, vinyl laurate, vinyl neodecanoate (for example VEOVA9 and VEOVA10), vinyl decanoate or vinyl benzoate. The vinyl ester is preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate.

[0254] As the optional at least one olefinically unsaturated monomer (B2) different from the monomer (B1), in principle it is possible to use any monomer which is polymerizable with the monomer (B1), for example the monomers defined below as B2a) and B2b):

[0255] The monomers B2a) are selected from: - N-vinyllactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, their derivatives substituted with C1-C8-alkyl groups, such as 3-methyl-, 4-methyl- or 5-methyl-N-vinylpyrrolidone; N-vinylamides, such as N-vinylformamide and its N-vinylamines which can be obtained by polymerization followed by hydrolysis, N-vinyl-N-methylacetamide and its derivatives.

[0256] Preferred monomers B2a) are vinyllactams, such as N-vinylpyrrolidone, 3-methyl-N-vinylpyrrolidone, 4-methyl-N-vinylpyrrolidone, 5-methyl-N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam.

[0257] More preferred monomers B2a) are N-vinylpyrrolidone, N-vinylcaprolactam.

[0258] A particularly preferred monomer B2a) is N-vinylpyrrolidone.

[0259] Suitable monomers B2b) are shown below: Salts, esters and amides of carboxylic acids, such as acrylic acid and derivatives thereof, such as substituted acrylic acids, in which the substituents are on the 2nd or 3rd carbon atom of the acrylic acid and are selected, independently of one another, from the group consisting of C1-C4-alkyl, -CN and -COOH. Preferred salts are the salts of these acids with alkanolamines, such as ethanolamine.

[0260] These monomers B2b) include, for example, those shown below: acrylic acid, for example acrylic acid itself or its anhydride, methacrylic acid, ethylacrylic acid, 3-cyanoacrylic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride or its half esters, itaconic acid or its half esters; - acrylamides, such as acrylamide itself, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-1-propylacrylamide, N-2-propylacrylamide, N-butylacrylamide, N-2-butylacrylamide, Nt-butylacrylamide, N-octylacrylamide, Nt-octylacrylamide, N-octadecylacrylamide, N-phenylacrylamide, N-dodecylacrylamide, lauryl acrylamide, stearyl acrylamide, N-2-hydroxyethylacrylamide, N-3-hydroxypropylacrylamide, N-2-hydroxypropylacrylamide; - methacrylamides, such as methacrylamide itself, N-methylmethacrylamide, N,N-dimethylmethacrylamide, N-ethylmethacrylamide, N-1-propylmethacrylamide, N-2-propylmethacrylamide, N-butylmethacrylamide, N-2-butylmethacrylamide, Nt-butylmethacrylamide, N-octylmethacrylamide, Nt-octylmethacrylamide, N-octadecylmethacrylamide, N-phenylmethacrylamide, N-dodecylmethacrylamide, N-laurylmethacrylamide, stearyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide; further amides, for example ethacrylamide, maleimides, fumaric acid monoamides, fumaric acid diimides; aminoalkyl(meth)acrylamides, such as (dimethylamino)methyl(meth)acrylamide, 2-(dimethylamino)ethyl(meth)acrylamide, 2-(dimethylamino)propyl(meth)acrylamide, 2-(diethylamino)propyl(meth)acrylamide, 3-(dimethylamino)propyl(meth)acrylamide, 3-(diethylamino)propyl(meth)acrylamide, 3-(dimethylamino)butyl(meth)acrylamide, 4-(dimethylamino)butyl(meth)acrylamide, 8-(dimethylamino)octyl(meth)acrylamide, 12-(dimethylamino)dodecyl(meth)acrylamide or analogues thereof which are quaternized with, for example, methyl chloride, ethyl chloride, dimethyl sulfate or diethyl sulfate, such as, for example, 3-(trimethylammonium)propyl(meth)acrylamidochloride; - acrylic esters, for example acrylic acid C1-C18-alkyl esters, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-methoxypropyl acrylate, 3-methoxypropyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxypropyl acrylate, 3-ethoxypropyl acrylate, glyceryl monoacrylate, alkylene glycol acrylates or acrylates of polyalkylene glycols having a total of 2 to 200 EO units and / or PO units and / or EO / PO units and having a hydroxy group, an amino group, a carboxylic acid group, a sulfonic acid group or an alkoxy group, e.g., a methoxy group or an ethoxy group, at the chain end ("EO" means "ethylene oxide" and "PO" means propylene oxide); methacrylic acid esters, for example methacrylic acid C1-C18-alkyl esters, for example methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxypropyl methacrylate, 3-methoxypropyl methacrylate, 2-ethoxyethyl methacrylate, 2-ethoxypropyl methacrylate, 3-ethoxypropyl methacrylate, glyceryl monomethacrylate, as well as alkylene glycol methacrylates or polyalkylene glycol methacrylates having a total of 2 to 200 EO units and / or PO units and / or EO / PO units and having a hydroxy group, an amino group, a carboxylic acid group, a sulfonic acid group or an alkoxy group, for example a methoxy group or an ethoxy group, at the chain end; - ethacrylic acid esters, for example ethacrylic acid C1-C18-alkyl esters, for example methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, isobutyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2-hydroxyethyl ethacrylate, 2-methoxyethyl ethacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl ethacrylate; - amino-C1-C18-alkyl (meth)acrylate esters, such as N,N-dimethylaminomethyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, N,N-dimethylaminohexyl (meth)acrylate, N,N-dimethylaminooctyl (meth)acrylate, N,N-dimethylaminododecyl (meth)acrylate, or analogs thereof which are quaternized with, for example, methyl chloride, ethyl chloride, dimethyl sulfate or diethyl sulfate; - alkyl esters, for example homogeneous or mixed diesters of maleic acid with methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, alkylene glycols or polyalkylene glycols having a total of 2 to 200 EO and / or PO and / or EO / PO units and carrying hydroxy, amino, carboxylic, sulfonic or alkoxy groups, for example methoxy or ethoxy groups, at the chain ends; - alkyl esters of C1-C40 linear, C3-C40 branched or C3-C40 carbocyclic carboxylic acids; vinyl ethers, for example methyl, ethyl, butyl or dodecyl vinyl ether; - ethers of allyl alcohol with polyethylene oxide and / or propylene oxide and / or poly(ethylene oxide-co-propylene oxide) having from 2 to 200 EO and / or PO and / or EO / PO units and carrying hydroxy, amino, carboxylic, sulfonic or alkoxy groups, such as methoxy or ethoxy groups, at the chain ends; - N-vinyloxazolines, such as N-vinyloxazoline, N-vinylmethyloxazoline, N-vinylethyloxazoline, N-vinylpropyloxazoline, N-vinylbutyloxazoline, N-vinylphenyloxazoline; - halides, such as vinyl or allyl halides, for example vinyl chloride, allyl chloride, vinylidene chloride; - olefinically unsaturated hydrocarbons, for example hydrocarbons having at least one carbon-carbon double bond, such as styrene, alpha-methylstyrene, tert-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, vinyltoluene; sulfonic acids, such as unsaturated sulfonic acids, such as acrylamidopropanesulfonic acid, more preferably their salts, such as styrenesulfonate; - Methyl vinyl ketone, vinyl furan, allyl alcohol.

[0261] Preferred monomers B2b) are the salts and esters of these acids, particularly preferably acrylic acid and methacrylic acid.

[0262] Very particularly preferred monomers B2b) are the esters of these acids, particularly preferably acrylic and methacrylic acid, and particularly preferably with C1-C10-alkanols, preferably C1-C6-alkanols.

[0263] In a particularly preferred embodiment, as monomers B2, only B2a monomers are present; in a further preferred embodiment, only N-vinylpyrrolidone is present as monomer B2.

[0264] In the case of at least one optional further monomer (B2), preferably only B2a monomers, more preferably vinyllactams and most preferably N-vinylpyrrolidone, are used to prepare the polymeric side chain (B) in the graft polymer according to the invention, the ratio of the essential vinyl ester monomer (B1) to said further monomer (B2) can be any value known to the skilled person; however, the amount of vinyl ester monomer (B1) is usually 1% by weight or more (relative to the sum of (B1) and (B2)). As a result, preferably, the polymeric side chain (B) can be obtained by radical polymerization of 1 to 100% by weight, more preferably 30 to 100% by weight of monomer (B1), most preferably vinyl acetate, with 0 to 99% by weight, more preferably 0 to 70% by weight of B2 monomer as optional further monomer (B2), most preferably N-vinylpyrrolidone.

[0265] Preferably, the polymer side chain (B) in connection with the present invention is (B1) 30 to 100% by weight (based on the total of (B1) and (B2)), preferably 60 to 100% by weight, more preferably 80 to 100% by weight, of at least one vinyl ester monomer (B1) preferably selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate; (B2) 0 to 70% by weight (based on the sum of (B1) and (B2)), preferably 0 to 40% by weight, more preferably 0 to 20% by weight, of at least optional further monomers (B2) as further monomers (B2), preferably only B2a monomers, more preferably only vinyl lactams, most preferably only N-vinylpyrrolidone, It can be obtained by free radical polymerization.

[0266] Thus, the graft polymers of the present invention comprise a polymer backbone (A) as defined above in accordance with the two structural definitions of the PAG-ester / polyalkylene oxide ester polymers detailed above, and a polymer side chain (B) attached to said polymer backbone, said polymer side chain (B) being (B1) 30 to 100% by weight (based on the total of (B1) and (B2)), preferably 60 to 100% by weight, more preferably 80 to 100% by weight, of at least one vinyl ester monomer (B1) preferably selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate; (B2) 0 to 70% by weight (based on the sum of (B1) and (B2)), preferably 0 to 40% by weight, more preferably 0 to 20% by weight, of at least optional further monomers (B2) as further monomers (B2), preferably only B2a monomers, more preferably only vinyl lactams, most preferably only N-vinylpyrrolidone, It is.

[0267] The grafted polymer of the present invention may contain a certain amount of ungrafted polymers ("ungrafted side chains") formed from vinyl esters, e.g. polyvinyl acetate when only vinyl acetate is used, and / or homo- and copolymers of vinyl esters and other monomers when further monomers are used. The amount of such ungrafted vinyl acetate homo- and copolymers can be high or low depending on the reaction conditions, but is preferably reduced and thus low. By this reduction, the amount of grafted side chains is preferably increased. This reduction can be achieved by suitable reaction conditions, e.g. the input amount of vinyl ester and radical initiator and their relative amounts plus the amount relative to the backbone present. This is generally known to those skilled in the art. The clarity of the polymer solution is also improved by keeping such amount of ungrafted vinyl ester polymer low, since it is known that homopolymers of vinyl esters, especially vinyl acetate, can cause turbidity even when present in aqueous solution at as low as 500 ppm.

[0268] The grafted polymers of the present invention can be characterized by their degree of grafting (the number of sites on the polymer backbone (A) where the polymer side chains (B) are grafted). The degree of grafting can be high or low depending on the reaction conditions. Preferably, the degree of grafting is low.

[0269] Adjustments to the degree of grafting and the amount of ungrafted polymer can be made to optimize performance in a particular area of ​​interest, such as desired performance in a particular (e.g., detergent) formulation, application area, or cleaning.

[0270] Further preferred in the context of the present invention, the polymeric side chains (B) are obtained by radical polymerization of 100% by weight (relative to the total amount of monomers used) of at least one vinyl ester monomer (B1), preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate.

[0271] In the context of the present invention, in the corresponding polymerization process to obtain the polymer side chain (B), more preferably no other monomers are used than at least one vinyl ester monomer (B1) and optionally at least any further optional monomers (B2), preferably only B2a monomers, more preferably only vinyl lactams as optional further monomers (B2), most preferably only N-vinylpyrrolidone.

[0272] However, in a preferred embodiment, if any further polymeric monomers are present other than the monomer according to (B1) and the optional preferred N-vinyl lactam (B2a), then such monomers (other than at least one N-vinyl lactam as B1 and B2a) are present in an amount of less than 1% of the total amount of monomers used to obtain the polymer side chain (B). Most preferably, the amount of said additional monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably no further monomers are present other than monomer (B1) and optionally at least the optional further monomer (B2), preferably only B2a monomers, more preferably a vinyl lactam as (B2), most preferably only N-vinylpyrrolidone.

[0273] The graft polymers of the present invention have at least one, and preferably two or more of the following properties, so that they can be successfully used in the various application fields targeted by the present invention: a) a certain level of biodegradation, such biodegradability being tested as defined elsewhere herein. To exhibit commercially useful biodegradation, the degree of biodegradation should be at least 25 percent, preferably at least 30%, more preferably at least 40%, even more preferably at least 60%, e.g., 35, 45, 55, 60, 65, 75, 80, 85 or more up to 100% (all percentages being weight percent based on total solids) within 56 days, and most preferably any of the percentages, preferred percentages, more preferred percentages, etc., set forth above within 28 days. b) It is necessary that the polymers exhibit some degree of water solubility so that they can be used in the aqueous environments that are typically present in the application fields that the present invention generally targets.Preferably, the polymers of the present invention should exhibit moderate to good solubility, more preferably good solubility, in the aqueous formulations typically used in such fields for various formulations, such as dishwashing, automatic dishwashing, hard surface cleaning, fabric washing, fabric care, agrochemical formulations, etc. c) The viscosity of the polymer solution must be such that it can be handled and provided to the user during and after production at a suitably high solid polymer concentration, for example as a "pure" (then normally liquid) product dissolved in a solvent, typically an aqueous solution comprising water and an organic solvent, water alone, or organic solvent alone, and the viscosity of such polymer or polymer solution is in a range that allows the usual technological process steps, such as pouring, pumping, dosing, etc. Thus, the viscosity should preferably be in the range of less than about 4000 mPas, more preferably up to 3500 mPas, more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750 or even up to 2600 or lower, such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150 or 100 mPas, with a polymer content (based on the total solids content of the polymer in the solution, which is defined as the weight percent of the dry polymer contained in the total weight of the polymer solution) of preferably at least 10% by weight, more preferably at least 20, even more preferably at least 40% by weight, most preferably at least 50% by weight, such as at least 60, 70, 80 or even 90% by weight. Viscosity can be measured either at 25°C or at elevated temperatures, such as at a temperature of 50°C or even at 60°C. This allows the polymer solution to be properly handled on a commercial scale. Of course, depending on the amount of solvent added, it is clear that as the amount of solvent increases, the viscosity decreases and vice versa, and can therefore be adjusted as desired. It is also clear that the measured viscosity depends on the measurement temperature, e.g. the viscosity of a given polymer with a given solids content, e.g. 80 wt%, will be higher when measured at a lower temperature and lower when measured at a higher temperature. In a preferred embodiment, the solids content of the as-prepared polymer without added solvent is between 70 and 99 wt%, more preferably between 75 and 85 wt%.In a more preferred embodiment, the solids content of the as-prepared polymer without added solvent is between 70-99 wt.%, more preferably between 75-95 wt.%, and the viscosity measured at 60° C. is less than 3000 mPas, more preferably less than 3250, or even less than 2750, less than 2600, less than 2500, less than 2000, less than 1750, less than 1500, less than 1250, less than 1000, less than 750, less than 500 or even less than 250 mPas.

[0274] To achieve these requirements, the following guidelines can be given as to how to achieve these properties of the grafted polymers of the present invention: Biodegradability is generally enhanced with at least one of the following conditions: · The molecular weight of the polymer backbone (A) is lower compared to the higher molecular weight; · A lower weight percentage of polymer side chains (monomer B) is grafted to the backbone compared to a higher weight percentage.

[0275] Of course, further criteria must be evaluated for the individual performance of a particular grafted polymer, and therefore for each individual formulation in a particular field of application. Because grafted polymers exhibit a wide variety of usefulness, no comprehensive overview can be given, but the present application and examples provide guidance on how to prepare and select useful grafted polymers having specific desired properties, and how to tailor the properties to the desired requirements.

