Agrochemical Compositions

Abstract

An agrochemical composition comprising: (i) an agrochemically active ingredient; and (ii) a graft polymer, the graft polymer being a polymer backbone (A) as a graft substrate, the polymer backbone being selected from the group consisting of C2 to C4 10 at least one alkylene oxide selected from the group consisting of alkylene oxides, preferably C2-C5-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; and optionally, C2-C 14 - at least one polyol selected from the group consisting of polyols, 14 - at least one polyamine selected from the group consisting of polyamines; and polymeric side chains (B) grafted onto the polymeric backbone (A), the polymeric side chains (B) being obtainable by polymerizing, in the presence of the polymeric backbone (A), a monomer comprising at least one vinyl ester monomer (B1). It has been found that the graft polymer of the composition of the invention is suitable as a dispersant for pesticides in the agrochemical composition. Moreover, the graft polymer usually exhibits a suitably high degree of biodegradability.

Description

[Technical Field]

[0001] The present invention relates to agrochemical compositions. [Background technology]

[0002] Agrochemicals (agriculture chemicals) such as pesticides (pesticidal active ingredients) are substances that control agricultural pests such as insects, pathogens, rodents, and weeds. Pesticidal active ingredients are usually applied to plants or their seeds by spraying a liquid composition containing the active ingredient.

[0003] Many pesticides are solid particles, crystalline particles, or oily liquids, which must be dispersed in a liquid composition to be uniformly applied. A composition containing a finely dispersed pesticide active ingredient is usually obtained by adding a dispersant. Examples of conventional dispersants include salts of condensation products of naphthalenesulfonic acid and formaldehyde, salts of lignosulfonic acid, salts of maleic anhydride copolymers, and salts of phenolsulfonic acid condensation products.

[0004] Unfortunately, many dispersants used in agrochemical compositions do not degrade significantly, remaining on the plant or seed and in the surrounding ground, resulting in undesirable accumulation on the plant or seed and in the soil in which the plant or seed is planted. This problem is particularly pronounced when the dispersant is based on an all-carbon backbone and produced by radical polymerization, since all-carbon backbones (backbones that do not contain heteroatoms such as oxygen) are particularly difficult for microorganisms to degrade. Even industrially important radically produced graft polymers with polyethylene glycol backbones exhibit only limited biodegradability in wastewater. Summary of the Invention [Problem to be solved by the invention]

[0005] It would be desirable to provide dispersants, particularly biodegradable dispersants, that are useful in agrochemical compositions.

[0006] U.S. Patent No. 5,318,719A relates to a biodegradable, water-soluble graft copolymer having building properties, anti-film formation properties, dispersibility, and threshold crystal inhibiting properties, the graft copolymer comprising an acid-functional monomer and, optionally, other water-soluble monoethylenically unsaturated monomers copolymerizable with the acid-functional monomer, grafted to a biodegradable substrate comprising a polyalkylene oxide and / or a polyalkoxylated material. The graft polymer is believed to be suitable for use as a detergent additive.

[0007] Chinese Patent No. 102030871A relates to a polyethylene glycol-block-biodegradable polyester comb-graft copolymer. The comb-graft copolymer is a homopolymer or copolymer that utilizes a degradable polyethylene glycol block polyester as a hydrophobic backbone. The polymer is said to self-assemble in water to form nanoparticles useful for preparing hydrophobic drug nanoparticles. [Means for solving the problem]

[0008] The present invention provides (i) an agrochemical active ingredient; (ii) a graft polymer; 1. An agrochemical composition comprising: This graft polymer is (A) a polymer backbone as a graft substrate, C2~C 10 at least one alkylene oxide selected from the group consisting of alkylene oxides, preferably C2-C5-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, Optionally, C2 to C 14 - at least one polyol selected from the group consisting of polyols or C2 to C 14 - at least one polyamine selected from the group of polyamines; The polymer main chain (A) can be obtained by polymerizing (B) a polymer side chain grafted to the polymer main chain (A), which can be obtained by polymerizing a monomer containing at least one vinyl ester monomer (B1) in the presence of the polymer main chain (A); and The present invention provides an agrochemical composition comprising:

[0009] The graft polymers of the compositions of the present invention have been found to be suitable as dispersants for pesticides in agrochemical compositions, and furthermore, the graft polymers generally exhibit a suitably high degree of biodegradability. DETAILED DESCRIPTION OF THE INVENTION

[0010] The graft polymer comprises a polymer main chain (A) as a graft substrate and a polymer side chain (B) grafted onto the polymer main chain (A).

[0011] The polymer main chain (A) of the graft polymer is C2 to C 10 - alkylene oxides, preferably C2-C5-alkylene oxides, for example at least one alkylene oxide selected from the group ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; and optionally C2-C 14 - at least one polyol selected from the group consisting of polyols or C2 to C 14 and at least one polyamine selected from the group consisting of polyamines.

[0012] When the polymer backbone (A) is obtained by polymerizing only one kind of alkylene oxide, the polymer backbone (A) is a homopolymer. In this case, the alkylene oxide is preferably selected from ethylene oxide, 1,2-propylene oxide, and 1,2-butylene. A copolymer backbone obtained by polymerizing ethylene oxide, i.e., a polyethylene glycol backbone, is particularly preferred as the polymer backbone (A).

[0013] When the polymer backbone (A) is obtained by polymerizing more than one alkylene oxide and, optionally, at least one polyol or at least one polyamine, the polymer backbone (A) is a copolymer. In this case, the polymer backbone can be any type of known copolymer, such as a block copolymer, an alternating copolymer, or a statistical copolymer. Statistical copolymers are also known as random copolymers.

[0014] As used herein, the term "block copolymer (backbone)" means that each polymer contains at least two, i.e., two or more, homopolymer subunits (blocks) linked by covalent bonds. A diblock copolymer (two block copolymer) has two different blocks (homopolymer subunits), a triblock copolymer has three different blocks (homopolymer subunits), and so on. The number of individual blocks within this type of block copolymer is not limited; thus, an "n-block copolymer" contains n different blocks (homopolymer subunits). The size / length of such blocks within each block (homopolymer subunit) can vary. The minimum length / size of a block is based on a minimum of two individual monomers. Various types of block copolymer backbones are commercially available, for example, the "Pluronic" trademark series (BASF SE, Ludwigshafen, Germany). Specific examples include Pluronic PE 6100, Pluronic PE 6800, and Pluronic PE 3100.

[0015] If more than one alkylene oxide is polymerized to obtain the polymer backbone (A), the alkylene oxide is preferably selected from ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide. In a preferred embodiment, ethylene oxide is polymerized with at least one alkylene oxide selected from 1,2-propylene oxide and / or 1,2-butylene oxide, preferably exclusively with 1,2-propylene oxide.

[0016] Optionally, at least one alkylene oxide can also be polymerized with at least one polyol or at least one polyamine to obtain the polymer backbone.

[0017] When at least one polyol is polymerized to obtain the polymer main chain (A), the polyol may be a C2 to C6 14 Polyols, preferably C2-C 12 Preferably, the polyol is a C2-C8 polyol, more preferably a C2-C8 polyol. This polyol can act as the "core" molecule from which the polymer chain grows. This means that it is preferred that this polyol is present at the start of the polymerization reaction to obtain the polymer backbone.