[0276] One such criterion used in the home care and particularly fabric care field is, of course, performance in washing, for example, subjecting a particular material having a stain of a particular substance to a prescribed washing procedure.

[0277] In the examples some guidelines are given for application in the area of ​​fabric cleaning, i.e. general fabric care.

[0278] The agrochemical formulation examples also provide guidance as to how such grafted polymers can be used to obtain useful and stable formulations of agrochemically active substances.

[0279] Similarly, other active ingredients from other fields can be formulated in a similar manner, following the general guidelines set forth herein. A straightforward approach to such use of the grafted poylmers of the present invention is, of course, to first replace the conventional grafted polymer with one having a similar composition, but based on conventional polyalkylene glycols, and then, following the teachings set forth herein, fine-tune the properties of the grafted polymer of the present invention to meet specific requirements.

[0280] Depending on the particular need for a polymer with a defined biodegradability, water solubility and viscosity (i.e., handleability), how such a polymer may be obtained will be guided by the general and specific teachings herein, but is not intended to be limited to the specific examples presented.

[0281] Graft polymer manufacturing process Another subject of the present invention is a process for preparing the graft polymers of the invention as described above. In the process for obtaining at least one graft polymer according to the invention, at least one monomer (B1) and optionally at least one further monomer (B2), preferably only B2a monomers, more preferably vinyllactams, most preferably only N-vinylpyrrolidone (B2), are polymerized in the presence of at least one block copolymer backbone (A).

[0282] Thus, the graft polymers of the present invention are prepared by using a polymer backbone (A) as defined above by the two structural definitions of PAG-ester / polyalkylene oxide ester polymers, and attaching polymer side chains (B) to the polymer backbone by radical polymerization using the monomers shown below in the given amounts: (B1) at least one vinyl ester monomer (B1) in an amount of 30 to 100% by weight (based on the total weight of (B1) and (B2)), preferably 60 to 100% by weight, more preferably 80 to 100% by weight, and (B2) At least one optional at least one further monomer (B2) as further monomer (B2), preferably only B2a monomers, more preferably vinyl lactams, most preferably only N-vinylpyrrolidone, in an amount of 0 to 70% by weight (based on the sum of (B1) and (B2)), preferably 0 to 40% by weight, more preferably 0 to 20% by weight.

[0283] It should be noted that the grafting process itself, in which a polymer backbone, such as a polyethylene glycol-polymer backbone, is grafted with polymer side chains, is in principle known to the skilled person, and any process related thereto and known to the skilled person can in principle be adopted for the present invention.

[0284] In the process of the invention, the polymeric side chains (B) are preferably obtained by radical polymerization.

[0285] The radical polymerization itself is also known to those skilled in the art. The skilled artisan also understands that the process of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). The skilled artisan also understands each of the components itself.

[0286] "Radical polymerization" as used in the context of the present invention includes free radical polymerization as well as its variants such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each of which is known to those skilled in the art along with suitable control agents.

[0287] More preferably, the process according to the invention comprises the step of reacting at least one monomer (B1) selected from vinyl esters, preferably vinyl acetate, vinyl propionate, vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, in the presence of at least one PAG-ester backbone (A), a free radical-forming initiator (C) and, optionally, up to 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B1), optionally (B2) and (C), with the aim of obtaining polymer side chains (B), The process comprises polymerizing monomer B1 with one or more optional further monomers (B2) selected from polymerizable olefinically unsaturated monomers, preferably selected from monomers B2a, more preferably N-vinyl lactams, more preferably only N-vinylpyrrolidone, at an average polymerization temperature such that the decomposition half-life of initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted graft monomer (B1) and optional (B2) and initiator (C) in the reaction mixture is always maintained in a quantitative deficiency relative to the PAG-ester backbone (A).

[0288] The amount of ((free) radical-forming) initiator (C) can be any generally known amount, but is preferably from 0.1 to 5% by weight, in particular from 0.3 to 3.5% by weight, based in each case on the polymer side chain (B).

[0289] In the process according to the invention, preferably, the steady-state concentration of radicals present at the average polymerization temperature is substantially constant and the grafting monomer (B1) or (B2) is always present in the reaction mixture only in low concentrations (for example less than 5% by weight), which makes it possible to control the reaction and to prepare in a controlled manner graft polymers with the desired low polydispersity.

[0290] To ensure safe temperature control from the start of the polymerization temperature while a large or total amount of monomer is present, it is wise and therefore preferred to use additional efficient means for temperature control. This can be done by external or internal cooling; such cooling can be done by internal or external coolers such as heat exchangers, or by using a reflux condenser when operating at the boiling point of the solvent or solvent mixture.

[0291] By controlling the radical concentration and the amount of available polymerizable monomer, the temperature is at least partially controlled by the propagation of the polymerization reaction, and thus such temperature control may not be a significant issue if the radical and monomer concentrations are kept consistently low, although depending on the scale at which the polymerization is carried out, it becomes much more important at larger scales.

[0292] Of course, depending on the scale of the polymerization reaction, such additional cooling as described above may be necessary if the scale becomes large enough that the surface to volume ratio of the polymerization mixture becomes very high, but this is generally known to those skilled in the art of conducting commercial scale polymerizations and can therefore be adapted to suit the needs.

[0293] The term "average polymerization temperature" is intended herein to mean that the process is substantially isothermal, although temperature fluctuations may occur due to the exothermic nature of the reaction, and are preferably maintained within a range of + / - 10°C, more preferably within a range of + / - 5°C.

[0294] According to the present invention, the decomposition half-life of the (radical-forming) initiator (C) at the average polymerization temperature must be 40 to 500 minutes, preferably 50 to 400 minutes, and more preferably 60 to 300 minutes.

[0295] According to the invention, the initiator (C) and the grafting monomers (B1) and / or (B2) are advantageously added in such a way that undecomposed initiator and grafting monomers (B1) and / or (B2) are present in the reaction mixture in a substantially constant low concentration. The proportion of undecomposed initiator in the reaction mixture as a whole is preferably ≦15% by weight, in particular ≦10% by weight, based on the total amount of initiator metered in during the monomer addition.

[0296] The average polymerization temperature is suitably in the range of 50 to 140°C, preferably in the range of 60 to 120°C, and more preferably in the range of 65 to 110°C.

[0297] Examples of suitable initiators (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140° C. are shown below: -tert-C 4 ~C 12 -Alkyl hydroperoxide and tert-(C 9 ~C 12 -aralkyl) hydroperoxides, for example, OC of tert-butyl peracetate, 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. 2 ~C 12 -acylated derivatives; -tert-C 8 ~C 14-Alkylenebisperoxides, such as di-OC of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene 4 ~C 12 -acylated derivatives; - Ji (C 2 ~C 12 -alkanoyl) and dibenzoyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, disuccinic acid peroxide, dicapryloyl 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; - Peroxy (C 4 ~C 12 -alkyl)carbonate tert-C 4 ~C 5 -Alkyl, for example, peroxy(2-ethylhexyl) tert-amyl carbonate; - Peroxydicarbonate (C 2 ~C 12 -alkyl), for example, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0298] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are: - Average polymerization temperature 50~60℃: tert-Butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate, and di(2-ethylhexyl) peroxydicarbonate; - Average polymerization temperature 60~70℃: tert-Butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl)peroxide; - Average polymerization temperature 70~80℃: tert-Butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; - Average polymerization temperature 80~90℃: tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; - Average polymerization temperature 90~100℃: tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl peroxide); - Average polymerization temperature 100~110℃: tert-Butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate; - Average polymerization temperature 110~120℃: tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl)carbonate.

[0299] The preferred initiator (C) is tert-C 4 ~C 5 -Alkyl hydroperoxide OC4 ~C 12 -acylated derivatives, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0300] Particularly advantageous polymerization conditions can be easily set by precisely adjusting the initiator (C) and the polymerization temperature. For example, the preferred average polymerization temperature when tert-butyl peroxypivalate is used is 60 to 80°C, and when tert-butyl peroxy-2-ethylhexanoate is used is 80 to 100°C.

[0301] The polymerization reaction of the present invention can be carried out in the presence of an organic solvent (D), preferably in small amounts. It is of course also possible to use mixtures of different solvents (D). It is preferred to use water-soluble or water-miscible solvents.

[0302] If the solvent (D) is used as a diluent, it is generally used in an amount of 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 on the sum of the components (A), (B1), optionally (B2) and (C) in each case.

[0303] Examples of suitable solvents (D) include the following: - monohydric alcohol, preferably aliphatic C 1 ~C 16 -alcohols, more preferably aliphatic C 2 ~C 12 -alcohols, most preferably C 2 ~C 4 alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; - polyhydric alcohols, preferably C 2 ~C 10 -diols, more preferably C 2 ~C 6 -diols, most preferably C 2 ~C 4- alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol; - alkylene glycol ethers, preferably alkylene glycol mono(C 1 ~C 12 -alkyl) ethers and alkylene glycol di(C 1 ~C 6 -alkyl) ethers, more preferably alkylene glycol mono- and di(C 1 ~C 2 -alkyl) ethers, most preferably alkylene glycol mono(C 1 ~C 2 -alkyl) ethers, for example, ethylene glycol monomethyl and -ethyl ether and propylene glycol monomethyl and -ethyl ether; - polyalkylene glycol, preferably 2 to 20 C 2 ~C 4 -Poly(C 2 ~C 4 -alkylene) glycols, 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, for example, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; - polyalkylene glycol monoethers, preferably poly(C 2 ~C 4 -alkylene)glycol mono(C 1 ~C 25 -alkyl) ethers, more preferably poly(C 2 ~C 4 -alkylene)glycol mono(C 1 ~C 20-alkyl) ethers, most preferably poly(C 1 2 ~C 3 -alkylene)glycol mono(C 1 ~C 16 -alkyl) ethers; - Carboxylic acid esters, preferably C 1 ~C 6 -C for carboxylic acid 1 ~C 8 -alkyl esters, more preferably C 1 ~C 3 -C for carboxylic acid 1 ~C 4 -alkyl esters, most preferably C 2 ~C 3 -C for carboxylic acid 2 ~C 4 - alkyl esters, for example, ethyl acetate and ethyl propionate; aliphatic ketones, preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; - Cyclic ethers, in particular tetrahydrofuran and dioxane.

[0304] The solvent (D) is advantageously a solvent that is also used when formulating the graft polymer of the invention (for example for washing and cleaning compositions) and may therefore remain in the polymerization product.

[0305] Preferred examples of such solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units, and in particular C 6 ~C 8 -Alcohol alkoxylation products (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0306] In this specification, highly branched C 8 ~C 16Particularly preferred are alkoxylated alcohols, which allow the formulation of polymer mixtures with a free flowing property at 40-70° C. and a very low polymer content at relatively low viscosities. Branching may also be present in the alkyl chain of the alcohol and / or in the polyalkoxylate moiety (copolymerized with at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of such alkoxylated compounds are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol ethylene oxide, C alkoxylated with 1-15 mol ethylene oxide and 1-3 mol propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 Or C 16 / C 18 The fatty alcohol 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide is preferred.

[0307] In one embodiment, the solvent (D) used is water alone and the radical initiator is dissolved in a small amount of an organic solvent as disclosed later in this specification.

[0308] In another embodiment, the polymerization is carried out without the use of a solvent (D), except for the solvent required for the introduction of the radical initiator as disclosed later in this specification.

[0309] Small amounts of organic solvents may be used, preferably for introducing the radical initiator and the grafting monomers (B1) and / or (B2), which are, for example, not soluble in water, but only soluble to a reasonable extent in this type of organic solvent. Suitable organic solvents can be isopropanol, ethanol, 1,2-propanediol and / or tripropylene glycol and / or other suitable alcohols, or organic solvents such as 1-methoxy-2-propanol, which are fairly cheap and available for large-scale use, or solvents such as ethyl acetate, methyl ethyl ketone and the like, with isopropanol, 1,2-propanediol, 1-methoxy-2-propanol, ethyl acetate and / or tripropylene glycol being preferred co-solvents, with ethyl acetate and tripropylene glycol being even more preferred, and preferably introduced into the reaction in as small amounts as possible only as a solvent for the radical initiator and / or the grafting monomers (B1) and / or (B2), preferably only for the radical initiator.

[0310] Thus, when the total amount of alcohol or other organic solvent is reduced compared to water, such organic solvent may remain in the final polymer, preferably less than 1 weight percent, preferably less than 0.5 weight percent, and more preferably less than 0.1 weight percent based on the total amount of all solvents.

[0311] In the case of solvents with a boiling point below 110° C. at atmospheric pressure, such solvents can be partially or essentially completely removed by high temperature or vacuum distillation or stripping with a gas such as steam or nitrogen, preferably with water vapor, all at normal pressure or under reduced pressure, while solvents with higher boiling points will usually remain in the resulting polymer product. Thus, solvents such as 1-methoxy-2-propanol, 1,2-propanediol and tripropylene glycol will remain in the polymer product, and therefore their amount should be minimized as much as possible by using the highest possible concentration of radical initiator.

[0312] The radical initiator is preferably used in the form of a highly concentrated solution in one of the abovementioned solvents. The concentration, of course, depends on the solubility of the radical initiator. This concentration is preferably as high as possible so as to allow as little organic solvent as possible to be introduced into the polymerization reaction.

[0313] In the most preferred embodiment, the solvent (D) used is water alone and the radical initiator is dissolved in a small amount of an organic solvent as disclosed later in this specification. In the process according to the invention, the PAG-ester backbone (A), the grafting monomers (B1) and optionally (B2), the initiator (C) and, if appropriate, the solvent (D) are usually heated in a reactor to the selected average polymerization temperature.

[0314] According to the invention, the polymerization is carried out so that there is always an excess of polymer backbone (A) and formed graft polymer (B) in the reactor. The quantitative ratio of polymer to non-grafted monomer and initiator is generally ≧10:1, preferably ≧15:1, more preferably ≧20:1.

[0315] The polymerization process according to the invention can in principle be carried out in various types of reactors.

[0316] The reactor used is preferably a stirred tank into which first all or part of the polymer backbone (A) is charged together with, if appropriate, the graft monomers (B1) and (B2), the initiator (C) and part of the solvent (D), generally up to 15% by weight of the specific total amount, heated to the polymerization temperature, and (B), (C) and, if appropriate, the remaining amount of (D) are metered in, preferably separately. (B), (C) and, if appropriate, the remaining amount of (D) are metered in over a period of preferably ≥ 2 hours, more preferably ≥ 4 hours, most preferably ≥ 5 hours.

[0317] If more than monomer B1 and / or more than one monomer B2 is used, such monomers can be added either as one or more mixtures of any monomer, for example all the vinyl esters in one mixture and all the monomers B2 in another mixture; such different mixtures can be added within the same or different time frames, preferably in parallel.

[0318] In the substantially solvent-free process variant thereof, which is particularly preferred, the entire amount of the polymer backbone (A) is initially charged as a melt, and the grafting monomers (B1) and, if appropriate, (B2) and, in addition, the initiator (C), which is preferably present in the form of a 10-50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled in such a way that the selected average polymerization temperature is maintained during the polymerization, in particular within the range of + / - 10°C, in particular within the range of + / - 5°C.

[0319] In a further particularly preferred variant, the low-solvent process, the procedure is as described above, except that the solvent (D) is metered in during the polymerization to limit the viscosity of the reaction mixture. It is also possible to start the metered addition of the solvent only at a later point in time once the polymerization has progressed, or to add it in small portions.

[0320] The polymerization can be effected at normal pressure or at reduced or elevated pressure. If at the selected pressure the boiling points of the monomers (B1) or (B2) or of the optional diluent (D) used are exceeded, the polymerization is carried out with reflux cooling.

[0321] 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 more than 0.5 hours and up to 3 hours, preferably about 1-2 hours, more preferably about 1 hour, with the radical initiator and the solvent for the initiator typically and preferably being the same as the solvent for the main polymerization reaction. Of course, a different radical initiator and / or a different solvent can also be used.

[0322] The main polymerization reaction can be allowed to proceed for a period of time between the post-polymerization and the main polymerization, after which the post-polymerization reaction can be started by commencing the addition of additional radical initiator.

[0323] The temperature of the post-polymerization process step may be the same as that of the main polymerization reaction (preferred in the present invention) or may be increased, typically by about 5 to 40°C, preferably 10 to 20°C.

[0324] In the case of solvents with atmospheric boiling points below about 110° C., such solvents can be partially or essentially completely removed by high temperature or vacuum distillation or stripping with a gas such as steam or nitrogen, preferably with water vapor, all at normal pressure or under reduced pressure, while higher boiling solvents will usually remain in the resulting polymer product. Thus, such high boiling solvents will usually remain in the polymer product and therefore their amount should be minimized as much as possible, for example by using as high a radical initiator concentration as possible, longer polymerization times, post-polymerization reaction steps, etc.

[0325] The grafted polymer of the present invention can be subjected to a concentration or drying means. The obtained grafted polymer solution can be concentrated by removing a portion of the solvent to increase the solid polymer concentration. This can be achieved by carrying out a distillation process, such as high temperature or vacuum distillation, until the desired solid content is reached. This type of process can be combined with a purification step, in which case the obtained grafted polymer solution is purified by removing a desired amount of solvent to remove some or all of the volatile components, such as volatile solvents and / or unreacted volatile monomers.

[0326] After the main polymerization and optional post-polymerization steps and optional purification steps, the grafted polymer solution can also be concentrated or dried by subjecting it to drying means such as roller-drum drying, spray drying, vacuum drying or freeze drying, preferably, mainly for cost reasons, spray drying. Such drying processes can also be combined with agglomeration processes, such as spray-agglomeration or drying in a fluidized bed dryer.

[0327] Use of PAG-ester based graft polymers / polyalkylene oxide polymers as polymer backbones In principle, the grafted polymers of the present invention can be used in any application replacing conventional grafted polymers having the same or very similar composition (in terms of the polymer backbone and the amount of grafted monomers, in particular the type and amount of grafted monomers are similar or equivalent or even nearly identical to conventional PEG or non-PEG PAG based grafted polymers). Examples of such applications are given below:

[0328] Cosmetics, personal care Compositions and formulations of this type include shampoos, lotions, gels, sprays, soaps, make-up powders, lipsticks and hairsprays.

[0329] technical application Compositions and formulations of this type include use as dispersants in any type of adhesive, non-aqueous and preferably aqueous liquid or solid formulations, any type of dispersion where it is typically required to disperse a solid or liquid in another liquid or solid, such as in oil field applications or automotive applications.

[0330] Lacquer, paint and colour formulations Compositions and formulations of this type include non-aqueous and preferably aqueous lacquers as well as stains, paints and finishes.

[0331] agricultural formulations Compositions and formulations of this type include those which contain agrochemically active materials in a liquid or solid environment.

[0332] fragrance formulation Compositions and formulations of this type include formulations in which the perfume is dissolved or dispersed in a liquid or solid composition so as to be uniformly dispersed and / or to maintain its stability in order to maintain its scent profile over time; also included are compositions which release the perfume over time, e.g., extended release or delayed release formulations.

[0333] Other subjects of the present invention are therefore the use of the grafted polymers in fabric care and home care products, in cosmetic and personal care formulations, as emulsion breakers for crude oil, in technical applications such as pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions, in agrochemical formulations, for example as dispersants, crystal growth inhibitors and / or solubilizers, in lacquer and colorant formulations, preferably in agrochemical and cleaning compositions and in fabric care and home care products, in particular in cleaning compositions, preferably laundry and / or dishwashing detergent formulations, more preferably liquid laundry and / or hand dishwashing detergent formulations, for improving the removal of oily and greasy soils, for removing solid soils such as clay, for preventing dark stains on fabric surfaces and / or as scale inhibitors, or in particular for use as dispersants, crystal growth inhibitors and / or solubilisers in agrochemical compositions.

[0334] Other subjects of the present invention are therefore cleaning compositions, fabric care and home care products, industrial cleaning products, cosmetic or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inkjet inks and inks containing the grafted polymers, electroplating products, cement-based compositions, lacquers or paints and dispersants for agrochemical formulations, comprising at least one grafted polymer as defined above.

[0335] In a preferred embodiment, it is a cleaning composition and / or a fabric and home care product and / or an institutional cleaning product comprising at least one grafted polymer as defined above.In particular, it is a cleaning composition for improving the removal of oily and greasy soils, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0336] In one embodiment, also preferred according to the invention, the cleaning composition further comprises (besides the at least one grafted polymer as defined above) at least one enzyme, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above indicated types.

[0337] Another subject of the present invention is therefore cleaning compositions, such as fabric care and home care products and institutional (I&I) cleaning products, comprising at least one grafted polymer as defined above, in particular cleaning compositions for removing oily and / or greasy soils.

[0338] At least one graft polymer described herein is present in the cleaning composition of the present invention at a concentration of 0.1 to 10, preferably about 0.25% to 5%, more preferably about 0.5% to about 3%, and most preferably about 1% to about 3%, based on the total weight of such composition, and such cleaning composition may further comprise, and preferably further comprises, about 1% to about 70% by weight of a surfactant system.

[0339] Preferably, such cleaning compositions of the present invention are fabric and home care products or institutional (I&I) cleaning products, preferably fabric and home care products, more preferably laundry detergents or hand dishwashing detergents comprising at least one polymer of the present invention and optionally further comprising at least one surfactant or surfactant system to enhance soil removal, dispersion and / or emulsification and / or modify treated surfaces and / or maintain the whiteness of treated surfaces.

[0340] More preferably, the cleaning compositions of the present invention comprising at least one grafted polymer of the present invention and optionally further comprising at least one surfactant or surfactant system are intended for primary cleaning (i.e., removal of stains) in laundry and hand dishwashing applications, more particularly for the removal of oily and fatty stains such as fabric and dish stains, and further comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above mentioned types of enzymes.

[0341] At least one grafted polymer as described herein and / or obtained or obtainable by the process of the present invention as detailed above is present in said compositions and products of the present invention at a concentration of about 0.05% to about 20%, preferably 0.05 to 10%, more preferably about 0.1% to 8%, even more preferably about 0.2% to about 6%, even more preferably about 0.2% to about 4%, and most preferably up to 2%, by weight based on the total weight of such composition or product, respectively, including any range generated by selecting any of the lower limits and any of the upper limits mentioned and any numerical values ​​therebetween; said composition or product can further comprise, and preferably does comprise, a surfactant system, at about 1% to about 70% by weight of the composition or product.

[0342] More preferably, the composition or product of the invention as detailed herein above, comprising at least one grafted polymer of the invention as detailed herein above and / or at least one grafted polymer obtained or obtainable by the process of the invention as detailed herein above, in the amount as specified in the paragraph above, and optionally further comprising at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, for primary cleaning (i.e. removing soils) in laundry applications, further comprising at least one enzyme selected from lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersin, pectinase, oxidoreductase, cutinase, lactase and peroxidase, more preferably at least two of the above mentioned types.

[0343] In one embodiment of the present invention, the grafted polymer of the present invention can be used for removing particulate soils and / or oily and greasy soils, as well as preferably for maintaining whiteness in laundry care. In another preferred embodiment, the grafted polymer of the present invention can be used to reduce dark stains on fabrics (anti-darkening stains).

[0344] In one preferred embodiment, the cleaning compositions of the present invention are liquid or solid laundry detergent compositions.

[0345] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g., powder or tablet / unit dose) detergent composition for hand dishwashing or for automatic dishwashing, preferably a liquid hand dishwashing detergent composition.

[0346] In another embodiment, the cleaning compositions of the present invention are hard surface cleaning compositions that can be used to clean a variety of surfaces such as hardwood, tile, ceramic, plastic, leather, metal, glass, and the like.

[0347] In other embodiments, the cleaning compositions are designed for use in cosmetic, personal care and pet care compositions, such as shampoo compositions, personal washes, liquid or bar soaps, etc.

[0348] In one embodiment, the grafted polymer of the present invention can be utilized in a cleaning composition comprising a surfactant system comprising C10-C15 alkylbenzene sulfonate (LAS) as a surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0349] In a further embodiment, the graft polymer of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, comprising a C8 to C18 linear or branched alkyl ether sulfate salt containing 1 to 5 ethoxy units as a surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0350] In a further embodiment, the grafted polymer of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, that contain a C12-C18 alkyl ethoxylate surfactant containing 5-10 ethoxy units as the surfactant base, and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

[0351] In one embodiment of the present invention, the grafted polymer is a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or hand dishwashing detergent formulation, each further comprising at least one surfactant, preferably at least one anionic surfactant.

[0352] In a further embodiment, the present invention also encompasses compositions comprising the grafted polymer as described herein above, such compositions being preferably detergent compositions, such compositions further comprising an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably in an amount ranging from 2 ppm to 5% by weight of the composition; and even more preferably 0.1 to 2% phenoxyethanol.

[0353] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition from microbial contamination or growth, such composition comprising a grafted polymer as described herein above, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the antimicrobial agents of the present disclosure as disclosed hereinafter, such antimicrobial agent being preferably 2-phenoxyethanol.

[0354] In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid laundry softener composition, each of which comprises a grafted polymer and / or a polymer backbone as described herein above, and each of which further comprises 4,4'-dichloro 2-hydroxydiphenyl ether, at a concentration of from 0.001 to 3%, preferably from 0.002 to 1%, more preferably from 0.01 to 0.6%, by weight of the composition.

[0355] In a further embodiment, the present invention also encompasses a method of laundering a fabric or cleaning a hard surface, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably with a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably with a liquid laundry detergent composition or a liquid laundry softener composition, such compositions comprising a grafted polymer and / or a polymer backbone, respectively, as described herein above, such compositions further comprising 4,4'-dichloro 2-hydroxydiphenyl ether.

[0356] The selection of additional surfactant agents and further ingredients in these embodiments can depend on the application and the benefit desired.

[0357] Description of cleaning compositions, formulations and their ingredients As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface.

[0358] "Industrial cleaning" compositions include cleaning compositions designed for use in industrial cleaning, e.g., for use in cleaning any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces.

[0359] "Fabric care and home care compositions" include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-wash detergents, laundry pre-treatments, laundry aids, spray products, dry cleaning agents or compositions, laundry rinsing additives, cleaning additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or within porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pre-treatments, laundry post-treatments, or may be added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation.

[0360] The cleaning compositions of the present invention can be in any form, i.e., liquid form; solids such as powders, granules, aggregates, pastes, tablets, sachets, bars, gels, etc.; emulsions; the type delivered in two or multiple compartment containers; single or multi-phase unit doses; spray or foam cleaners; wet wipes (i.e., the cleaning composition is combined with a nonwoven material such as those described in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes that are activated by the user or consumer by wetting with water (i.e., the cleaning composition is combined with a nonwoven material such as those described in U.S. Pat. No. 5,980,931 to Fowler et al.); or other homogeneous, heterogeneous, or single or multi-phase cleaning products.

[0361] The liquid cleaning compositions of the present invention preferably have a viscosity of 50 to 10000 mPa·s, the liquid manual dish wash cleaning composition compositions (or liquid manual "dish wash compositions") preferably have a viscosity of 100 to 10000 mPa·s, more preferably 200 to 5000 mPa·s, and most preferably 500 to 3000 mPa·s, at 20 1 / s and 20°C, and the liquid laundry cleaning compositions preferably have a viscosity of 50 to 3000 mPa·s, more preferably 100 to 1500 mPa·s, and most preferably 200 to 1000 mPa·s, at 20 1 / s and 20°C.

[0362] The liquid cleaning composition of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4-14. More preferably, the composition has a pH of 6-13, even more preferably 6-10, and most preferably 7-9. The pH of the composition may be adjusted using pH adjusting ingredients known in the art, measured at a product concentration of 10% in demineralized water at 25°C. For example, NaOH may be used, the actual weight % of NaOH may vary, and a desired pH, such as pH 8.0, may be achieved. In one embodiment of the present invention, the pH may be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0363] Cleaning compositions, such as fabric care and home care products and commercial cleaning formulations, more specifically laundry and hand dishwashing detergents, are known to those skilled in the art. Any compositions known to those skilled in the art related to the respective application can be used in the context of the present invention by including at least one of the polymers of the present invention, preferably at least one polymer, in an amount suitable for developing specific properties in such compositions, especially when such compositions are used in their field of use.

[0364] An aspect of the present invention is also the use of the polymers of the present invention in detergent formulations, in particular liquid detergent formulations, preferably concentrated liquid detergent formulations or as single doses for laundry.

[0365] The cleaning compositions of the present invention may, and preferably do, contain cleaning adjuncts (sometimes abbreviated herein as "adjuncts"), which are preferably in addition to the surfactant system defined above.

[0366] Suitable cleaning adjuncts include builders, co-builders, structurants or thickeners, clay soil removal / anti-resoil agents, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric degreasers, solubilizers, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, optical brighteners, malodor control agents, pigments, dyes, opacifying agents, color correctors, color transfer inhibitors, chelating agents, foam boosters, foam suppressors (defoamers), color speckles, silver care agents, anti-tarnish and / or corrosion inhibitors, alkalizing agents, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antimicrobial agents, antioxidants, softening agents, carriers, processing aids, fragrance precursors, and fragrances.

[0367] The liquid cleansing composition may additionally comprise, and preferably does comprise, at least one of a rheology control / regulator, an emollient, a moisturizer, a skin rejuvenation active, and a solvent.

[0368] The solid composition may additionally comprise, and preferably does comprise, at least one of a filler, a bleaching agent, a bleach activator, and a catalytic material.

[0369] Suitable examples of such cleaning auxiliaries and amounts used are described in WO 99 / 05242, US Pat. No. 5,576,282, US Pat. No. 6,306,812 B1 and US Pat. No. 6,326,348 B1.

[0370] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that is useful in cleaning, removing stains or laundering soiled materials.

[0371] Thus, cleaning compositions of the present invention, such as fabric care and home care products and institutional cleaning formulations, more particularly laundry and hand dishwashing detergents, preferably additionally comprise a surfactant system as described above and in more detail below, and more preferably further comprise adjuvants.

[0372] The surfactant system can be composed of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. Those skilled in the art will understand that a detergent surfactant system includes any surfactant or mixture of surfactants that is beneficial for cleaning, removing stains or laundering soiled materials.

[0373] The cleaning compositions of the present invention preferably contain a surfactant system in an amount sufficient to impart the desired cleaning properties. In some embodiments, the cleaning composition contains from about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition contains from about 2% to about 60% of the surfactant system by weight of the composition. In further embodiments, the cleaning composition contains from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may include a cleaning surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof.

[0374] (a) Laundry composition In laundry formulations, anionic surfactants usually constitute the largest and by far the largest proportion of surfactants contained in such formulations.Thus, preferably, the cleaning composition of the present invention for use in laundry comprises at least one anionic surfactant and, optionally, further surfactants selected from any of the surfactant classes described herein, preferably nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0375] In one embodiment of the invention, the laundry formulation according to the invention further comprises at least one enzyme.

[0376] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the aforementioned types.

[0377] Such enzymes may be incorporated at levels sufficient to provide an effective amount for cleaning. A preferred amount is in the range of 0.001% to 5% by weight of the detergent composition according to the invention of active enzyme. Enzyme stabilizing systems may also be used together with the enzymes, such as, for example, calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids. The short chain carboxylic acids relevant to the present invention are selected from monocarboxylic acids having 1 to 3 carbon atoms per molecule and from dicarboxylic acids having 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH 2 ) 3 COOH, adipic acid and mixtures of at least two of the above, as well as the respective sodium and potassium salts.

[0378] Preferably, the at least one enzyme is a detergent enzyme.

[0379] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). This EC number assignment is in accordance with the Enzyme Nomenclature, Recommendations, Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including addenda published in 1993-1999. Preferably, the enzyme is a hydrolase (EC 3).