[0018] The polyol is an organic compound containing multiple hydroxyl groups. The polyol is preferably an aliphatic or alicyclic polyol, especially an aliphatic polyol. The polyol is preferably selected from diols containing two hydroxyl groups and polyols containing 3 to 10 hydroxyl groups.

[0019] Suitable aliphatic diols include aliphatic diols, i.e., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, triethylene glycol, and neopentyl glycol. A suitable cycloaliphatic diol is cyclohexanedimethanol.

[0020] Suitable polyols containing 3 to 10 hydroxyl groups include aliphatic and alicyclic polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, glucose, fructose, sucrose and lactose, especially glycerin.

[0021] In one embodiment, the polymer backbone is obtained by polymerizing ethylene oxide and at least one alkylene oxide selected from 1,2-propylene oxide and / or 1,2-butylene oxide, preferably only 1,2-propylene oxide, and at least one polyol, in particular diethylene glycol and / or glycerin.

[0022] When at least one polyamine is polymerized to obtain the polymer backbone (A), the polyamine may be a C2-C 14 Polyamines, preferably C2-C 12 Polyamines, more preferably C2-C8-polyamines, which can act as "core" molecules from which the polymer chains grow, meaning that they are preferably present at the start of the polymerization reaction to obtain the polymer backbone.

[0023] The polyamine is an organic compound containing multiple amino groups. The polyamine is preferably an aliphatic or alicyclic polyamine, particularly an aliphatic polyamine. The polyamine is preferably selected from alkylene polyamines such as ethylene diamine, propylene diamine, diethylene triamine, and dipropylene triamine.

[0024] In a preferred embodiment, the polymer backbone is C2-C 10 In a more preferred embodiment, the polymer main chain is obtained by polymerizing at least one alkylene oxide selected from the group consisting of C2 to C6 alkylene oxides in the absence of polyamine. 10-alkylene oxides, in the absence of a polyol and in the absence of a polyamine.

[0025] Those skilled in the art are familiar with the methods for obtaining various types of copolymers, for example, a suitable discussion is given in EP 0 362 688 A2.

[0026] Preferably, the number average molecular weight M of the polymer main chain (A) n is 500 to 12,000 g / mol, preferably 9,000 g / mol or less, more preferably 6,000 g / mol or less, even more preferably 3,800 g / mol or less or 3,500 g / mol or less, particularly 3,000 g / mol or less, for example, 2,750 g / mol or less, 2,700 g / mol or less, or 2,650 g / mol or less, and is at least 1,000 g / mol, more preferably at least 1,500 g / mol. n The smaller the molecular weight, the higher the biodegradability. The molecular weight can be determined as described later in the experimental section.

[0027] The polymer backbone (A) can be based on varying amounts of hydrophilic ethylene glycol units (-C2H4-O) derived from ethylene oxide, which influences the overall properties of the graft polymer. The total EO content (%EO), which represents the total amount of ethylene glycol units in the polymer backbone (A), is defined as follows: %EO = m(EO) / (m(whole main chain)) where m(EO) is the total mass of ethylene glycol units and m(total backbone) is the total mass of the polymer backbone (A). The polymer backbone can have low, medium or high total EO content, i.e., %EO, which affects the biodegradability and performance of the agrochemical composition. The ranges are defined as follows: Low: 5~20% EO Moderate: 21~50%EO High: 51-90% EO.

[0028] In a preferred embodiment, the total EO content (% EO) is in the range of 10-80%, preferably at least 20%, and preferably at most 70%.

[0029] It has been found that graft polymers containing a copolymer backbone (A) with a moderate total EO content, i.e., 21-50% EO, exhibit particularly high biodegradability. Graft polymers containing a polymer backbone (A) obtained by polymerizing ethylene oxide also exhibit particularly high biodegradability.

[0030] The graft polymer comprises polymeric side chains (B) grafted onto a polymeric backbone (A), said polymeric side chains (B) being obtained by polymerizing, in the presence of the polymeric backbone (A), monomers comprising at least one vinyl ester monomer (B1) and, optionally, at least one secondary monomer (B2).

[0031] Preferably, the polymeric side chains (B) are obtained by radical polymerization of monomers, including at least one vinyl ester monomer (B1) and optionally at least one auxiliary monomer (B2), in the presence of the polymeric backbone (A).

[0032] As the vinyl ester monomer (B1), any vinyl ester known to those skilled in the art can be used, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, or vinyl benzoate. Preferably, the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate, and vinyl laurate, in particular vinyl acetate and vinyl laurate. In a particularly preferred embodiment, the polymer side chain (B) is obtained by radical polymerization of vinyl acetate.

[0033] The auxiliary monomers (B2) are preferably selected from nitrogen-containing olefinically unsaturated monomers, especially vinyl lactams, such as vinyl lactams and vinyl imidazoles; and vinyl ethers.

[0034] Suitable vinyl lactams include N-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam, preferably N-vinylpyrrolidone and N-vinylcaprolactam, and particularly preferably N-vinylpyrrolidone (NVP).

[0035] Suitable vinylimidazoles include 1-vinylimidazole and C1-C8-alkyl substituted derivatives of 1-vinylimidazole such as 2-methyl-1-vinylimidazole, preferably 1-vinylimidazole.

[0036] Suitable vinyl ethers include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether, in particular n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether.

[0037] When an auxiliary monomer (B2) is used to obtain the polymer side chain (B), the weight ratio of the vinyl ester monomer (B1) to the auxiliary monomer (B2) is not particularly limited. However, the amount of the vinyl ester monomer (B1) is usually 1% by weight or more based on the total amount of monomers constituting the polymer side chain (B). In this case, the polymer side chain (B) can be obtained by polymerizing, especially radically polymerizing, 1 to 100% by weight of the monomer (B1), most preferably vinyl acetate, with 0 to 99% by weight of at least one auxiliary monomer (B2).

[0038] In one embodiment, the polymer side chain (B) is - 10 to 100% by weight, preferably 25 to 100% by weight, more preferably 50 to 100% by weight, most preferably 75 to 100% by weight of at least one vinyl ester monomer (B1), based on the total amount of monomers constituting the polymer side chains (B), and optionally - 0 to 90% by weight, preferably 0 to 75% by weight, more preferably 0 to 50% by weight, most preferably 0 to 25% by weight of at least one auxiliary monomer (B2), based on the total amount of monomers constituting the polymer side chain (B), It can be obtained by polymerization, particularly (free) radical polymerization, in the presence of the polymer main chain (A).

[0039] In a preferred embodiment, the polymer side chain (B) is - 65 to 100% by weight, preferably 70 to 100% by weight, more preferably 75 to 100% by weight, most preferably 80 to 100% by weight of at least one vinyl ester monomer (B1), based on the total amount of monomers constituting the polymer side chains (B), and optionally - 0 to 35% by weight, preferably 0 to 30% by weight, more preferably 0 to 25% by weight, most preferably 0 to 20% by weight of at least one auxiliary monomer (B2), relative to the total amount of monomers constituting the polymer side chain (B), It can be obtained by polymerization, particularly (free) radical polymerization, in the presence of the polymer main chain (A).

[0040] In a preferred embodiment, the polymer side chains (B) are obtained by polymerizing at least one vinyl ester monomer (B1), in particular vinyl acetate, in the presence of the polymer backbone (A) in the absence of further monomers.