[0380] In a preferred embodiment, the enzyme is: Protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, cutinase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonuclease, phosphodiesterase, phytase, carbohydrase, The enzyme is selected from the group consisting of galactanase, xanthanase, xyloglucanase, oxidoreductase, perhydrolase, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersin, and combinations of at least two of the above mentioned types. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, deoxyribonuclease, dispersin, pectinase, oxidoreductase, and cutinase, and combinations of at least two of the above mentioned types. Most preferably, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin protease.

[0381] Preferably, the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and with the amino acid substitution R101E (according to the BPN residue numbering). Preferably, the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1.

[0382] Such enzymes may be incorporated into the compositions at a level sufficient to provide an effective amount to achieve a beneficial effect, preferably a primary cleaning effect and / or a secondary cleaning effect such as an anti-blackening or anti-pilling effect (e.g., in the case of cellulases). Preferably, the enzyme is present in the composition at a level such that the enzyme protein is from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, and even more preferably from about 0.001% to about 0.5% by weight of the composition.

[0383] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0384] Preferably, the enzyme-containing compositions described herein comprise from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6% of an enzyme stabilization system by weight of the composition. The enzyme stabilization system can be any stabilization system compatible with the enzyme.

[0385] Preferably, the enzyme stabilization system comprises at least one compound selected from the group consisting of a polyol (preferably 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol or sorbitol), an inorganic salt (preferably CaCl2, MgCl2 or NaCl), a short-chain (preferably C1-C3) carboxylic acid or a salt thereof (preferably formic acid, a formate (preferably sodium formate), acetic acid, an acetate or a lactate), a borate, boric acid, a boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), a peptide aldehyde, a peptide acetal and a peptide aldehyde hydrosulfite adduct. Preferably, the enzyme stabilization system comprises a combination of at least two compounds selected from the group consisting of salts, polyols and short chain carboxylic acids, preferably one or more compounds selected from the group consisting of borate, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehyde, peptide acetal and peptide aldehyde hydrosulfite adduct. In particular, when a protease is present in the composition, a protease inhibitor preferably selected from borate, boric acid, boronic acid (preferably 4-FPBA), peptide aldehyde (preferably a peptide aldehyde such as Z-VAL-H or Z-GAY-H), peptide acetal and peptide aldehyde hydrosulfite adduct can be added.

[0386] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0387] Antimicrobial agents are compounds that kill or inhibit the growth or reproduction of microorganisms. The microorganisms can be bacteria, yeasts or molds. Preservatives are antimicrobial agents that can be added to aqueous products and compositions to maintain the original performance, properties and integrity of the products and compositions by killing or inhibiting the growth of contaminating microorganisms.

[0388] The composition / formulation may contain one or more antimicrobial agents and / or preservatives listed on pages 35-39 of WO 2021 / 115912 A1 ("Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes").

[0389] Any of the following antimicrobial and / or preservative agents are of particular interest for cleaning compositions and fabric care and home care products, specifically for laundry formulations: 4,4'-Dichloro-2-hydroxydiphenyl ether (other names: 5-chloro-2-(4-chlorophenoxy)phenol (Diclosan, DCPP), Tinosan® HP 100 (30% by weight of DCPP in 1,2-propylene glycol);2-phenoxyethanol (other names: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol);2-bromo-2-nitropropane-1,3-diol (other names: 2-bromo-2-nitro-1,3-propanediol, bronopol);glutaraldehyde (other names: 1,5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde);glyoxal (other names: ethanedial, oxyaldehyde, 1,2-ethanedial);5-bromo-5-nitro-1,3 -Dioxane (other names: 5-bromo-5-nitro-m-dioxane, Bronidox®);Phenoxypropanol (other names: Propylene glycol phenyl ether, Phenoxyisopropanol 1-phenoxy-2-propanol, 2-phenoxy-1-propanol);Glucoprotamine (chemical description: reaction product of glutamic acid and alkylpropylenediamines, other names: Glucoprotamine 50);Cyclohexylhydroxyldiazenium-1-oxide, potassium salt (other names: N-cyclohexyl-diazenium dioxide, potassium HDO, Xyligene);Formic acid (other names: Methanoic acid, Protectol® FM, Protectol® FM 75, Protectol® FM 85, Protectol® FM 99, Lutensol® FM) and its salts (e.g., sodium formate); tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (other names: 3,5-dimethyl-1,3-5-thiadiazinan-2-thione, dazomet; 2,4-dichlorobenzyl alcohol (other names: dichlorobenzyl alcohol, 2,4-dichloro-benzenemethanol, (2,4-dichloro-phenyl)-methanol, DCBA);1-Propanol (other names: n-propanol, propan-1-ol, n-propyl alcohol); 1,3,5-tris-(2-hydroxyethyl)-hexahydro-1,3,5-triazine (other names: hexyhydrotriazin, tris(hydroethyl)-hexyhydrotriazine, hexyhydro-1,3-5-tris(2-hydroxyethyl)-s-to 2-Butyl-benzo[d]isothiazol-3-one ("BBIT"); 2-Methyl-2H-isothiazol-3-one ("MIT"); 2-Octyl-2H-isothiazol-3-one ("OIT"); 5-Chloro-2-methyl-2H-isothiazol-3-one ("CIT" or "CMIT"); 5-Chloro-2-methyl-2H-isothiazol mixtures of 2-methyl-2H-isothiazol-3-one ("CMIT") and 2-methyl-2H-isothiazol-3-one ("MIT") (mixtures of CMIT / MIT); 1,2-benzisothiazol-3(2H)-one ("BIT"); hexa-2,4-dienoic acid (commonly known as "sorbic acid") and its salts, e.g., calcium sorbate, sodium sorbate; (E,E)-potassium hexa-2,4-dienoate (potassium sorbate); lactic acid and its salts; L-(+)-lactic acid; in particular sodium lactate. sodium;benzoic acid and its salts such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoic acid, potassium benzoate;salicylic acid and its salts such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate;benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate;didecyldimethylammonium chloride ("DDAC");N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine ("diamine");peracetic acid;hydrogen peroxide.;

[0390] At least one antimicrobial agent or preservative may be added to the composition of the present invention at a concentration of 0.001 to 10% by weight of the total composition.

[0391] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0392] The invention also includes a method of protecting an aqueous composition according to the invention from microbial contamination or growth, which method comprises adding at least one antimicrobial agent or preservative, preferably 2-phenoxyethanol.

[0393] The present invention also relates to a method of imparting antimicrobial benefit to textiles after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, bars, etc.), liquid laundry detergent, fabric softener, or post-rinse treatment agent containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0394] Formulations according to the invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0395] Further optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, foam enhancing or foam reducing agents, fragrances, dyes, optical brighteners and color transfer inhibitors.

[0396] (b) Dishwashing compositions Another aspect of the present invention is a dishwashing composition comprising at least one of the inventive polymers described above.

[0397] Thus, an aspect of the present invention is the use of the inventive polymers described above in dishwashing applications, such as for hand dishwashing or automatic dishwashing applications.

[0398] The dishwashing compositions according to the invention can be in the form of liquids, semi-liquids, creams, lotions, gels or solid compositions, with solid embodiments including, for example, powders and tablets. Liquid compositions are typically preferred for hand dishwashing applications, while solid and sachet formulations (sachets may contain solids in addition to liquid components) are typically preferred for automatic dishwashing compositions, although in some parts of the world liquid automatic dishwashing compositions are also used and therefore are of course encompassed by the term "dishwashing composition".

[0399] Dishwashing compositions are intended for direct or indirect application to tableware such as drinking and other glasses, beakers, dishes, and cookware such as pots and pans, and cutlery such as forks, spoons, knives, and the like, as well as metal and glass surfaces.

[0400] The method of the present invention for cleaning dishware, metal and / or glass surfaces comprises the step of applying the dishwashing composition, preferably in liquid form, directly or by means of a cleaning implement, i.e. undiluted, to the surface. The composition is applied directly to the surface to be treated without significant dilution (neat) prior to application and / or to a cleaning implement or implement such as a dish cloth, sponge or dishwashing brush. The cleaning implement or implement is preferably moistened before or after delivering the composition thereto. In the method of the present invention, the composition can also be applied in diluted form.

[0401] The formulations of the invention, which contain at least one inventive polymer, exhibit excellent cleaning performance, i.e., extremely good degreasing properties, whether applied neat or diluted. The presence of the inventive polymer reduces the effort required to remove greasy and / or oily soils from dishware, metal and / or glass surfaces, even if a lower amount of surfactant is used than in conventional compositions.

[0402] Preferably, the compositions are formulated to provide superior grease cleaning (degreasing) performance, foam retention and / or ease of viscosity control upon exposure to low temperatures, preferably at least two and more preferably all three of these performance attributes are present in the dishwashing compositions of the present invention. Optional (and preferably present) additional benefits of the hand dishwashing compositions of the present invention include stain removal, shine and / or hand protection, more preferably at least two and most preferably all three of these additional benefits are present in the dishwashing compositions of the present invention.

[0403] In one embodiment of the invention, the polymer of the present invention is a component of a hand dishwashing formulation additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0404] In another embodiment of the present invention, the polymer of the present invention is a component of a hand dishwashing formulation additionally comprising at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric and / or zwitterionic surfactants. In a preferred embodiment of the present invention, the hand dishwashing formulation comprises at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or a mixture thereof, to aid in the foaming, cleaning power and / or mildness of the detergent composition.

[0405] Examples of suitable anionic surfactants have already been described above for the laundry compositions. Preferred anionic surfactants for dishwashing compositions are selected from C10-C15 linear alkylbenzene sulfonates, C10-C18 alkyl ether sulfates containing 1-5 ethoxy units and C10-C18 alkyl sulfates.

[0406] Preferably, the hand dishwashing detergent formulation of the present invention contains one or more of the above-mentioned anionic surfactants in a range of at least 1% to 50% by weight, preferably in a range of from about 3% to about 35% by weight, more preferably in a range of from 5% to 30% by weight, and most preferably in a range of from 5% to 20% by weight, based on the total specific composition including other ingredients and water and / or solvent.

[0407] The dishwashing compositions of the present invention may comprise at least one amphoteric surfactant.

[0408] Examples of suitable amphoteric surfactants for dishwashing compositions are as already described above for laundry compositions.

[0409] Preferred amphoteric surfactants for dishwashing compositions are selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-di(hydroxyethyl)amine oxides.

[0410] The detergent composition for hand dishwashing of the present invention preferably contains an amphoteric surfactant, preferably an amine oxide surfactant, in an amount of 1% to 15% by weight of the composition, preferably 2% to 12% by weight, more preferably 3% to 10% by weight. Preferably, the composition of the present invention contains a mixture of an anionic surfactant and an alkyldimethylamine oxide in a weight ratio of less than about 10:1, more preferably less than about 8:1, more preferably from about 5:1 to about 2:1.

[0411] The addition of an amphoteric surfactant imparts good foaming properties to the dishwashing composition.

[0412] Hand dishwashing formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0413] Examples of suitable antimicrobial agents for dishwashing compositions are as already described above for laundry compositions.

[0414] Antimicrobial agents may be added to the hand dishwashing formulation of the invention at a concentration of 0.0001% to 10% by weight relative to the total weight of the composition. Preferably, the formulation comprises 4,4'-dichloro 2-hydroxydiphenyl ether at a concentration of 0.01% to 5%, more preferably 0.1% to 2%, 2-phenoxyethanol and / or at a concentration of 0.001% to 1%, more preferably 0.002% to 0.6% by weight (in all cases relative to the total weight of the composition).

[0415] Further ingredients include, but are not limited to, conditioning polymers, detersive polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, structurants, emollients, moisturizers, skin rejuvenation actives, carboxylic acids, scrubbing particles, bleaches and bleach activators, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antimicrobial agents, pH adjusters such as NaOH, alkanolamines such as monoethanolamine, buffering means, and the like.

[0416] Since the polymers of the invention are biodegradable and, in particular, the pH of cleaning formulations is usually about 7 or higher, and in addition, such cleaning formulations often also contain enzymes to degrade biodegradable stuffs such as grease, proteins, polysaccharides, etc., present in stains and dirt and which need to be removed by the cleaning composition, it is necessary to take into account the formulation of the biodegradable polymers of the invention in some way. Such suitable formulations are known in principle and include solid as well as liquid and semi-liquid formulations, in which, in the case of solids, the enzymes and the polymers can be separated by a coating or added as separate particles mixed together, and in the case of liquids and semi-liquids, the polymers and the enzymes can be separately formulated in different compartments, for example in different compartments of a multi-chambered sachet or a multi-chambered bottle, from which a predetermined amount of liquid is poured out simultaneously to ensure that each component is applied in the correct amount according to the individual point of use. Such multi-chambered sachets and bottles are also known to those skilled in the art.

[0417] (c) General cleaning compositions and formulations In a preferred embodiment, the grafted polymers according to the present invention are used in laundry detergents.

[0418] The liquid laundry detergent according to the present invention comprises: 0.05 to 20% of at least one polymer of the present invention; Surfactant 1-50% Builder, cobuilder and / or chelating agent in an amount of 0.1 to 40%; Other auxiliary substances are 0.1 to 50%. The amount of water that makes the whole 100% and It consists of:

[0419] Preferred liquid laundry detergents according to the present invention include: 0.2 to 6% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS and C10 to C18 alkyl ether sulfate salts containing 1 to 5 ethoxy units; 1.5 to 10% of a nonioic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 2-20% of a soluble organic builder / cobuilder selected from C10-C18 di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids; 0.05 to 5% of an enzyme system comprising at least one enzyme suitable for detergents and preferably further comprising an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol; Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0420] The solid laundry detergent according to the present invention (e.g. powder, granule or tablet) comprises: 0.05 to 20% of at least one of the polymers of the present invention; Surfactant 1-50% 0.1 to 80% of a builder, cobuilder and / or chelating agent; With 0-50% bulking agent, 0-40% bleach activator, 0.1-30% of other auxiliary substances and / or water, It is composed of The sum of the ingredients equals 100%.

[0421] Preferred solid laundry detergents according to the present invention include: 0.2 to 6% of at least one polymer of the present invention; 5 to 30% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl sulfate ester salts, and C10 to C18 alkyl ether sulfate ester salts containing 1 to 5 ethoxy units; 1.5 to 7.5% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 5-50% of an inorganic builder selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicate, and sodium sulfate; 0.5 to 15% of a cobuilder selected from C10 to C18 di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, and polycarboxylic acids; 0.1 to 5% of an enzyme system comprising at least one enzyme suitable for detergents and preferably further comprising an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol; Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0422] In a preferred embodiment, the polymers according to the present invention are used in hand dishwashing detergents.

[0423] The liquid hand dishwashing detergent according to the present invention comprises: 0.05 to 10% of at least one polymer of the present invention; Surfactant 1-50% Other auxiliary substances are 0.1 to 50%. The amount of water that makes the whole 100% and It consists of:

[0424] The liquid hand dishwashing detergent according to the present invention comprises: 0.2 to 5% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl ether sulfate salts containing 1 to 5 ethoxy units, and C10 to C18 alkyl sulfate salts; Cocamidopropyl betaine 2 10% Lauramine oxide 0-10% A non-ionic surfactant, preferably a C10 Guerbet alcohol alkoxylate, at 0-2%; 0-5% of an enzyme, preferably an amylase, and preferably also an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol; Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0425] The liquid formulations disclosed above and below may contain 0-2%, preferably about 1%, of 2-phenoxyethanol in addition to all other ingredients mentioned.

[0426] The liquid formulations disclosed above and below may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenylethe. The bleach-free solid laundry compositions may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenylethe.

[0427] The liquid formulations disclosed above and below may contain, in addition to all other ingredients mentioned, one or more enzymes selected from those disclosed herein above, more preferably a protease and / or an amylase, more preferably a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147 B1 and having the amino acid substitution R101E (according to the numbering of BPN residues), and the amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881 A1, such enzymes being preferably present in the formulation at a level such that the enzyme protein is from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, even more preferably from about 0.001% to about 0.5% by weight of the composition.