[0041] The graft polymer of the present invention may contain a certain amount of ungrafted polymer ("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 auxiliary monomers when one or more auxiliary monomers (B2) are used. The amount of such ungrafted vinyl ester homo- and copolymers can be high or low depending on the reaction conditions, but a low amount is preferred. That is, an increased amount of grafted side chains is preferred. A reduction in the amount of ungrafted vinyl ester homo- and copolymers can be achieved by suitable reaction conditions, such as the input and relative amounts of vinyl ester and radical initiator, as well as their amounts relative to the main chain present. This is generally known to those skilled in the art.

[0042] The graft polymer of the present invention can be characterized by its degree of grafting (the number of sites on the polymer main chain (A) where the polymer side chains (B) are grafted). A low degree of grafting is preferred.

[0043] The degree of grafting and the amount of ungrafted polymer can be adjusted to optimize performance, application range, or desired agrochemical performance in a particular area of ​​interest, e.g., a particular agrochemical composition.

[0044] In one embodiment of the present invention, the polymer side chains (B) of the graft polymer according to the invention are hydrolyzed in whole or at least in part after obtaining the graft polymer itself, which means that the hydrolysis of the polymer side chains (B) of the graft polymer in whole or in part is carried out after the polymerization process of the polymer side chains (B) is completed.

[0045] By completely or at least partially hydrolyzing the polymer side chain (B) of the graft polymer according to the present invention in this way, each side chain unit derived from at least one vinyl ester monomer (B1) is converted from an ester functional group to an alcohol functional group in the polymer side chain (B). It should be noted that the corresponding vinyl alcohol is not suitable as a monomer for use in the polymerization process of the polymer side chain (B) in terms of stability. Therefore, to obtain an alcohol functional group (hydroxy substituent) in the polymer side chain (B) of the graft polymer according to the present invention, the alcohol functional group is usually introduced by hydrolyzing the ester functional group of the side chain.

[0046] Theoretically, each ester functional group in the polymer side chain (B) can be replaced with an alcohol functional group (hydroxy group). In that case, the polymer side chain is completely hydrolyzed (saponified). Note that when an auxiliary monomer (B2) such as N-vinylpyrrolidone is used, the units derived from N-vinylpyrrolidone used as the auxiliary monomer (B2) in the polymer side chain (B) are usually not hydrolyzed.

[0047] Hydrolysis can be carried out by any method known to those skilled in the art, for example, hydrolysis can be induced by the addition of a suitable base such as sodium hydroxide or potassium hydroxide.

[0048] In this embodiment, it is preferred to hydrolyze only a portion of the polymer side chains (B), for example the units derived from the vinyl ester monomers (B1), in an amount of up to 20%, 40% or 60% by weight, based on the total weight of the vinyl ester monomers (B1).

[0049] In one embodiment, the polymeric side chains (B) are obtained by radical polymerization of monomers, including at least one vinyl ester monomer (B1) and at least one auxiliary monomer (B2); and The polymer side chains (B) are hydrolyzed after polymerization in whole or in part, preferably to an extent of up to 50% relative to the at least one vinyl ester monomer (B1) used in the polymerization.

[0050] In a preferred embodiment, the polymer side chains (B) are not hydrolyzed after polymerization.

[0051] Preferably, in each polymerization process to obtain the polymeric side chain (B), no other monomers are used other than those defined above in connection with the at least one vinyl ester monomer (B1) and the optional auxiliary monomer (B2). However, if further monomers other than those according to (B1) and (B2) are present during the polymerization, it is preferred that such further monomers (other than B1 and B2) are present in an amount of less than 1% by weight, relative to the total amount of monomers used to obtain the polymeric side chain (B). Preferably, the amount of said additional monomers is less than 0.5% by weight, more preferably less than 0.01% by weight, relative to the total amount of monomers used to obtain the polymeric side chain (B).

[0052] In a preferred embodiment, no monomers containing acid functionality are used, and in particular the monomers used to obtain the polymer side chains (B) of the graft polymer according to the invention preferably do not contain acid-functional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinylacetic acid and / or acryloylpropionic acid.

[0053] The weight ratio of the polymer backbone (A) to the polymer side chains (B) in the graft polymer of the present invention is not particularly limited. However, typically, the graft polymer contains at least 0.2 wt. % of the polymer side chains (B) based on the total weight of the graft polymer. Preferably, the graft polymer contains at least 1 wt. % of the polymer side chains (B) based on the total weight of the graft polymer.

[0054] In a preferred embodiment, the graft polymer contains 25 to 90% by weight, preferably 30 to 85% by weight, more preferably 35 to 80% by weight, for example 40 to 75% by weight, particularly 45 to 70% by weight of the polymer main chain (A) relative to the total weight of the graft polymer.

[0055] In a preferred embodiment, the graft polymer contains polymer side chains (B) in an amount of 10 to 75% by weight, preferably 15 to 70% by weight, more preferably 20 to 65% by weight, even more preferably 25 to 60% by weight, and most preferably 30 to 55% by weight, based on the total weight of the graft polymer. By keeping the proportion of polymer side chains (B) within this range, it is possible to improve biodegradability.

[0056] Therefore, the graft polymer preferably contains, relative to the total weight of the graft polymer, 25 to 90% by weight of the polymer main chain (A) and 10 to 75% by weight of the polymer side chain (B); preferably 30 to 85% by weight of the polymer main chain (A) and 15 to 70% by weight of the polymer side chain (B); more preferably 35 to 80% by weight of the polymer main chain (A) and 20 to 65% by weight of the polymer side chain (B); for example, 40 to 75% by weight of the polymer main chain (A) and 25 to 60% by weight of the polymer side chain (B); and particularly 45 to 70% by weight of the polymer main chain (A) and 30 to 55% by weight of the polymer side chain (B).

[0057] In a preferred embodiment, the present invention provides (i) an agrochemical active ingredient; (ii) a graft polymer; 1. An agrochemical composition comprising: This graft polymer is (A) Number average molecular weight M n a polymer main chain as a graft substrate having a molecular weight of 500 to 3,800 g / mol, C2~C 10- alkylene oxides, preferably C2-C5-alkylene oxides, for example at least one alkylene oxide selected from the group ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; and optionally C2-C 14 -At least one polyol selected from polyols or C2 to C 14 and at least one polyamine selected from the group consisting of polyamines; (B) a polymer side chain grafted onto the polymer backbone (A), - 65 to 100% by weight of at least one vinyl ester monomer (B1), based on the total amount of monomers constituting the polymer side chains (B), and optionally - at least one auxiliary monomer (B2) is present in an amount of 0 to 35% by weight, preferably 0 to 30% by weight, based on the total amount of monomers constituting the polymer side chain (B); A monomer comprising The polymer side chain (B) can be obtained by polymerization in the presence of the polymer main chain (A). The present invention provides an agrochemical composition comprising:

[0058] In a further preferred embodiment, the present invention provides a method for producing a pharmaceutical composition comprising: (i) an agrochemical active ingredient; (ii) a graft polymer; 1. An agrochemical composition comprising: This graft polymer is (A) Number average molecular weight M n a polymer main chain as a graft substrate having a molecular weight of 500 to 3,800 g / mol, C2~C 10- alkylene oxides, preferably C2-C5-alkylene oxides, for example at least one alkylene oxide selected from the group ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; and optionally C2-C 14 -At least one polyol selected from polyols or C2 to C 14 and at least one polyamine selected from the group consisting of polyamines; (B) a polymer side chain grafted onto the polymer backbone (A), - 65 to 100% by weight of at least one vinyl ester monomer (B1), based on the total amount of monomers constituting the polymer side chains (B), and optionally - at least one auxiliary monomer (B2) is present in an amount of 0 to 35% by weight, preferably 0 to 30% by weight, based on the total amount of monomers constituting the polymer side chain (B); A monomer comprising The polymer side chain (B) can be obtained by polymerization in the presence of the polymer main chain (A). Including, The graft polymer contains 25 to 90% by weight, particularly 45 to 70% by weight, of the polymer main chain (A) and 10 to 75% by weight, particularly 30 to 55% by weight, of the polymer side chain (B), based on the total weight of the graft polymer. Agrochemical compositions are provided.

[0059] The specific embodiments set forth below highlight particular aspects of the graft polymer, and it is understood that the descriptions and embodiments set forth above also apply to the specific embodiments set forth below, where applicable.

[0060] In a first particular embodiment, the graft polymer is: (A) a polymer backbone as a graft substrate, C2~C 10the polymer backbone (A) obtainable by polymerizing at least one alkylene oxide selected from the group consisting of alkylene oxides, preferably C2-C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide; (B) a polymeric side chain grafted onto the polymeric backbone (A), which can be obtained by copolymerizing, in the presence of the polymeric backbone (A), monomers comprising at least one vinyl ester monomer (B1) and at least one auxiliary monomer (B2), wherein the auxiliary monomer (B2) is (B2a) at least one nitrogen-containing olefinically unsaturated monomer selected from C1-C8-alkyl substituted derivatives of 1-vinylimidazole, such as 1-vinylimidazole or 2-methyl-1-vinylimidazole, preferably 1-vinylimidazole, and optionally (B2b) at least one further nitrogen-containing olefinically unsaturated monomer, preferably selected from N-vinyl lactams such as N-vinyl pyrrolidone, N-vinyl piperidone and N-vinyl caprolactam, more preferably selected from N-vinyl pyrrolidone and N-vinyl caprolactam, most preferably selected from N-vinyl pyrrolidone, The polymer side chain (B) comprises Includes.

[0061] In this embodiment, the graft polymer preferably comprises, based on the total weight of the graft polymer: - 1 to 30% by weight, preferably 3 to 25% by weight, more preferably 5 to 20% by weight, most preferably 10 to 20% by weight of a vinyl ester monomer (B1), - 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 20 to 40% by weight, most preferably 25 to 35% by weight of auxiliary monomer (B2), Includes.

[0062] Furthermore, in this embodiment, the auxiliary monomer (B2) preferably comprises 10 to 100 wt. %, preferably 20 to 90 wt. %, more preferably 30 to 80 wt. %, and most preferably 40 to 70 wt. % of the nitrogen-containing olefinically unsaturated monomer (B2a), based on the total weight of the auxiliary monomer (B2).

[0063] Furthermore, in this embodiment, it is particularly preferred that the vinyl ester monomer (B1) is vinyl acetate, the nitrogen-containing olefinically unsaturated monomer (B2a) is 1-vinylimidazole and the nitrogen-containing olefinically unsaturated monomer (B2b) is N-vinylpyrrolidone.

[0064] In a second particular embodiment, the graft polymer is: (A) a statistical copolymer backbone as a graft substrate, C2~C 10 - an alkylene oxide, preferably a C2-C5-alkylene oxide, such as at least two alkylene oxides selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, and (B) a polymeric side chain grafted onto the statistical copolymer backbone (A), said polymeric side chain (B) being obtainable by polymerizing a monomer comprising at least one vinyl ester monomer (B1) in the presence of the statistical copolymer backbone (A); Includes.

[0065] In this embodiment, the number average molecular weight M nis preferably 500 to 6,000 g / mol, preferably 5,500 g / mol or less, more preferably 5,000 g / mol or less, even more preferably 4,500 g / mol or less, particularly 4,000 g / mol or less, for example 3,800 g / mol or less or 3,500 g / mol or less, particularly 3,000 g / mol or less, even more preferably 2,750 g / mol or less, most preferably 2,700 g / mol or less or 2,650 g / mol or less, and preferably at least 800 g / mol or at least 1,000 g / mol, more preferably at least 1,200 g / mol.

[0066] In a third particular embodiment, the graft polymer is: (A) a polymer backbone as a graft substrate, The polymer main chain (A) can be obtained by polymerizing ethylene oxide; (B) a polymer side chain grafted onto the statistical copolymer main chain (A), said polymer side chain (B) being obtainable by polymerizing a monomer comprising at least one vinyl ester monomer (B1) in the presence of the polymer main chain (A); Includes.

[0067] In this embodiment, the number average molecular weight M n is preferably 500 to 5,000 g / mol, preferably 4,000 g / mol or less, more preferably 3,800 g / mol or less or 3,500 g / mol or less, even more preferably 3,000 g / mol or less, for example 2,750 g / mol or less, and most preferably 2,700 g / mol or less or 2,650 g / mol or less.

[0068] Further in this embodiment, preferably, the compound of formula P: P = [molecular weight of polymer main chain M n (g / mol)] × [grafting ratio of vinyl acetate based on the total weight of the polymer (grafting ratio as a percentage of the weight of the polymer, where the weight of the polymer is set to "1")] is 1500 or less, preferably 1200 or less, more preferably 1000 or less, even more preferably 800 or less, and most preferably 600 or less, for example 400 or less, or even 300 or less, and is at least 100, preferably at least 150, and more preferably at least 200.

[0069] In a fourth particular embodiment, the graft polymer is: (A) a block copolymer main chain as a graft substrate, which can be obtained by block copolymerizing at least two alkylene oxides selected from ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, and 2,3-pentene oxide; (B) polymeric side chains grafted onto the block copolymer backbone, said polymeric side chains (B) being obtainable by polymerizing monomers comprising at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone (B2); Includes.

[0070] In this embodiment, the alkylene oxide is preferably selected from ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide. Preferably, one of the at least two alkylene oxides used is ethylene oxide, and preferably, the second alkylene oxide used is 1,2-propylene oxide. Most preferably, the block copolymer backbone (A) is obtainable by block copolymerizing ethylene oxide and 1,2-propylene oxide. Preferably, the number (x) of individual blocks in the block copolymer backbone (A) is an integer, where x is 3 to 10, preferably 3 to 5, and more preferably x is 3.

[0071] Suitable block copolymer backbones (A) are described, for example, in EP 0 362 688 A2. Preferably, the alkylene oxides used to prepare the individual blocks of the block copolymer backbone (A) are added sequentially. However, when transitioning from one alkylene oxide supply to another, a so-called "dirty structure" may occur at the end / boundary of each block within the individual block under consideration, in which a small amount of alkylene oxide from each adjacent block may be contained. However, it is preferred that the block copolymer backbone (A) according to the present invention does not contain a so-called "dirty structure" or "dirty passage" at the boundary of each block.