[0428] The following table shows certain types of typical cleaning compositions, which correspond to typical compositions corresponding to typical cleaning conditions commonly adopted in different regions and countries of the world. At least one of the polymers of the present invention can be added to such formulations in the appropriate amounts as outlined herein.

[0429] The compositions shown here that do not contain the grafted polymer of the present invention are comparative compositions, and are considered to be within the scope of the present invention when they contain the grafted polymer of the present invention, particularly in amounts within the ranges described herein as preferred, more preferred, etc.

[0430] [Table 9]

[0431] [Table 10]

[0432] Preferably, in each laundry detergent, cleaning composition and / or fabric care and home care product, the at least one grafted polymer is present in an amount in the range of about 0.01% to about 20%, preferably in the range of about 0.05% to 15%, more preferably in the range of about 0.1% to about 10%, and most preferably in the range of about 0.5% to about 5% by weight of the total weight of such composition or product.

[0433] The specific embodiments described throughout this disclosure are included as part of the present invention; various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" options of a particular embodiment may be individually and independently selected (unless such independent selection is impossible due to the nature of the feature or unless such independent selection is expressly excluded) and combined within any other embodiment (where such other options and preferences may also be individually and independently selected), and each and every such possible combination is included as part of the present invention, as an individual embodiment.

[0434] Agrochemical Compositions The present invention also relates to an agrochemical composition comprising an agrochemical active ingredient and a graft polymer according to the invention.

[0435] The term "agrochemical active ingredient" refers to a substance that imparts a desired biological activity to an agrochemical formulation. Typically, the agrochemical active ingredient is a pest control agent. The agrochemical active ingredient may be selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and / or growth regulators. In one embodiment, the agrochemical active ingredient is an insecticide. In another embodiment, the agrochemical active ingredient is a fungicide. In yet another embodiment, the agrochemical active ingredient is a herbicide. The skilled artisan is familiar with such pesticides, which are described, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, insecticides classified as METI acaricides, and insecticides such as chlorpicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amithras, hydramethylnon, acequinocyl, fluacrypyrim, rotenone or derivatives thereof. Suitable fungicides include dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic diamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines,Hydroxy-(2-amino)pyrimidine, hydroxyanilide, imidazole, imidazolinone, inorganic substances, isobenzofuranone, methoxyacrylate, methoxycarbamate, morpholine, N-phenylcarbamate, oxazolidinedione, oxyiminoacetate, oxyiminoacetamide, peptidylpyrimidine nucleoside, phenylacetamide, phenylamide, phenylpyrrole, phenylurea, phosphonate, phosphorothiolate, phthalamic acid, phthal ... Fungicides classified as thalimides, piperazines, piperidine, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, and triazoles. Suitable herbicides include acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroanilines, dinitrophenols, diphenyl ethers, glycine, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinedione, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, Herbicides classified as phenylpyridazine, phosphinic acid, phosphoramidate, phosphorodithioate, phthalamate, pyrazole, pyridazinone, pyridine, pyridine carboxylic acid, pyridine carboxamide, pyrimidinedione, pyrimidinyl (thio)benzoate, quinoline carboxylic acid, semicarbazone, sulfonylaminocarbonyl triazolinone, sulfonylurea, tetrazolinone, thiadiazole, thiocarbamate, triazine, triazinone, triazole, triazolinone, triazolocarboxamide, triazolopyrimidine, triketone, uracil, and urea are suitable plant growth regulators.Suitable micronutrients are compounds containing boron, zinc, iron, copper, manganese, chlorine and molybdenum. Suitable nitrification inhibitors are linoleic acid, alpha-linoleic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), karanjin, brachialactone, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin 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-thiodiazole (Telazol, Etriazol), 2-sulfanilamide thiazole (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 derived from neem components, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tertaboard, 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").3,4-dimethylpyrazole glycolate (3,4-dimethylpyrazolium glycolate, hereinafter referred to as "DMPG") and / or its isomers and / or its derivatives; 3,4-dimethylpyrazole citric acid (3,4-dimethylpyrazolium citrate, hereinafter referred to as "DMPC") and / or its isomers and / or its derivatives; 3,4-dimethylpyrazole lactate (3,4-dimethylpyrazolium lactate, hereinafter referred to as "DMPL") and / or its isomers and / or its derivatives; 3,4-dimethylpyrazole mandelic acid (3,4-dimethylpyrazolium mandelate, hereinafter referred to as "DMPM") and / or its isomers and / or its derivatives. and / or its isomers and / or derivatives thereof; 1,2,4-triazole (hereinafter referred to as "TZ") and / or its derivatives and / or salts thereof; 4-chloro-3-methylpyrazole (hereinafter referred to as "ClMP") and / or its isomers and / or its derivatives and / or salts thereof; addition product of dicyandiamide, urea and formaldehyde or triazonyl-formaldehyde-dicyandiamide adduct; 2-cyano-1-((4-oxo-1,3,5-triazinan-1-yl)methyl)guanidine, 1-((2-cyanoguanidino)methyl)urea; 2-cyano-1-((2-cyanoguanidino)methyl)guanidine; 3,4-dimethylpyrazole phosphate; allylthiourea and chlorate salts. Examples of contemplated urease inhibitors include N-(n-butyl)thiophosphoric triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric triamide (NPPT), 2-nitrophenylphosphoric triamide (2-NPT), further NXPTs known to those skilled in the art, phenyl phosphorodiamidates (PPD / PPDA), hydroquinone, ammonium thiosulfate and mixtures of NBPT and NPPT (see, for example, U.S. Pat. No. 8,075,659). Such mixtures of NBPT and NPPT may contain NBPT in an amount of 40-95% by weight, preferably 60-80% by weight, based on the total amount of active substance. Such mixtures are commercially available as LIMUS, which contains about 16.9% by weight of NBPT, about 5.6% by weight of NPPT and about 1.0% by weight of NPPT.The composition comprises about 77.5% by weight of other ingredients including solvents and adjuvants. In one embodiment, the agrochemical active is a fungicide, preferably one or more of the following group: fluxapyroxad, azoxystrobin, mefentrifluconazole, or chlorothalonil. In another embodiment, the agrochemical active is a herbicide, preferably atrazine.

[0436] Agrochemical compositions typically contain a biologically, e.g., pesticidal, effective amount of the agrochemical active ingredient. The term "effective amount" refers to an amount of the composition or agrochemical active ingredient that is sufficient to control harmful fungi on cultivated plants or to protect the material and does not cause substantial damage to the treated plants. Such amounts can vary widely and depend on various factors, such as the fungal species to be controlled, the cultivated plants or materials to be treated, the climatic conditions, and the specific agrochemical active ingredient used.

[0437] The agrochemical composition typically comprises the agrochemical active ingredient at a concentration of 1-70% by weight, preferably 10-50% by weight, more preferably 20-45% by weight, based on the total weight of the agrochemical composition. The agrochemical composition typically comprises at least 5% by weight, preferably at least 15% by weight, more preferably at least 25% by weight, most preferably at least 35% by weight, based on the total weight of the agrochemical composition. The agrochemical composition typically comprises up to 95% by weight, preferably up to 65% by weight, more preferably at least 45% by weight, based on the total weight of the agrochemical composition. The active substance is used at a purity of 90%-100%, preferably 95%-100%.

[0438] The agrochemical composition comprises a graft polymer according to the invention. The concentration of the graft polymer in the agrochemical composition is typically 0.5-20% by weight, preferably 0.5-10% by weight, more preferably 1-8% by weight, based on the total weight of the agrochemical composition. The concentration of the graft polymer is typically up to 15% by weight, more preferably up to 9% by weight, most preferably up to 7% by weight, based on the total weight of the agrochemical composition. The concentration of the graft polymer is typically at least 2% by weight, preferably at least 2.5% by weight, based on the total weight of the agrochemical composition.

[0439] The grafted polymer according to the present invention is typically present in dissolved form in the agrochemical composition, especially when the agrochemical composition is an aqueous agrochemical composition.

[0440] The grafted polymer may be present as solid particles, such as dispersed particles, especially when the agrochemical composition is a non-aqueous composition, such as a solid composition, or is an agrochemical composition having a continuous organic phase.

[0441] The weight ratio of agrochemically active ingredient to grafted polymer in the agrochemical composition is typically from 5:1 to 30:1, preferably from 7:1 to 20:1.

[0442] The agrochemical composition can be any type of agrochemical composition that is conventionally used, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules and mixtures thereof. Types of compositions include, for example, suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, solid fumigants, wettable powders or wettable dusts (e.g., WP, SP, WS, DP, DS), pressings (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal articles (e.g., LN) and gel-like formulations (e.g., GF) for treating plant propagation materials such as seeds. These and further composition types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. Preferred formulation types are suspensions, wettable powders or wettable powders and granules, especially suspensions, with SCs being most preferred.

[0443] The composition is prepared by known methods, for example as described in 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. The agrochemical composition is typically prepared by contacting the graft polymer with an agrochemical active ingredient. In the case of an agrochemical composition, this method typically involves forming a mill base by contacting the agrochemical active ingredient with water. This premix is ​​then typically subjected to grinding or milling to form a final suspension. The graft polymer may be added to the mill base or to the final suspension.

[0444] If the agrochemical composition is a granule, this is typically obtained by preparing a premix containing the agrochemical active ingredient, the graft polymer, the filler and typically up to 5% by weight of water, and then extruding the premix. The extrudate is then dried and converted into the granule.

[0445] Suitable auxiliaries which may be added to the agrochemical compositions are solvents, liquid carriers, solid carriers or extenders, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, water repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoam agents, colorants, crystal growth inhibitors, tackifiers and binders.

[0446] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling fractions of mineral oils, e.g., kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g., toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g., ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g., cyclohexanone; esters, e.g., lactate esters, carbonate esters, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonate esters; amines; amides, e.g., N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.

[0447] Suitable solid carriers or extenders are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, such as grain flour, bark flour, wood flour, nut shell flour and mixtures thereof.

[0448] 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, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

[0449] Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof.Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters.Examples of phosphates are phosphoric acid esters.Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0450] 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 alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for the alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

[0451] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are block polymers of the AB or ABA type, including blocks of polyethylene oxide and polypropylene oxide, or block polymers of the ABC type, including alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybasics. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybasics are polyvinylamines or polyethyleneamines.

[0452] Suitable adjuvants are compounds that have negligible or even no pesticidal activity of their own, but enhance the biological performance of compound I on the target. Examples are surfactants, mineral or vegetable oils and other adjuvants. Further examples are described in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable defoamers are silicones, long-chain alcohols and salts of 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, ferricyanide) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes and cellulose ethers.

[0453] Examples of types of compositions and methods for their preparation are given below: i) Water-soluble (SL, LS) 10-60% by weight of the agrochemical active substance, 5-15% by weight of the wetting agent (e.g., alcohol alkoxylate), and 1-15% by weight of the graft polymer are dissolved in water and / or a water-soluble solvent (e.g., alcohol) to a total of 100% by weight. The active substance dissolves when diluted with water.

[0454] ii) Dispersible concentrate (DC) 5-25% by weight of an agrochemically active ingredient, 1-10% by weight of a graft polymer, and optionally a further dispersant (e.g. polyvinylpyrrolidone) are dissolved in an organic solvent (e.g. cyclohexanone) to a total of 100% by weight. Dilution with water results in a dispersion.

[0455] iii) Emulsion (EC) 15-70% by weight of an agricultural chemical active ingredient, 1-15% by weight of a graft polymer, and 5-10% by weight of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., aromatic hydrocarbon) so that the total amount becomes 100% by weight. When diluted with water, it becomes an emulsion.

[0456] iv) Emulsions (EW, EO, ES) 5-40% by weight of an agricultural chemical active ingredient, 1-15% by weight of a graft polymer, and 1-10% by weight of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon). Using an emulsifier, this mixture is introduced into water so that the total amount becomes 100% by weight, and made into a homogeneous emulsion. When diluted with water, it becomes an emulsion.

[0457] v) Suspension agents (SC, OD, FS) In an agitator ball mill, 20-60% by weight of the agrochemical active ingredient is ground to a powder with 1-10% by weight of graft polymer, optional further dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylates), 0.1-2% by weight of a thickener (e.g. xanthan gum) and water to make up to 100% by weight, to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. In the case of the FS type, up to 40% by weight of a binder (e.g. polyvinyl alcohol) is added.

[0458] vi) Water dispersible granules and water-soluble granules (WG, SG) 50-80% by weight of the agrochemical active ingredient is milled with the addition of graft polymers, optional further dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylates) to a total of 100% by weight, and then water-dispersible granules or water-soluble granules are prepared by using technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution with water results in a stable dispersion or solution of the active substance.

[0459] vii) Wettable powders (powder) and water-soluble powders (WP, SP, WS) 50-80% by weight of the agrochemical active ingredient is milled in a rotor-stator mill with 1-5% by weight of the graft polymer and optionally further dispersing agent (e.g. sodium lignosulfonate), 1-3% by weight of a wetting agent (e.g. alcohol ethoxylate) and a total of 100% by weight of a solid carrier (e.g. silica gel). Dilution with water results in a stable dispersion or solution of the active substance.

[0460] viii) Gel preparations (GW, GF) In an agitator ball mill, 5-25% by weight of the agrochemical active ingredient is milled to powder form with 3-10% by weight of graft polymer and optional further dispersing agent (e.g. sodium lignosulfonate), 1-5% by weight of a thickener (e.g. carboxymethylcellulose) and water to make up 100% by weight, to obtain a fine suspension of the active substance. Dilution with water results in a stable gel of the active substance.

[0461] iv) Microemulsion (ME) 5-20% by weight of an agrochemical active ingredient is added to 5-30% by weight of a blend of organic solvents (e.g., fatty acid dimethylamides and cyclohexanone), 10-25% by weight of a blend of surfactants (e.g., alcohol ethoxylates and arylphenol ethoxylates), 1-25% by weight of a graft polymer, and 100% water. The mixture is stirred for 1 hour, and a thermodynamically stable microemulsion spontaneously forms.

[0462] iv) Microcapsules (CS) An oil phase containing 5-50% by weight of an agrochemical active ingredient, 0-40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and 2-15% by weight of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). By initiating radical polymerization with a radical initiator, microcapsules of poly(meth)acrylate are formed. Alternatively, an oil phase containing 5-50% by weight of an agrochemical active ingredient, 0-40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanate) is dispersed in an aqueous solution containing a protective colloid (e.g., polyvinyl alcohol). By adding a polyamine (e.g., hexamethylenediamine), polyurea microcapsules are formed. The amount of monomer is 1-10% by weight. The weight percentages relate to the entire CS composition. The microcapsules can then be dispersed in an aqueous composition. For this purpose, CS formulations are obtained by mixing 1-40% by weight of the microcapsules with 2-10% by weight of the graft polymer and optionally further dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylates), 0.1-2% by weight of a thickener (e.g. xanthan gum) and water to make up 100%.

[0463] ix) Powder (DP, DS) 1-10% by weight of the agrochemically active ingredient is finely ground and intimately mixed with 1-20% by weight of the graft polymer and a total of 100% by weight of a solid carrier (eg, finely divided kaolin).

[0464] x) Granules (GR, FG) 0.5-30% by weight of the agrochemical active ingredient is finely ground and combined with 1-20% by weight of the graft polymer and a total of 100% by weight of a solid carrier (e.g. a silicate). Granulation is carried out by extrusion, spray drying or in the fluidized bed.

[0465] xi) Ultra-low volume liquid (UL) 1 to 50% by weight of an agriculturally active ingredient and 1 to 30% by weight of a graft polymer are dissolved in an organic solvent (for example, an aromatic hydrocarbon) so that the total amount becomes 100% by weight.

[0466] The compositions of types i) to xi) may optionally contain further adjuvants, for example 0.1 to 1% by weight of a bactericide, 5 to 15% by weight of an antifreeze agent, 0.1 to 1% by weight of an antifoaming agent and 0.1 to 1% by weight of a coloring agent.