[0072] Further in this embodiment, the block copolymer backbone (A) is preferably a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG), preferably having a structure according to formula (A1) or formula (A2), wherein formula (A1) is defined as follows: [ka] (In the formula, n is an integer ranging from 2 to 100, preferably from 3 to 80; m is an integer ranging from 2 to 100, preferably from 10 to 70, and more preferably from 14 to 54; Formula (A2) is defined as follows: [ka] (In the formula, o is an integer ranging from 2 to 100, preferably from 5 to 50, and more preferably from 8 to 27; p is an integer ranging from 2 to 100, preferably from 5 to 50, and more preferably from 7 to 24; The structure (A2) is particularly preferred. By using the block copolymer main chain (A) having the structure (A2), it is possible to achieve a particularly high biodegradability.

[0073] Further in this embodiment, preferably, the graft polymer is such that the copolymer (A) is a triblock copolymer of polyethylene oxide and polypropylene oxide, and the number average molecular weight M of the triblock copolymer backbone (A) is n is less than 6,000 g / mol, preferably less than 5,000 g / mol, more preferably less than 3,800 g / mol or less than 3,650 g / mol, even more preferably less than 3,000 g / mol, for example less than 2,750 g / mol or less than 2,700 g / mol.

[0074] Of the four specific embodiments shown above, the third and fourth embodiments are particularly preferred.

[0075] The graft polymer of the composition of the present invention preferably has a weight average molecular weight M w is 1,000 to 100,000 g / mol, preferably 2,000 to 45,000 g / mol, and more preferably 3,000 to 30,000 g / mol. It has been found that the biodegradability of a graft polymer increases as the weight average molecular weight of the graft polymer decreases.

[0076] The graft polymer of the composition of the present invention preferably has a low polydispersity. Preferably, the polydispersity M of the graft polymer w / M n is less than 7, preferably less than 5, more preferably less than 3, especially less than 2.5, for example less than 2.3, and most preferably in the range of 1.0 to 2.2 (M w is the weight average molecular weight, and M n is the number average molecular weight, and 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 part.

[0077] To be successfully utilized as an agrochemical composition, the graft polymer of the composition of the present invention preferably has at least one, and in particular two or more, of the following properties: - a certain level of biodegradability, preferably at least 30%, more preferably at least 40%, most preferably at least 50%, for example 35, 45, 55, 60, 65, 75, 80, 85 or more up to 100% biodegradation within 28 days according to OECD 301F (all percentages are by weight based on total solids). The polymer should have some water solubility so that it can be utilized in the aqueous environments typically present in agrochemical applications. Preferably, the polymers of the present invention should exhibit moderate to good water solubility, more preferably very good water solubility. 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 reasonably high polymer solids concentration, e.g., as a "pure" (in which case it is usually liquid) product, dissolved in a solvent, typically an aqueous solution comprising water and an organic solvent, water alone, or an organic solvent alone, and the viscosity of such polymer or polymer solution must be in a range that allows the usual technological process steps, such as pouring, pumping, dosing, etc.

[0078] Thus, the viscosity is preferably less than about 4000 mPa·s, more preferably at most 3500 mPa·s, even more preferably at most 3000 mPa·s, such as at most 4500, 3750, 3250, 2750, or even 2600 or less, for example in the range of 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPa·s, at a polymer concentration (defined as the weight percent of dry polymer in the total weight of the polymer solution, based on the total solids content of the polymer in the solution) of preferably at least 10 wt%, more preferably at least 20 wt%, even more preferably at least 40 wt%, and most preferably at least 50 wt%, for example at least 60, 70, 80, or even 90 wt%. Viscosity can be determined as described below in the experimental section.

[0079] Viscosity measurements can be performed at either 25°C or at elevated temperatures, e.g., 50°C or even 60°C, thereby allowing for suitable handling of the polymer solution on a commercial scale. It goes without saying that depending on the amount of solvent added, the viscosity will decrease as the amount of solvent increases, and vice versa, and can therefore be adjusted if desired. It is also clear that the measured viscosity depends on the measurement temperature; for example, the viscosity of a given polymer with a given solids content, e.g., 80% by weight, 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 alone, without added solvent, is between 70 and 99% by weight, more preferably between 75 and 85% by weight. In more preferred embodiments, the solids content of the as-prepared polymer alone, without added solvent, is between 70 and 99 wt. %, more preferably between 75 and 95 wt. %, and the viscosity measured at 60°C is less than 3000 mPa·s, 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 mPa·s.

[0080] Biodegradability increases under each of the following conditions: - the molecular weight of the polymer backbone (A) is lower compared to the higher molecular weight; and / or - a lower weight percentage of polymer side chains (B) grafted to the main chain compared to a higher weight percentage.

[0081] Preferred graft polymers are obtained using at least one of the following conditions: I) Number average molecular weight M of polymer main chain (A) n is 3,800 g / mol or less, preferably 3,500 g / mol or less, more preferably 3,000 g / mol or less, more preferably 2,750 g / mol or less, and most preferably 2,700 g / mol or less or 2,650 g / mol or less; II) the weight percentage of the polymer side chains of the graft polymer is greater than 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight, even more preferably at least 30% by weight, up to 75% by weight, more preferably at most 70% by weight, even more preferably at most 65% by weight, most preferably at most 60% by weight or at most 55% by weight, based on the total weight of the graft polymer; III) The weight percentage of ethylene oxide (EO) moieties relative to the total alkylene oxide moieties present in the main chain (A) of the graft polymer is at least 10%.

[0082] The graft polymer of the composition of the present invention can be prepared by polymerizing at least one monomer (B1) and, optionally, at least one auxiliary monomer (B2) in the presence of a polymer backbone (A). The grafting process of grafting polymer side chains onto a polymer backbone is well known. Any grafting process known to those skilled in the art can be employed in the present invention.

[0083] Preferably, the polymer side chains (B) are obtained by radical polymerization, which is known to those skilled in the art. The grafting process can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D), suitable representatives of which are well known.

[0084] The term "radical polymerization" as used herein includes free radical polymerization as well as variations thereof, 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.

[0085] More preferably, the process for obtaining the graft polymer is carried out by a method comprising polymerizing, to obtain the polymer side chains (B), at least one monomer (B1) selected from vinyl acetate or vinyl propionate and N-vinylpyrrolidone as the optional auxiliary monomer (B2) in the presence of the polymer backbone (A), a free radical-forming initiator (C), and, optionally, at most 50% by weight of at least one organic solvent (D), based on the total weight of the components (A), (B1), optional (B2) and (C), at an average polymerization temperature such that the decomposition half-life of the initiator (C) is between 40 and 500 minutes, and in such a way that the proportion of unconverted monomer (B1) and optional (B2) and initiator (C) in the reaction mixture is always maintained in a quantitative deficit relative to the polymer backbone (A).

[0086] The amount of initiator (C) is preferably 0.1 to 5% by weight, in particular 0.3 to 3.5% by weight, based in each case on the polymer side chains (B).

[0087] Preferably, the steady-state concentration of radicals present at the average polymerization temperature is substantially constant, and monomers (B1) and, optionally, (B2) are always present in the reaction mixture in only low concentrations (e.g., a total of 5% by weight or less), which allows the reaction to be controlled and allows the controlled preparation of graft polymers with the desired low polydispersity.

[0088] The term "average polymerization temperature" is understood 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.

[0089] The decomposition half-life of the 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.

[0090] The initiator (C) and the monomers (B1) and optionally (B2) are advantageously added so that the undecomposed initiator and the monomers (B1) and (B2) are present in the reaction mixture at a substantially constant low concentration, preferably less than 15% by weight, in particular less than 10% by weight, based on the total amount of initiator added during the monomer addition.

[0091] 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.

[0092] 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-C4~C 12 -Alkyl hydroperoxide and tert-(C9-C 12 -aralkyl)hydroperoxides of O-C2 to C 12acylated derivatives, such as 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; - tert-C8~C 14 -Alkylenebisperoxide di-O-C4~C 12 - acylated derivatives, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene; - Diperoxide (C2-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; - tert-C4-C5-Alkyl peroxycarbonate (C4-C 12 -alkyl), for example, tert-amyl peroxycarbonate (2-ethylhexyl); - Peroxydicarbonate di(C2-C 12 -alkyl), for example, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0093] Examples of particularly suitable initiators (C), depending on the average polymerization temperature, are given below: - 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(2-ethylhexyl) peroxycarbonate; - Average polymerization temperature 110~120℃: tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl(2-ethylhexyl) peroxycarbonate.

[0094] Preferred initiators (C) are tert-C4-C5-alkyl hydroperoxides O-C4-C 12 -acylated derivatives, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0095] Particularly advantageous polymerization conditions can be established 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.

[0096] The polymerization reaction can be carried out in the presence of an organic solvent (D), preferably in small amounts. Of course, it is also possible to use mixtures of different solvents (D). It is preferred to use water-soluble or water-miscible solvents.

[0097] When 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, and most preferably 2 to 25% by weight, based in each case on the sum of components (A), (B1), optionally (B2) and (C).

[0098] Examples of suitable solvents (D) include: - monohydric alcohols, preferably aliphatic C1-C 16 -Alcohols, more preferably aliphatic C2-C 12alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; - Polyhydric alcohols, preferably C2-C 10 -diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol; - alkylene glycol ethers, preferably alkylene glycol mono(C1-C 12 -alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, such as ethylene glycol monomethyl and -ethyl ethers and propylene glycol monomethyl and -ethyl ethers; - polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2 to 20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2 to 20 ethylene glycol units and polypropylene glycols having 2 to 10 propylene glycol units, most preferably polyethylene glycols having 2 to 15 ethylene glycol units and polypropylene glycols having 2 to 4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; - polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C 25 -alkyl) ethers, more preferably poly(C2-C4-alkylene) glycol mono(C1-C4) ethers having 2 to 20 alkylene glycol units, 20 -alkyl) ethers, most preferably poly(C2-C3-alkylene) glycol mono(C1-C3-alkylene) glycol mono(C1-C3-alkylene) ethers having 3 to 20 alkylene glycol units,16 -alkyl) ethers; carboxylic acid esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as ethyl acetate and ethyl propionate; 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;

[0099] The solvent (D) can advantageously also be used in the formulation of the agrochemical composition and may therefore remain in the polymerization product, and may be selected from polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units and in particular alkoxylation products of C6-C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0100] Highly branched C8~C 16 Alkoxylation products of alcohols are particularly preferred, and their use makes it possible to obtain polymer mixture compositions that are free-flowing at 40-70°C, have relatively low viscosity, and have a very low polymer content. Branching may 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 preferred examples of such alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide, C alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 Or C 16 / C18 Preferred is 2-propylheptanol, a fatty alcohol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide.

[0101] The polymer backbone (A), the monomers (B1) and optionally (B2), the initiator (C) and, if appropriate, the solvent (D) are typically heated in a reactor to the selected average polymerization temperature.

[0102] The polymerization is preferably carried out so that there is always an excess of polymer (polymer backbone (A) and formed graft polymer (B)) in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally at least 10:1, preferably at least 15:1, more preferably at least 20:1.

[0103] The polymerization process can be carried out in various types of reactors.

[0104] The reactor used is preferably a stirred tank into which all or part of the polymer backbone (A) is initially charged together with, if appropriate, the monomers (B1) and optionally (B2), the initiator (C) and part of the solvent (D), generally up to 15% by weight of the specified total amount, heated to the polymerization temperature, and the remaining amounts of (B1), (B2), (C) and, if appropriate, (D) are metered in, preferably separately, over a period of preferably at least 2 hours, more preferably at least 4 hours, and most preferably at least 5 hours.

[0105] In the case of a variant thereof, a particularly preferred substantially solvent-free process, the entire polymer backbone (A) is initially charged as a melt, and the monomers (B1) and optionally (B2) and, in addition, the initiator (C), preferably in the form of a 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled during the polymerization so as to maintain the selected average polymerization temperature, in particular within a range of + / - 10°C, in particular within a range of + / - 5°C.

[0106] In a further particularly preferred variant, the low-solvent process, the procedure is as described above, except that solvent (D) is metered in during the polymerization to limit the viscosity of the reaction mixture. It is also possible to start metering in the solvent only at a later point in time once the polymerization has progressed, or to add it in portions.

[0107] The polymerization can be carried out under normal pressure or under reduced or elevated pressure. If the pressure selected exceeds the boiling point of the monomers (B1) or (B2) used or the optional diluent (D), the polymerization is carried out with reflux cooling.

[0108] After polymerization is complete, the volatiles can be removed under vacuum.

[0109] The agrochemical compositions of the present invention include, in addition to the graft polymer, an agrochemical active ingredient. The graft polymer of the compositions of the present invention has been found to be suitable as a dispersant for a wide variety of agrochemical active ingredients. The term "agrochemical active ingredient" refers to a substance that imparts a desired biological activity to the agrochemical composition.

[0110] Agrochemical active ingredients include pesticides, safeners, nitrification inhibitors, urease inhibitors, micronutrients and / or plant growth regulators. Typically, agrochemical active ingredients are pesticides. Pesticides include insecticides, herbicides, fungicides, algicides, rodenticides, molluscicides and nematicides. Those skilled in the art are familiar with pesticides, and they are described, for example, in Pesticide Manual, 16th Edition (2013), The British Crop Protection Council, London.

[0111] Preferably, the agrochemical active ingredient is selected from insecticides, fungicides and herbicides.

[0112] Suitable insecticides include carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, insecticides classified as METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amithras, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, afidopyropene, amidrazone, dinpropylidaz, fipronil, or derivatives thereof.

[0113] Suitable fungicides include dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides such as fluxapyroxad and diflufenican, carboxylic acid diamides, chloronitriles such as chlorothalonil, cyanoacetamide oximes, cyanoimidazoles, cyanobenzoates, cyclohexyl ... Chloropropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranone, methoxyacrylates such as azoxystrobin, methoxycarbamates, morpholines, N-phenylcarbamates oxazolidinediones, oximinoacetic acids, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles such as fludioxonil, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidineamines, pyrimidines, pyrimidinonehydrazone ...imidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidines, pyrimidines, pyrimidinonehydrazones, pyrimidines, pyrimidines, pyrimidine These fungicides include chloroquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, tetrazolinones such as methyltetraprole, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines and triazoles, in particular, fungicides classified as triazoles such as mefentrifluconazole, triticonazole, prothioconazole and tebuconazole.Particularly preferred fungicides are azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, methyltetraprole, mefentrifluconazole and tebuconazole, especially azoxystrobin, fluxapyroxad and chlorothalonil and diflufenican, especially azoxystrobin.