[0467] In one embodiment, the agrochemical composition is a suspension formulation, preferably a SC formulation.

[0468] Agrochemical suspensions typically contain the agrochemical active ingredient at a concentration of 1 to 65% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and most preferably 30 to 50% by weight, based on the total weight of the agrochemical suspension.

[0469] Agrochemical suspensions contain at least a part of the agrochemical active substances as solid particles suspended in a continuous phase, preferably an aqueous continuous phase.Therefore, agrochemical suspensions are preferably aqueous agrochemical suspensions, each based on the total weight of the suspension, and contain at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, most preferably at least 20% by weight, particularly preferably at least 25% by weight, for example at least 30% by weight, particularly preferably at least 40% by weight, of water.Agrochemical compositions can contain up to 95% by weight, preferably up to 80% by weight, more preferably up to 70% by weight, most preferably up to 60% by weight, for example up to 50% by weight, of water, each based on the total weight of the suspension.

[0470] Agrochemically active ingredients are typically practically insoluble in water. The water solubility of the agrochemically active substances may be 10 g / l or less, preferably 1 g / l or less, more preferably 0.5 g / l or less, and most preferably 0.1 g / l or less at 20° C. and pH 7.

[0471] The agrochemical active ingredient is present in the form of particles suspended in the agrochemical suspension agent. The particles can be characterized by a particle size distribution determined by dynamic light scattering techniques. A suitable dynamic light scattering measuring device is, inter alia, that manufactured under the trade name Malvern Mastersizer 3000. The particles can be characterized by their median diameter, usually abbreviated as D50 value. The D50 value represents the specific particle diameter below which half of the volume of the particle population is smaller than this diameter. The D50 value is typically determined according to ISO 13320:2009. The D50 value of the particles can be between 0.05 μm and 30 μm, preferably between 0.1 μm and 20 μm, more preferably between 0.5 μm and 20 μm, most preferably between 0.5 μm and 15 μm, and particularly preferably between 0.5 μm and 10 μm. The D50 value of the particles is typically at least 0.75 μm, preferably at least 1 μm, with an upper limit preferably not greater than 2 μm.

[0472] The suspended particles can be in the form of crystalline particles or amorphous particles that are solid at 20°C.

[0473] Typically, at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight, 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.

[0474] The agrochemical suspension may contain a further active ingredient which may be selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biopesticides, nitrification inhibitors, urease inhibitors and / or growth regulators. This further active ingredient may be present in the agrochemical suspension in dissolved form or as suspended particles. The concentration of the further active ingredient is typically 1-50% by weight, preferably 10-25% by weight, based on the total weight of the agrochemical suspension.

[0475] Agrochemical suspensions can in principle be prepared at any pH. Preferably, the pH of the agrochemical suspensions according to the invention is below 9, more preferably between 4 and 8.

[0476] Agrochemical suspending agents typically contain a thickening agent. The term "thickening agent" usually refers to inorganic clays (organically modified or unmodified), such as bentonite, attapulgite, hectorite and smectite clays and silicates (e.g. colloidal hydrous magnesium silicate, colloidal hydrous aluminum silicate, colloidal hydrous aluminum magnesium silicate, hydrous amorphous silicon dioxide); and organic clays, such as polycarboxylates (e.g. poly(meth)acrylates and modified poly(meth)acrylates), polysaccharides (e.g. xanthan gum, agarose, rhamsan gum, pullulan, tragacanth gum, carob bean gum, guar gum, tara gum, Whelan cum, casein, dextrin, diutan gum, cellulose, ethyl cellulose, hydroxyethyl cellulose, methylhydroxypropyl cellulose), polyvinyl ethers, polyvinylpyrrolidone, polypropylene oxide-polyethylene oxide (polyethylene oxide), polyvinyl ethers, polyvinyl pyrrolidone, polypropylene oxide-polyethylene oxide), polyvinyl ethers, polyvinyl pyrrolidone, polypropylene oxide-polyethylene oxide, polyvinyl ethers ... ocide condensation products, polyvinyl acetate, maleic anhydride, polypropylene glycol, polyacrylonitrile block copolymers, proteins and carbohydrates.

[0477] The present invention also relates to the use of the graft polymers according to the invention for dispersing an agrochemically active ingredient in an agrochemical composition, such as a suspension.

[0478] Chapter: Preferred Agrochemical Compositions - Embodiments The following preferred agrochemical composition embodiments are illustrative of the invention in which a graft polymer according to the invention is used to disperse or incorporate an agrochemical active ingredient in an agrochemical composition, and represent preferred embodiments thereof both by themselves and in combination:

[0479] In one embodiment, the agrochemical composition comprises a grafted polymer as defined herein and at least one agrochemical active ingredient, preferably any of the preferred actives mentioned herein, more preferably the composition is a suspension, even more preferably the composition comprises a continuous aqueous phase and the grafted polymer is preferably present in dissolved form.

[0480] In a preferred embodiment of the above mentioned embodiments, the composition comprises the agrochemically active ingredient in the form of suspended particles.

[0481] The composition of any of the embodiments described above in this section preferably comprises 1-60% by weight of an agrochemical active ingredient, based on the total weight of the agrochemical composition, the agrochemical active ingredient preferably having a water solubility of 5 g / l or less at 20°C, preferably 1 g / l or less at 20°C, and / or comprises 0.5-10% by weight of a grafted polymer, based on the total weight of the agrochemical composition.

[0482] In an alternative embodiment, the pesticide comprises a grafted polymer as defined herein and at least one agrochemical active ingredient, preferably any of the preferred actives mentioned herein, more preferably the composition is a suspension, even more preferably the composition comprises a continuous aqueous phase, the grafted polymer is preferably present at least partially in dissolved form and the agrochemical active ingredient is in the form of suspended particles.

[0483] The compositions of the embodiments described above in this chapter preferably comprise 1-60% by weight of an agrochemical active ingredient, based on the total weight of the agrochemical composition, the water solubility of the agrochemical active ingredient is preferably 5 g / l or less at 20°C, preferably 1 g / l or less at 20°C, and / or comprise 0.5-10% by weight of a grafted polymer, based on the total weight of the agrochemical composition.

[0484] The compositions of the two embodiments described above in this chapter are in the form of wettable powders or wettable powders (dust).

[0485] The present invention further includes a method for preparing an agrochemical composition according to any of the embodiments described above in this section, comprising contacting an agrochemically active ingredient with a grafted polymer.

[0486] The present invention further encompasses a method for controlling phytopathogenic fungi and / or unwanted plant growth and / or unwanted attack by insects or mites and / or for regulating plant growth, which comprises applying an agrochemical composition as defined in any of the embodiments set out above in this section disclosing an agrochemical composition to a particular pest, its habitat or a plant to be protected from a particular pest, to the soil and / or to the undesired plants and / or to the useful plants and / or their habitat.

[0487] The present invention further encompasses a method for combating or controlling an invertebrate pest, the method comprising contacting the pest or its food source, habitat or breeding ground with a pesticidally effective amount of an agrochemical composition, the agrochemical composition being as defined in any of the embodiments set forth above in this section disclosing such compositions.

[0488] The invention further includes a method for protecting a growing plant from attack or infestation by an invertebrate pest, the method comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of an agrochemical composition, the agrochemical composition being as defined in any of the embodiments set forth above in this section disclosing such compositions.

[0489] The present invention also encompasses seeds comprising an agrochemical composition in an amount of from 0.1 g to 10 kg per 100 kg of seed, the agrochemical composition being as defined in any of the embodiments set out above in this section disclosing such compositions.

[0490] The present invention also includes a method for treating or protecting an animal from infestation or infection by an invertebrate pest, comprising contacting the animal with a pesticidally effective amount of an agrochemical composition, as defined in any of the embodiments set forth above in this section disclosing such compositions.

[0491] For the treatment of plant propagation material, in particular seeds, usually solutions for seed treatment (LS), suspoemulsions (SE), flowables for seed treatment (FS), powders for dry seed treatment (DS), wettable powders for seed treatment slurry (WS), water-soluble powders for seed treatment (SS), emulsions for seed treatment (ES), emulsifiable concentrates (EC) and gel formulations (GF) are used. The ready-to-use preparations obtained by diluting the target composition 2-10 times have an active substance concentration of 0.01-60% by weight, preferably 0.1-40% by weight. Application can be carried out before or during sowing. Methods for applying agrochemical compositions to plant propagation material, in particular seeds, include dressing, covering, pelleting, dusting, immersion and in-furrow application methods on the propagation material. Preferably, the agrochemical compositions are applied to the plant propagation material in a manner that does not induce germination, for example, by seed dressing, pelleting and dusting.

[0492] The present invention also relates to a method for controlling the growth of phytopathogenic fungi and / or unwanted plants and / or unwanted attack by insects or mites and / or for regulating plant growth, which comprises applying an agrochemical composition to specific pests, their habitats or plants to be protected from specific pests, to the soil and / or to the undesired plants and / or to the useful plants and / or their habitats.

[0493] In one embodiment, the method is for controlling phytopathogenic fungi, in another embodiment, the method is for controlling undesirable vegetation, in another embodiment, the method is for inhibiting undesirable infestation by insects or mites.

[0494] These methods typically involve treating the plant to be protected, the locus in which it grows, phytopathogenic fungi and / or unwanted plant growth and / or unwanted attack by insects or mites with an agrochemical composition.

[0495] Suitable treatment methods include, among others, soil treatment, seed treatment, furrow application, and foliar application. Soil treatment methods include soil drench, drip irrigation (drip application to soil), soaking of roots, tubers or bulbs, or soil injection. Seed treatment methods include seed dressing, seed covering, seed dusting, seed soaking, and seed pelleting. Furrow application usually includes the steps of making furrows in cultivated land, sowing seeds in the furrows, applying a pesticidal compound to the furrows, and backfilling the furrows.

[0496] The application rates of the agrochemically active substances when used in plant protection are, depending on the type of effect desired, between 0.001 and 2 kg per hectare, preferably between 0.005 and 2 kg per hectare, more preferably between 0.05 and 0.9 kg per hectare, in particular between 0.1 and 0.75 kg per hectare.

[0497] When used in the protection of materials or stored products, the application rates of active substance vary depending on the area of ​​application and the type of effect desired. The application rates customarily used in the protection of materials are between 0.001 g and 2 kg, preferably between 0.005 g and 1 kg, of active substance per cubic meter of treated material.

[0498] In the treatment of plant propagation material such as seeds, for example by dusting, coating or irrigating the seeds, it is generally necessary to use an amount of active substance of 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g, most preferably 5 to 100 g per 100 kilograms of plant propagation material (preferably seeds).

[0499] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pest control agents (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the agrochemical composition as a premix or, if appropriate, are not added until just before use (tank mix). These agents can be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0500] The user usually applies the agrochemical composition according to the invention from a predosage device, a backpack sprayer, a spray tank, a spray aircraft or an irrigation system. Usually, the agrochemical composition is formulated to the desired application concentration with water, buffers and / or further adjuvants, thus obtaining a ready-to-use spray solution or agrochemical composition according to the invention. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray solution are applied per hectare of agronomically useful area.

[0501] The present invention also relates to methods for combating or controlling invertebrate pests, comprising contacting the pests or their food source, habitat or breeding grounds with a pesticidally effective amount of the agrochemical composition; methods for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting the plants or the soil or water in which the plants grow with a pesticidally effective amount of the agrochemical composition; and methods for treating or protecting animals from infestation or infection by invertebrate pests, comprising contacting the animals with a pesticidally effective amount of the agrochemical composition.

[0502] Invertebrate pests according to the present invention are typically arachnids, mollusks or insects, preferably insects.

[0503] According to one embodiment, the individual components of the composition according to the invention, for example the components of a kit or of a binary or ternary mixture, may be mixed by the user himself in a spray tank, with further auxiliaries being able to be added if appropriate.

[0504] In a further embodiment, either the individual components of the composition according to the invention or the partially premixed components may be mixed by the user in a spray tank, and further auxiliaries may be added if appropriate.

[0505] In further embodiments, either the individual components or partially premixed components of the compositions according to the invention may be applied together (e.g. after tank mixing) or sequentially.

[0506] The following examples will further illustrate the invention without limiting its scope. EXAMPLES

[0507] Polymer Measurements The K value is a measure of the relative viscosity of a diluted 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 tends to increase. The K value is measured according to the method of H. Fikentscher in "Cellulosechemie", 1932,13,58, in a 3% by weight NaCl solution at 23°C, with a polymer concentration of 1% polymer.

[0508] The number average molecular weight Mn, weight average molecular weight Mw and polydispersity Mw / Mn of the polalkylene oxide polymer (esterified mixture) for use as the polymer backbone A were measured in tetrahydrofuran by gel permeation chromatography. Tetrahydrofuran containing 0.035 mol / L of diethanolamine was used as the mobile phase (eluent). The concentration of the esterified polymer in tetrahydrofuran was 2.0 mg / mL. After filtering (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four different columns (heated to 60° C.) were used for the separation (SDV precolumn, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL / min. A DRI Agilent 1100 was used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) with molecular weights Mn ranging from 106 to 1378000 g / mol were used for calibration.

[0509] The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity Mw / Mn of the graft polymer of the present invention were measured in tetrahydrofuran by gel permeation chromatography. Tetrahydrofuran containing 0.035 mol / L of diethanolamine was used as the mobile phase (eluent). The concentration of the graft polymer in tetrahydrofuran was 2.0 mg / mL. After filtering (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four different columns (heated to 60° C.) were used for separation (SDV precolumn, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL / min. A DRI Agilent 1100 was used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) with molecular weights Mn of 106 to 1378000 g / mol were used for calibration.

[0510] The biodegradability of polyalkylene oxide polymers for use as polymer backbone A was tested in triplicate in wastewater using the OECD 301B manometric respirometry method. 30 mg / mL of the test substance is inoculated into water taken from the wastewater treatment plant in Mannheim (Germany) and incubated for 28 days at 25°C in a closed flask. The oxygen consumed during this period is measured as the pressure change in the flask using an OxiTop C (WTW). The CO2 evolved is absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population while the test substance is biodegraded is expressed as a percentage of the theoretical oxygen demand ("ThOD") after correction with a blank.

[0511] The biodegradation of the grafted polymers in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance is inoculated into wastewater taken from the Mannheim Wastewater Treatment Plant and incubated in closed flasks at 25°C for 28 days. The oxygen consumed during this period is measured as the pressure change in the flask using an OxiTop C (WTW). The CO2 evolved is absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as a % of ThOD (theoretical oxygen demand) after correction with a blank.

[0512] Polyalkylene oxide polymers for use as polymer backbone A - synthesis Examples 1-10 - Oxidation of PAG In Examples 1-10, polyalkylene oxides having two primary OH end groups (called "diols") were oxidized to obtain mixtures containing polyalkylene oxides having at least two COOH end groups (called "diacids") and polyalkylene oxides having one primary OH and one COOH end group (called "monoacids"), and optionally a remainder polyalkylene oxide having two primary OH end groups. The mixtures were prepared as follows:

[0513] Platinum on charcoal (5.0 wt% Pt on C, water content: 59.7 wt%, 283 g, 29.2 mmol Pt) was suspended in a mixture of polyalkylene oxide with two primary OH end groups (see Table 1 for details) and water (see Table 1 for details), heated to 52°C and stirred at 800 rpm. While stirring the mixture, oxygen was bubbled (20 nL / h) through a glass tube equipped with a glass frit and the temperature was raised to 60°C. The oxygen supply and temperature were maintained for the time stated in Table 1, then the oxygen supply was stopped and the mixture was cooled 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 by evaporation from the liquid mixture using a thin film evaporator (total height: 87.2 cm, diameter: 3.54 cm, wiped height: 43 cm, feed rate: 4.0 mL / min, 44°C, 1.8 kPa abs, 600 rpm). The sump product from the thin film evaporator was analyzed. The hydroxyl value was measured to determine the OH group content, and the acid value was measured to determine the COOH group content. The conversion rate of polyalkylene oxide in partial oxidation was derived from this acid value.

[0514] For partially oxidized mixtures based on low molecular weight polyalkylene oxides with Mw values ​​of 200 g / mol, the distribution of diols, monoacids and diacids was determined by gas chromatography. To this end, 0.1 g of a dry sample of partially oxidized polyalkylene oxide was heated to 80° C. together with 1 g of N-methyl-N-(trimethylsilyl)trifluoroacetamide and maintained at this temperature for 1 hour. The resulting mixture was then analyzed by gas chromatography. For other mixtures based on polyalkylene oxides with 400 g / mol or more, the distribution was calculated from the total content of OH and COOH groups, assuming that each OH group is oxidized with equal probability regardless of whether it is part of a diol or a monoacid. The respective values ​​are shown in Table 1.

[0515] Examples 11-21 and 22 - Esterification Examples 11-21 relate to the esterification of the oxidized polyalkylene oxide mixtures obtained from Examples 1-10 and the determination of the biodegradability of the polyalkylene oxide ester polymers obtained thereby. Example 22 relates to a comparative example determining the biodegradability of conventional polyethylene oxide ("PEG").

[0516] In Examples 11-21, 98 g of polyalkylene oxide mixture obtained by the oxidation procedure described in Examples 1-10, hereinafter referred to as inducer mixture (see Tables 2a and 2b for details), was mixed with 2 g of water with an esterification catalyst (see Tables 2a and 2b for details) and heated under reduced pressure of 1 kPa abs for the period of time described in Tables 2a and 2b, starting from 125°C and slowly increasing the temperature to 145°C.

[0517] The resulting esterified mixture was then analyzed to determine the K value, the number-average molar mass Mn and the molecular weight distribution Mw as described above. Biodegradability was determined by the OECD 301B degradation test as described above.

[0518] The average number of ester and ether groups in the polyalkylene oxide ester polymers was estimated from the estimated average molecular weight of each polyalkylene oxide ester polymer and each polyalkylene oxide used in the preceding oxidation step. For each polyalkylene oxide ester polymer, the number average molecular weight Mn was used, which is a good indicator of the average molecular weight on a molecular scale. Alternatively, the molecular average molecular weight Mw can be used for each polyalkylene oxide used in the preceding oxidation step, since polyethylene oxides typically have a low polydispersity PD, slightly above 1, so that Mw and Mn differ only slightly.

[0519] The number of ester groups in the polyalkylene oxide ester polymer based on the use of partially oxidized polyethylene oxide (with a ratio of oxidized OH groups of around 50%) was estimated as follows. First, the number of structural units was estimated by (1) taking into account two end groups and correcting the number of 18 g / mol of the number of the polyalkylene oxide ester polymer, and dividing it by (2) the average molecular weight of the esterified structural elements. The latter was calculated by subtracting 18 g / mol from the molecular average molecular weight Mw of the polyethylene oxide used, taking into account the separation of water by esterification, and adding 16 g / mol and subtracting 2 g / mol, taking into account the arithmetic average formation of one -CO- unit from each -CH2- unit per structural element. In the case of the structural element of formula (I), there is exactly one per structural element, and in the case of the combination of structural elements of formulas (II) and (III), there are two and zero, which also average out to one. Next, subtract 1 from the number of structural units to account for the fact that each ester group in the example polyalkylene oxide ester polymer links two structural elements, thereby resulting in one more structural element than there are ester groups.

[0520] The above estimation is specifically explained with reference to Example 12. The number average molecular weight Mn of the polyalkylene oxide ester polymer was 2400 g / mol, so the value of 2382 g / mol was obtained. The average molecular weight of the structural elements used in the esterification was (400-4) g / mol = 396 g / mol. From this, the average number of structural units is 2382 / 396 = 6.0, and therefore the average number of ester groups is 5.0. Alternatively, this can be expressed by the formula:

number

[0521] The number of ether groups in the polyalkylene oxide ester polymer based on the use of partially oxidized polyethylene oxide (with a ratio of oxidized OH groups of around 50%) was estimated as follows. First, (1) taking into consideration that terminal groups are formally formed by the addition of one water molecule per polyethylene oxide molecule during polymerization, 18 g / mol was subtracted from the molecular average molecular weight Mw of the polyethylene oxide used, and then (2) the number of ethylene oxide units of the polyethylene oxide used was determined by dividing by 44 g / mol, which is the molecular weight of the -CH2CH2-O- unit. Next, taking into consideration that the number of ether groups in each polyethylene oxide is one less than the number of ethylene oxide units, 1 was subtracted from the number of ethylene oxide units. The result is the average number of ether groups in the polyethylene oxide. Next, this number was further multiplied by the number of structural units of the polyalkylene oxide ester polymer determined as described above.

[0522] The above estimation will be specifically explained with reference to Example 12. The molecular average molecular weight Mw of the polyethylene oxide used was 400 g / mol, so a value of 382 g / mol is obtained. By dividing this by 44 g / mol, the number of -CH2CH2-O- units is 8.7, and as a result, the average number of ether units in the polyethylene oxide is 7.7. Since the average number of structural units of the polyalkylene oxide ester polymer was estimated above to be 6.0, the average number of ether groups in the polyalkylene oxide ester polymer is 46. Or the formula:

number

[0523] For the examples based on the use of fully oxidized polyethylene oxide (with a proportion of oxidized OH groups of around 95-100%) and therefore requiring the addition of a diol as a second component, the estimation of the number of ester and ether groups was performed in a similar manner to that described above, with the main difference being that the molecular weight Mw of the polyethylene oxide used in the calculation was the arithmetic average of the molecular weight Mw of the polyalkylene oxide used for the oxidation and the molecular weight Mw of the polyalkylene oxide used as the diol component. This approach is based on the simplifying assumption that both structural units are evenly distributed in the polyalkylene oxide ester polymer.

[0524] This modified estimation is illustrated with reference to Example 14, in which polyethylene oxide with Mw=600 g / mol was almost completely oxidized and polyethylene oxide with Mw=1500 g / mol was used as the diol component. The formula for this estimation of the ester group is as follows:

number

number

[0525] The polyalkylene oxide ester polymers obtained in Examples 11-21 all had weight average molecular weights Mw ranging from 4050 to even 18300 g / mol, yet the measured biodegradability was in the range of 73-89% as measured against theoretical CO2 production after 28 days, in contrast to the conventional polyethylene oxide with Mw=8720 g / mol, which showed a much poorer biodegradability of only 16% as measured against theoretical CO2 production within 28 days, despite having an Mw value well below 10000 g / mol.

[0526] In addition, the biodegradability of the polyalkylene oxide ester polymer used is much better than that of the conventional PEG 9000 polymer, with the biodegradability of the polyalkylene oxide ester polymer being as high as 73-79%, while that of the conventional PEG 9000 polymer is very low at 16%.

[0527] Further examples 23-29 were also tested for biodegradability and are shown in the polymer backbone - Table 3.

[0528] [Table 11]

[0529] [Table 12]

[0530] [Table 13]

[0531] [Table 14]

[0532] [Table 15]

[0533] Graft polymer examples The (general) procedure set out below was carried out using grafted polymers - starting materials ("derived sources") and ratios and amounts further indicated in Table 1.

[0534] Procedure for Comparative Example 1: Graft Polymerization of Vinyl Acetate onto Poly(ethylene glycol) - (Comparative Example 1; CE2 and 3 were prepared as follows, except that the graft polymers used were in the amounts of monomers shown in Table 1) First, 600 g of poly(ethylene glycol) was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0535] Feed 1, consisting of 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed into the stirred tank at 90° C. over 6 hours and 10 minutes. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (400 g of vinyl acetate) was started at a constant feed rate over 6 hours at 90° C. Upon completion of Feeds 1 and 2, the temperature was increased to 95° C. and Feed 3, consisting of 3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was dosed at a constant flow rate at 95° C. within 56 minutes. Upon completion of the feed addition, the mixture was stirred at 95° C. for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0536] Graft Polymers - General Synthesis (Details of Graft Polymers below - Table 1) In each of Examples G1 to G20, 500 g of polymer backbone A was charged into a 2.5 L vessel equipped with a stainless steel anchor-type impeller (and two other necks) and heated to 90°C. The vinyl monomer charge was started and continued at a constant feed rate for 6 hours. At the same time, the initiator t-butyl peroxy-2-ethylhexanoate was charged at a constant feed rate as a 26% tripropylene glycol solution for a total of 6 hours and 45 minutes. The temperature was then raised to 105°C and stirred for an additional 90 minutes to complete the reaction. Finally, the volatile components were stripped at 115°C for 90 minutes while feeding nitrogen at a rate of 6L N2 / h, followed by completion of the removal of the volatiles by vacuum distillation at 60°C and 40 mbar for about 1 hour.

[0537] Grafted polymers - Table 1 provides further details such as monomer composition, ratio of polymer backbone A to monomer B and biodegradation test results, along with the basic relationships of the polymerizations used to obtain the grafted polymers / polymer compositions and the results of the OECD 301F degradation tests.

[0538] "Inducer": The number is the experiment number for the preparation of PAG-esters as described in the Experimental Section above.

[0539] For the more biodegradable examples, the biodegradation test results were verified by repeating them at least once, and the results shown are the average of these at least two times.

[0540] [Table 16]

[0541] [Table 17]

[0542] Graft polymer performance testing The performance evaluation of the graft polymer can be obtained by washing and cleaning experiments. The washing experiments can be performed in a washing machine or in an apparatus such as a Launderometer or a Tergotometer for performing modeled washing experiments. When testing the anti-resoiling effect, a white cloth was washed together with a soiled cloth in the presence of a detergent composition containing the graft polymer, and the reflectance of the white cloth was measured before and after washing. When testing the stain removal effect, a soiled cloth was washed in the presence of a detergent composition containing the graft polymer, and the reflectance of the soiled cloth was measured before and after washing. The amount of the graft polymer added was selected to be 0.5-5% by weight of the detergent composition. The amount of detergent added was selected to be in the range of 1500-4500 ppm of the washing liquid. The hardness of the water in the washing test (Ca2+ and Mg2+ concentration in the washing liquid) was set between 1-3 mmol of hardness. The washing temperature was selected to be between 20°C and 40°C.

[0543] Cleaning performance The cleaning performance (primary cleaning performance, secondary cleaning performance (prevention of dark stains / prevention of re-soiling)) of the degradable graft polymer samples was tested by preparing a cleaning solution in a launderometer (1 L beaker) using 2.5 g / L of the test liquid detergent LD1 (see the composition in the table below) and water with a hardness of 14° dH (2.5 mmol / L; Ca:Mg:HCO3 4:1:8) containing 2.0% of each of the polymers of the present invention.

[0544] In detergent Tables 1-3 shown below, three liquid detergent formulations were selected to differentiate the grafted polymers.

[0545] [Table 18]

[0546] [Table 19]

[0547] [Table 20]

[0548] The first test criterion (primary cleaning performance) was chosen to focus on cleaning performance against sebum, a primarily difficult stain (wfk 20D). This test was performed on two relatively large 10cm x 10cm cloths (wfk 20D).

[0549] Other criteria relate to the greying properties of cotton and other fabrics, which are particularly desirable to avoid (anti-greying).

[0550] The dark stain prevention test was also carried out in a launderometer (model LP2 from SDL Atlas, Inc.) equipped with a 1 L beaker. A washing solution (0.25 L) was run at 25° C. with one multi-stain monitor (MS1) and 2.5 g of cotton ballast cloth (liquor ratio 1:10) for one wash cycle (60 min). After one cycle, the multi-stain monitor was rinsed with water and then dried overnight at ambient room temperature. The multi-stain monitor MS1 and MS2 (see below) were fabrics with dimensions of 5.0×5.0 cm and 4.5×4.5 cm, respectively, with eight and four standardized stains, respectively, sewn at both ends onto a polyester support.

[0551] Standard artificially soiled cloth used for cleaning performance (primary cleaning performance) evaluation: MS1: CFT CS-10: Milk fat with colorant on cotton CFT CS-62: Colored lard on cotton CFT CS-78: Pigmented soybean oil on cotton EMPA 112: Cocoa on cotton EMPA 141 / 1: Lipstick on cotton EMPA 125: Surfactant and lipase sensitive stains on cotton. wfk20D: Pigments and sebum-based fats on polyester / cotton blends CFT CS-70: Chocolate / mousse cream on cotton MS2: CFT CS-10: Milk fat with colorant on cotton CFT CS-62: Colored lard on cotton CFT CS-61: Colored tallow on cotton CFT PC-S-04: Polyester / cotton (65 / 35) soaked in colored olive oil.

[0552] The overall cleaning degree was evaluated using color measurements. The reflectance values ​​of the stains on the standard soiled cloth were measured using a sphere reflectance spectrometer (Model SF 500 from Datacolor, USA, wavelength range 360-700 nm, optical geometry d / 8°) equipped with a 460 nm UV cut-off filter. Here, the lightness L*, a* value on the red-green axis, and b* value on the yellow-green axis were measured before and after cleaning using the CIE-Lab color space classification, and the average values ​​were calculated for the eight stains on the standard soiled cloth. The change in color value (Delta E, ΔE) value was defined and was automatically calculated by the color evaluation means according to the following formula ΔE=ΔDelta a*2+ΔDelta b*2+ΔDelta L*2, which is a measure of the achieved cleaning effect. All experiments were repeated three times, and the average values ​​were obtained.

[0553] A higher Delta E value indicates better cleaning. For any stain, a person skilled in the art can visually distinguish a difference of 1 unit. A non-trained person can easily distinguish a difference of 2 units. The Delta E values ​​of the MS1 eight stains and the formulations for selected single stains are shown in "Washing Test - Table 1". The calculation of Delta E values ​​is software based and is performed automatically. Launderometer results tend to indicate better cleaning performance.

[0554] [Table 21]

[0555] [Table 22]

[0556] [Table 23]

[0557] The superior dark stain resistance of the grafted polymers of the present invention was demonstrated by comparison with prior art compounds using a Launderometer as shown below: Several test white cloths were washed together with the soiled cloth EMPA 101 / SBL 2004 and 20 steel balls in water at 40°C containing a selected composition containing two or more compounds of formula (I) or a comparative compound. The pH value of the washing solution was adjusted to 8.0. The compositions containing two or more compounds and comparative compounds used are outlined in Table 1. After washing, the test cloths were rinsed and spun dry.

[0558] This wash cycle was repeated twice with fresh soiled cloths and fresh wash solution. After the third wash, the test cloths were rinsed, spun dry, and air dried.

[0559] The washing conditions are as follows (adopted from a published patent application):

[0560] [Table 24]

[0561] The dark stain resistance was determined by measuring the reflectance value of the soiled fabric before and after washing at 460 nm using a spectrometer from Fa.Datacolor (Elrepho 2000). The result is a delta delta value, which means an improved reflectance compared to the result without polymer. The higher the ΔE value, the better the performance. The results are also summarized in the table above. From the results, it can be inferred that the composition of the present invention, which contains two or more compounds of formula (I), has better dark stain resistance compared to the prior art compounds.

[0562] Agrochemical compound experimental section Agrochemical Example 1: Graft Polymer GX Step 1: Preparation of polyethylene glycol monocarboxylic acid PEG 600 was used as the starting material and essentially the procedures outlined in the PAG-ester polymer experimental section for Examples 1-10 were followed.

[0563] Step 2: Preparation of polyetherester BX The polyethylene glycol monocarboxylic acid obtained in step 1 (100.0 g, purity 98%, water 2%, K value: 10.4, acid value 47.68 mg KOH / g) was mixed with 0.4 g of tin octoate catalyst, the pressure was reduced to 100 mbar, and the temperature was raised from 125 to 145°C and heated for 96 hours. The acid value and K value were monitored as the esterification reaction progressed. The K value was 20.2 and the MW was about 3000-4000.

[0564] Step 3: Preparation of graft polymer GX The graft polymer GX was prepared by reacting the polyetherest...