[0114] Suitable herbicides include acetamides, amides, aryloxyphenoxypropionic acid esters, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridyliums, carbamates, cinmethylins, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenols, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids such as glufosinate, phosphoro Herbicides are classified into amidates, phosphorodithioates, phthalamates, pyrazoles such as pyroxasulfone, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines such as atrazine, indaziflam, and terbuthylazine, triazinones such as metribuzin, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils including aryluracils such as saflufenacil, and ureas. Particularly preferred herbicides are atrazine, indaziflam, saflufenacil, pyroxasulfone, glufosinate, cinmethylin, terbuthylazine and metribuzin, especially atrazine.

[0115] In a particularly preferred embodiment, the agrochemical active ingredient is selected from azoxystrobin, fluxapyroxad, fludioxonil, chlorothalonil, atrazine, methyltetraprole, mefentrifluconazole, prothioconazole, tebuconazole, terbuthylazine, diflufenican and metribuzin, preferably from azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, terbuthylazine and atrazine, most preferably from azoxystrobin.

[0116] Suitable safeners include (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oximinophenylacetonitrile, acetphenoxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic acid amide, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazolecarboxylic acid, phosphorothiolates and N-alkyl-O-phenylcarbamates and agriculturally acceptable salts thereof, and agriculturally acceptable derivatives thereof, such as amides, esters and thioesters, provided that they contain an acid group.

[0117] Suitable nitrification inhibitors include 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, Etridiazole), 2-sulfanilamide thiazole (ST), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole thiourea (TU), N-(1H-pyrazolyl-methyl)acetamide, e.g., N- ((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide and N-(1H-pyrazolyl-methyl)formamide, for example, 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") and / or their derivatives and / or salts; glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium glycolate, hereinafter referred to as "DMPG") and / or its isomers and / or derivatives;Citrate addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium citrate, hereinafter referred to as "DMPC") and / or its isomers and / or derivatives; lactic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium lactate, hereinafter referred to as "DMPL") and / or its isomers and / or derivatives; mandelic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium mandelate, hereinafter referred to as "DMPM") and / or its isomers and / or derivatives; 1,2,4-triazole (hereinafter referred to as "TZ") and / or its derivatives and / or and its salts; 4-chloro-3-methylpyrazole (hereinafter referred to as "ClMP") and / or its isomers and / or derivatives and / or salts thereof; addition reaction 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.

[0118] Examples of urease inhibitors include N-(n-butyl)thiophosphoric triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric triamide (NPPT), 2-nitrophenylphosphoric triamide (2-NPT), other NXPTs known to those skilled in the art, phenylphosphorodiamidates (PPD / PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see, e.g., 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, a composition containing approximately 16.9% by weight of NBPT, approximately 5.6% by weight of NPPT, and approximately 77.5% by weight of other ingredients, including solvents and adjuvants.

[0119] Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, dwarfing agents, growth promoters and further unclassified plant growth regulators.

[0120] Suitable micronutrients are compounds containing boron, zinc, iron, copper, manganese, chlorine and molybdenum.

[0121] Agrochemical compositions typically contain a biologically effective, e.g., pesticidal, amount of an agrochemical active ingredient. The term "effective amount" refers to an amount of a composition or agrochemical active ingredient that is sufficient to control harmful fungi on cultivated plants or to protect materials, for example, without causing 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 being treated, climatic conditions, and the specific agrochemical active ingredient used.

[0122] Agrochemical compositions typically contain the agrochemical active ingredient at a concentration of 1 to 70% solids by weight (% ws), preferably 1 to 60% ws, more preferably 10 to 50% ws, and most preferably 20 to 45% ws, based on the total weight of the agrochemical composition. Agrochemical compositions typically contain at least 5% ws, preferably at least 15% ws, more preferably at least 25% ws, and most preferably at least 35% ws, based on the total weight of the agrochemical composition. Agrochemical compositions typically contain up to 95% ws, preferably up to 65% wt, more preferably at least 45% wt, based on the total weight of the agrochemical composition. The purity of the active ingredient used, as determined by nuclear magnetic resonance (NMR) spectroscopy, is 90% to 100%, preferably 95% to 100%.

[0123] Agrochemical compositions typically contain the graft polymer at a concentration of 0.5 to 20% ws, preferably 0.5 to 10% ws, and more preferably 1 to 8% ws, based on the total weight of the agrochemical composition. The concentration of the graft polymer is typically up to 15% ws, more preferably up to 9% ws, and most preferably up to 7% ws, based on the total weight of the agrochemical composition. The concentration of the graft polymer is usually at least 2% ws, preferably at least 2.5% ws, based on the total weight of the agrochemical composition.

[0124] The graft polymer according to the present invention is usually present in dissolved form in the agrochemical composition, especially when the agrochemical composition is an aqueous agrochemical composition. Typical solvents include those described below as adjuvants.

[0125] The graft polymer can be present as solid particles, such as dispersed particles, particularly when the agrochemical composition is a non-aqueous composition, such as a solid composition, or an agrochemical composition having a continuous organic phase.

[0126] The weight ratio of agrochemical active ingredient to graft polymer in the agrochemical composition is typically in the range of 1:1 to 30:1, preferably 5:1 to 30:1, more preferably 7:1 to 20:1.

[0127] The agrochemical compositions can be any type of conventional agrochemical composition, 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, SE, DC), 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 compositions for treating plant propagation material such as seeds (e.g., GF). These and further composition types are defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

[0128] Preferred types of compositions are suspensions, emulsifiable concentrates (EC), wettable powders or water-dispersible dusts and granules, especially suspensions. Preferred suspensions include suspension concentrates (SC), suspoemulsions (SE), and dispersible concentrates (DC). The most preferred suspensions are suspension concentrates (SC).

[0129] The composition is prepared by known methods, such as those 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 a graft polymer with an agrochemical active ingredient. When the agrochemical composition is a suspension, the method typically includes forming a millbase by contacting the agrochemical active ingredient with water. This premix is ​​then typically subjected to grinding or milling to form the final suspension. The graft polymer may be added to either the millbase or the final suspension, and is preferably added to the millbase.

[0130] When the agrochemical composition is a granule, it is typically obtained by preparing a premix containing the agrochemical active ingredient, the graft polymer, the filler, and typically not more than 5% by weight of water, and then extruding this premix. The extrudate is then dried and converted into granules.

[0131] 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, antifoaming agents, colorants, crystal growth inhibitors, tackifiers and binders.

[0132] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling fractions of mineral oil, e.g., kerosene, light oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g., toluene, paraffin, tetrahydronaphthalene, alkylated naphthalene; 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.

[0133] 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.

[0134] 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 Edition or North American Edition).

[0135] Suitable anionic surfactants include alkali metal, alkaline earth metal, or ammonium salts of sulfonates, sulfates, phosphates, and carboxylates, and mixtures thereof. Examples of sulfonates include alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, and sulfosuccinamates. Examples of sulfates include sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, and sulfates of fatty acid esters. Examples of phosphates include phosphoric acid esters. Examples of carboxylates include alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

[0136] Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates include compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters, which are 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 include fatty acid glucamides or fatty acid alkanolamides. Examples of esters include fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants include sorbitan, ethoxylated sorbitan, sucrose and glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants include homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate.

[0137] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are AB or ABA type block polymers containing polyethylene oxide and polypropylene oxide blocks, or ABC type block polymers containing 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 polyvinylamine or polyethyleneamine.