Claims

1. A graft polymer comprising (A) a polymer main chain as a graft matrix and (B) a polymer side chain grafted to the polymer main chain A, wherein the polymer main chain (A) has a weight average molecular weight M ｗ of 500 to 50,000 g / mol, a polydispersity PD of 2 to 6, and contains 10 to 560 ether groups and 2 to 51 ester groups bonded to an alkylene group, and is a polyalkylene oxide ester polymer, and the polyalkylene oxide ester polymer contains 1 to 51 structural elements of the general formula (I): 【Chemical Formula 1】 (In the formula, - The -O- unit on the left is bonded to the -CO- unit of an adjacent unit of the polymer to form an ester unit, - The -CO- unit on the right is bonded to the -O- unit of an adjacent unit of the polymer to form a further ester unit, - R １ 、R ２ 、R ３ 、R ４ 、R ５ independently of one another represent a hydrogen atom or a C １～１２ alkyl group, - a, b, c, d, e independently of one another represent an integer of 0 or 1, and the sum of a to e is 1 to 5, - X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, and the alkylene oxide units independently of one another contain 2 to 6 carbon atoms in a chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently of one another contain either two hydrogen atoms or one hydrogen atom and one C １～１２ alkyl group), The polymer side chain (B) can be obtained by polymerizing i) at least one monomer selected from at least one vinyl ester monomer (B1) and ii) an optional at least one further olefinically unsaturated monomer (B2) polymerizable with monomer B1. graft polymer.

2. A graft polymer comprising (A) a polymer main chain as a graft matrix and (B) a polymer side chain grafted onto the polymer main chain, The polymer main chain (A) is at least one of i) to iii), i) a diol of polyalkylene oxide (PAG-DO), ii) a dicarboxylic acid of PAG (PAG-DC), iii) a mono-carbonic acid mono-alcohol of PAG (PAG-MC) and an optional other non-polymeric dicarboxylic acid compound that can be present in addition to compound ii), which can be obtained by condensation, either a compound selected from at least iii) is present, or when only i) and ii) are present, at least two internal ester groups are present. The PAG is obtained by polymerizing at least one monomer selected from 1,2-alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; or is obtained by polymerizing at least one monomer selected from 1,4-diols or their cyclic or oligomeric analogs, or the PAG is based on a polymer ether of this type of 1,4-diol; or is obtained by polymerizing at least one monomer selected from 1,6-diols or their cyclic or oligomeric analogs, or the PAG is based on a polymer ether of this type of 1,6-diol; or any of these arbitrary mixtures are polymerized in any ratio to obtain, as blocks of specific polymer units, or as statistical polymer structures, or polymers containing one or more homoblocks of a specific monomer and one or more statistical blocks containing more than one monomer, and any combination of these, for example, polymers having several different blocks of different monomers, or polymers having blocks of two different monomers, polymers having blocks of a statistical mixture of two or more monomers, etc., The polymer side chain (B) can be obtained by radical polymerization of i) at least one monomer selected from at least one vinyl ester monomer (B1) and ii) an optional at least one further olefinically unsaturated monomer (B2) polymerizable with monomer B1. The graft polymer according to claim 1.

3. The polymer main chain A has a weight average molecular weight Mw of 500 to 50,000 g / mol, a polydispersity PD of 2 to 6, preferably 2 to 4, more preferably 2.2 to 3.5, and contains 10 to 560 ether groups and 2 to 51 ester groups bonded to the alkylene group. In addition to the compound iii), it can further contain a low molecular weight dicarboxylic acid. The graft polymer according to claim 1.

4. A graft polymer comprising (A) a polymer main chain A and (B) a polymer side chain grafted onto the polymer main chain A, The polymer main chain A can be obtained from at least one, preferably at least two, more preferably at least three different polymer sub-units bonded by covalent ester bonds: optionally further containing a low molecular weight dicarboxylic acid compound, and the polymer main chain is, a) an esterification reaction of at least one monoalcohol monocarboxylic acid (PAG-MC) of a polyalkylene oxide (PAG) with itself; b) an esterification reaction of at least one diol (PAG-DO) of a polyalkylene oxide (PAG) with at least one PAG (PAG-DC) containing two carbonic acids as terminal groups, that is, containing carbonic acid groups at both ends of the PAG; or c) an esterification reaction of at least one monoalcohol monocarboxylic acid (PAG-MC) of a polyalkylene oxide (PAG) with at least one diol (PAG-DO) of a polyalkylene oxide (PAG) and at least one PAG (PAG-DC) containing two carbonic acids as terminal groups, that is, containing carbonic acid groups at both ends of the PAG; can be obtained by, Optionally, in each of a), b) and c), in addition to the compound "PAG-DC", at least one low molecular weight dicarboxylic acid may be contained; The polymer side chain (B) can be obtained by radically polymerizing i) at least one monomer selected from at least one vinyl ester monomer (B1) and ii) optionally at least one further olefinically unsaturated monomer (B2) polymerizable with monomer B1. The graft polymer according to claim 1.

5. The graft polymer according to claim 4, wherein the polymer main chain can be obtained from the reaction according to option c).

6. The graft polymer according to claim 1, wherein the PAG of the PAG-DO, PAG-DC and PAG-MC can be independently selected from PAG units consisting of 1, 2, 3, 4 or more different alkylene oxide monomers, preferably only 3, more preferably only 2, and most preferably only 1; When more than one alkylene oxide monomer is included, the structure of the PAG is a polymer containing a block copolymer, a random polymer or a structure in which block units (each block is a homoblock or itself is a random block) and a statistical / random part composed of two or more alkylene oxides are mixed; The alkylene oxide is preferably selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, 2,3-pentene oxide or C5-C10-alkylene oxide, preferably C2-C4, more preferably C2 and C3, and most preferably only C2; Each PAG unit can be a block polymer, a random polymer or a polymer with a mixed block-random structure. When more than one PAG-DO, PAG-DC and / or PAG-MC is used, each PAG-DO, PAG-DC and PAG-MC can be independently selected from the structures described for the PAG unit. The graft polymer.

7. The graft polymer according to claim 1, wherein the polymer side chain (B) is contained in an amount of more than 0.2%, preferably more than 1% by weight (based on the total weight of the graft polymer).

8. The graft polymer according to claim 1, wherein the polymer main chain (A) is contained in an amount of 20 to 95% by weight and the polymer side chain (B) is contained in an amount of 5 to 80% by weight (based on the total weight of the graft polymer).

9. The graft polymer according to claim 1, wherein the polymer main chain A is contained in an amount of 40 to 85% by weight, more preferably 50 to 80% by weight, still more preferably 55 to 75% by weight, and the polymer side chain (B) is contained in an amount of 15 to 60% by weight, preferably 20 to 50% by weight, more preferably 20 to 50% by weight, still more preferably 25 to 45% by weight (based on the total weight of the graft polymer), and the polymer main chain preferably consists only of ethylene oxide as a PAG unit.

10. The graft polymer according to claim 1, having a weight average molecular weight Mw of 500 to 500,000 g / mol, preferably 2,000 to 200,000 g / mol, more preferably 5,000 to 100,000 g / mol, still more preferably 7,500 to 50,000 g / mol.

11. The graft polymer according to claim 1, having a polydispersity Mw / Mn in the range of 1.2 to 6, preferably preferably 4 or less, more preferably 3.5 or less, still more preferably 3 or less, and most preferably 1.5 to 2.

5.

12. The graft polymer according to claim 1, The polymer side chain (B) contains at least one vinyl ester monomer (B1) and optionally at least one olefinically unsaturated monomer (B2) different from the monomer (B1). Preferably, at least 10 weight percent of the total amount of the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably from vinyl acetate. The remaining amount of the vinyl ester can be any other known vinyl ester. As the vinyl ester, preferably at least 80 weight percent, more preferably at least 90 weight percent, is vinyl acetate used, and most preferably, basically only vinyl acetate (i.e., about 100 weight percent or even 100 weight percent) is used, a graft polymer.

13. The graft polymer according to claim 1, The optionally at least one olefinically unsaturated monomer (B2) is selected from monomer B2a and monomer B2b as defined herein, B2 is preferably selected from N-vinyl lactams, such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, and derivatives thereof substituted with C1-C8-alkyl groups, such as 3-methyl-, 4-methyl- or 5-methyl-N-vinyl pyrrolidone, preferably from N-vinyl pyrrolidone, N-vinyl caprolactam, and more preferably from N-vinyl pyrrolidone. B2b is preferably a carboxylic acid selected preferably from salts and esters of acrylic acid and its derivatives, such as substituted acrylic acids where the substituent is on the 2- or 3-carbon atom of said acrylic acid and is independently selected from the group consisting of C1-C4-alkyl, -CN and -COOH, for example methacrylic acid, said salts being preferably salts of these acids with alkanolamines, for example preferably ethanolamine, and said esters being preferably esters of acrylic acid and methacrylic acid, particularly more preferably esters of acrylic acid and methacrylic acid with C1-C10-alkanols, more preferably C1-C6-alkanols, graft polymers.

14. The graft polymer according to claim 1, The amount of vinyl ester monomer (B1) is 1 to 100% by weight, preferably 30 to 100% by weight, more preferably 60 to 100% by weight, most preferably 80 to 100% by weight of at least one vinyl ester monomer (B1), said at least one vinyl ester monomer being preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably from vinyl acetate, The amount of said optional at least one further monomer (B2), preferably only B2a-monomer (as defined herein), more preferably only N-vinyl lactam, most preferably only N-vinyl pyrrolidone, is 0 to 99%, preferably 0 to 70% by weight, more preferably 0 to 40% by weight, most preferably 0 to 20% by weight, graft polymer.

15. A process for obtaining at least one graft polymer according to claim 1, i) at least one vinyl ester monomer (B1) and, ii) optionally at least one further olefinically unsaturated monomer (B2) polymerizable with monomer B1, A process of polymerizing [[ID=]] in the presence of at least one polymer main chain (A) by radical polymerization using a suitable radical initiator. **Claim 16** The process according to claim 15, wherein the amount of the at least one vinyl ester monomer (B1) is 1 to 100% by weight, preferably 30 to 100% by weight, more preferably 60 to 100% by weight, most preferably 80 to 100% by weight, based on the total amount of monomer B; the at least one vinyl ester monomer is preferably selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably from vinyl acetate; the remaining amount of the vinyl ester can be any other known vinyl ester; as the vinyl ester, preferably at least 80% by weight, more preferably at least 90% by weight of the total weight of monomer B1 is vinyl acetate used, and most preferably, basically only vinyl acetate (i.e., about 100% by weight or even 100% by weight) is used. The optional at least one olefinically unsaturated monomer (B2) is selected from monomer B2a and monomer B2b as defined herein. - B2a is preferably selected from -N-vinyl lactams, such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, and derivatives thereof substituted with C1-C8 alkyl groups, such as 3-methyl-, 4-methyl- or 5-methyl-N-vinyl pyrrolidone, preferably from N-vinyl pyrrolidone, N-vinyl caprolactam, and more preferably from N-vinyl pyrrolidone. - B2b is preferably selected from carboxylic acids, salts and esters, preferably selected from acrylic acid and its derivatives, for example, substituted acrylic acids where the substituent is on the 2- or 3-carbon atom of said acrylic acid and is independently selected from the group consisting of C1-C4-alkyl, -CN and -COOH, such as methacrylic acid. Said salts are preferably salts of these acids with alkanolamines, for example, preferably ethanolamine. Said esters are preferably esters of acrylic acid and methacrylic acid, particularly more preferably esters of acrylic acid and methacrylic acid with C1-C10-alkanols, more preferably C1-C6-alkanols. The amount of (B2) is 0 to 99%, preferably 0 to 70% by weight, more preferably 0 to 40% by weight, most preferably 0 to 20% by weight, based on the total amount of monomer B.

17. The process according to claim 15, wherein the monomer B2 is only N-vinyl lactam, preferably N-vinyl pyrrolidone.

18. The process according to claim 15, In order to obtain the polymer side chain (B), at least one monomer (B1) and the optional at least one further monomer (B2) are reacted in the presence of at least one polymer main chain (A), a free radical forming initiator (C), and optionally, up to 50% by weight, based on the sum of components (A), (B1), optional (B2) and (C), of at least one organic solvent (D), at an average polymerization temperature at which the decomposition half-life of the initiator (C) is 40 to 500 minutes, in such a form that the proportion of unconverted graft monomers (B1) and optional (B2) and initiator (C) in the reaction mixture is always maintained in a quantitatively deficient state with respect to the polymer main chain (A).

19. At least one graft polymer according to claim 1 or at least one graft polymer obtainable by the process according to claim 15, Use in cleaning compositions, fabric care and home care products, industrial cleaning products, cosmetics or personal care products, oilfield formulations such as crude oil emulsion breakers, pigment dispersions for inkjet inks and inks containing said graft polymer, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations.

20. Use according to claim 19 in a cleaning composition and / or in a fabric care and home care product, preferably in a cleaning composition, wherein the cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation, and wherein the at least one graft polymer is present in the cleaning composition in an amount of from about 0.1% by weight to about 20% by weight, preferably from about 0.25% by weight to 15% by weight, more preferably from about 0.5% by weight to about 10% by weight, still more preferably from about 1% by weight to about 5% by weight, most preferably from about 0.5% by weight to about 5% by weight, for example at a concentration of 3% by weight or less, based on the total weight of such composition or product. Such a cleaning composition or product comprises at least one of i) to iv). i) a surfactant system in an amount of from about 1% by weight to about 70% by weight. ii) at least one enzyme, preferably one or more enzymes selected from the group consisting of lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersin, pectinase, oxidoreductase, cutinase, lactase and peroxidase, more preferably at least two of the types mentioned above. iii) an antibacterial agent selected from the group consisting of 2-phenoxyethanol; preferably said antibacterial agent is included in an amount in the range of 2 ppm to 5% by weight of said composition; more preferably phenoxyethanol is included at 0.1 to 2%. iv) 4,4'-dichlorohydroxydiphenyl ether at a concentration of from 0.001 to 3%, preferably from 0.002 to 1%, more preferably from 0.01 to 0.6% by weight of said composition respectively. further comprising, wherein the cleaning composition is preferably for removing oily and fatty stains, for removing solid stains such as clay, for preventing blackening stains on the fabric surface, for reducing or avoiding re-staining, and / or as an anti-scaling agent, in fabric care and home care products or industrial and institutional (I&I) cleaning products, use.

21. A cleaning composition or a fabric care and home care product comprising at least one graft polymer according to claim 1 or at least one graft polymer obtainable by the process according to claim 15 for use according to claim 19.

22. An agrochemical composition comprising at least one graft polymer according to claim 1 or at least one graft polymer obtainable by the process according to claim 15 and at least one agrochemical active ingredient, preferably containing the graft polymer in an amount of 0.5 to 10% by weight based on the total weight of the agrochemical composition, wherein the agrochemical composition is preferably in the form of a granule wettable powder or a wettable powder (powder), or in the form of a composition comprising at least one liquid phase and further, optionally, at least one dispersed phase, agrochemical composition.

23. A method for controlling phytopathogenic fungi and / or unwanted plant growth and / or unwanted attacks by insects or mites and / or for regulating plant growth, comprising applying the agrochemical composition according to claim 22 to a specific pest, its habitat, or a plant, soil and / or unwanted plant and / or useful plant and / or its habitat to be protected from said specific pest.

24. A method for controlling or preventing invertebrate pests, comprising contacting said pest or its food source, habitat or breeding ground with a pesticidally effective amount of the agrochemical composition according to claim 22.

25. A method for protecting a growing plant from attack or infestation by an invertebrate pest, comprising contacting the plant or the soil or water in which the plant is growing with a pesticidally effective amount of the agrochemical composition according to claim 22. **Claim 26** A seed comprising from 0.1 g to 10 kg of the agrochemical composition according to claim 22 per 100 kg of seeds. **Claim 27** A method for treating or protecting an animal from infestation or infection by an invertebrate pest, comprising contacting the animal with a pesticidally effective amount of the agrochemical composition according to claim 22.

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