[0138] 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 include 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.

[0139] Suitable thickeners include polysaccharides (e.g., xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides include bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents include ethylene glycol, propylene glycol, urea, and glycerin. Suitable antifoaming agents include silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g., red, blue, or green) include low-water-soluble pigments and water-soluble dyes. Examples include inorganic colorants (e.g., iron oxide, titanium oxide, hexacyanoferrate) and organic colorants (e.g., alizarin, azo, and phthalocyanine colorants). Suitable tackifiers or binders include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biologically derived or synthetic waxes, and cellulose ethers.

[0140] Examples of types of compositions and their preparation methods are given below:

[0141] i) Water-soluble concentrate (SL, LS) 10-60% by weight of the agrochemical active substance, 5-15% by weight of a wetting agent (e.g., alcohol alkoxylate), and 1-15% by weight of a graft polymer are dissolved in water and / or a water-soluble solvent (e.g., alcohol) to a total weight of 100%. The active substance dissolves when diluted with water.

[0142] ii) Dispersible Concentrate (DC) 5 to 25% by weight of an agriculturally active ingredient, 1 to 10% by weight of a graft polymer, and optionally an additional dispersant (e.g., polyvinylpyrrolidone) are dissolved in an organic solvent (e.g., cyclohexanone) to a total weight of 100%. Dilution with water results in a dispersion.

[0143] iii) Emulsifiable concentrate (EC) 15-70% by weight of an agriculturally 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) to a total weight of 100%. Dilution with water results in an emulsion.

[0144] iv) Emulsions (EW, EO, ES) 5-40% by weight of an agriculturally 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., an aromatic hydrocarbon). This mixture is added to water using an emulsifier so that the total is 100% by weight, resulting in a homogeneous emulsion.

[0145] v) Suspension agents (SC, OD, FS) In an agitator ball mill, 20-60% by weight of the agrochemical active ingredient is ground to a fine suspension of the active substance with 1-10% by weight of a graft polymer, optional additional 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% by weight of the total. Upon dilution with water, a stable suspension of the active substance results. For FS-type compositions, up to 40% by weight of a binder (e.g., polyvinyl alcohol) is added. Suspoemulsions (SE) can be obtained by mixing a suspension with an emulsifier or emulsion, such as an oil-in-water emulsion (EW).

[0146] 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 and 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.

[0147] 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 a graft polymer and optionally a further dispersant (e.g., sodium lignosulfonate), 1-3% by weight of a wetting agent (e.g., alcohol ethoxylate), and a solid carrier (e.g., silica gel) to make up 100% by weight. Dilution with water results in a stable dispersion or solution of the active substance.

[0148] viii) Gel-type preparations (GW, GF) In an agitator ball mill, 5-25% by weight of the agrochemical active ingredient is finely ground with 3-10% by weight of the graft polymer and optionally a further dispersant (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. Upon dilution with water, a stable gel of the active substance is formed.

[0149] 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 dimethylamide and cyclohexanone), 10-25% by weight of a blend of surfactants (e.g., alcohol ethoxylate and arylphenol ethoxylate), 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.

[0150] 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). Radical polymerization is initiated with a radical initiator to form microcapsules of poly(meth)acrylate. 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 of a protective colloid (e.g., polyvinyl alcohol).

[0151] Polyurea microcapsules are formed by adding a polyamine (e.g., hexamethylenediamine). The total amount of monomers is 1-10% by weight. This weight percentage relates to the total CS composition. The microcapsules can then be dispersed in an aqueous composition. For this purpose, 1-40% by weight of the microcapsules are mixed with 2-10% by weight of the graft polymer and optional further dispersants and wetting agents (e.g., sodium lignosulfonate and alcohol ethoxylate), 0.1-2% by weight of a thickener (e.g., xanthan gum), and water to make up 100% of the CS composition.

[0152] ix) Powder (DP, DS) 1 to 10% by weight of the agrochemical active ingredient is finely ground and intimately mixed with 1 to 20% by weight of the graft polymer and a solid carrier (eg, finely divided kaolin) totaling 100% by weight.

[0153] x) Granules (GR, FG) 0.5 to 30% by weight of the agrochemical active ingredient is finely ground and combined with 1 to 20% by weight of the graft polymer and a solid carrier (e.g., silicate) in a total amount of 100% by weight. Granulation is carried out by extrusion, spray drying, or fluidized bed.

[0154] 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.

[0155] Compositions of types i) to xi) may optionally contain further adjuvants such as those mentioned above, 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 colorant.

[0156] In one embodiment, the agrochemical composition is a suspension, preferably a suspension concentrate, which typically contains 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.

[0157] Agrochemical suspensions contain at least a portion of 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 water in an amount of 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.Agrochemical compositions can contain water in an amount of up to 95% by weight, preferably at most 80% by weight, more preferably at most 70% by weight, most preferably at most 60% by weight, for example, at most 50% by weight, each based on the total weight of the suspension.

[0158] Agrochemical active ingredients typically have low water solubility, which may be 10 g / L or less, preferably 5 g / L or less, more preferably 1 g / L or less, most preferably 0.5 g / L or less, and especially 0.1 g / L or less at 20° C. and pH 7.

[0159] The agrochemical active ingredient is present in the form of particles suspended in the agrochemical suspension. The particles can be characterized by a particle size distribution determined by dynamic light scattering. A suitable dynamic light scattering measuring device is, inter alia, that manufactured under the trade name Malvern Mastersizer 3000.

[0160] Particles of agrochemically active ingredients can be characterized by their median diameter, commonly abbreviated as the D50 value. The D50 value represents the specific particle diameter below which half of the volume of the particle population is smaller. The D50 value is typically determined in accordance with ISO 13320:2009. The D50 value of particles can be in the range of 0.05 μm to 25 μm, preferably in the range of 0.1 μm to 20 μm, more preferably in the range of 0.5 to less than 20 μm, most preferably in the range of 0.5 μm to 15 μm, and particularly preferably in the range of 0.5 μm to 10 μm. The D50 value of particles is typically at least 0.75 μm, preferably at least 1 μm, with the upper limit preferably being 3 μm or less or 2 μm or less.

[0161] Particles of an agrochemically active ingredient can be further characterized by their D90 value. The D90 value represents the specific particle size below which 90% of the particle population by volume is smaller. The D90 value is typically determined according to ISO 13320:2009. The D90 value of a particle can be less than 30 μm to 3 μm, particularly less than 20 μm or less than 15 μm, and particularly less than 10 μm or less than 8 μm or less than 6 μm or less than 5 μm.

[0162] Particles of an agrochemical active ingredient can also be characterized by their D10 value. The D10 value represents the specific particle size below which 10% of the particle population by volume is smaller. The D10 value is typically determined in accordance with ISO 13320:2009. The D10 value of a particle can generally be less than 2 μm, for example in the range of 0.05 to <2 μm, particularly in the range of 0.1 to 1.5 μm or in the range of 0.1 to 1 μm.

[0163] Preferably, the particles have a D50 value in the range of 0.5 to 10 μm, in particular in the range of 0.5 to 3 μm or in the range of 0.75 to 2 μm, and a D90 value in the range of 3 to less than 10 μm.

[0164] The suspended particles can be in the form of crystalline particles or amorphous particles that are solid at 20°C.

[0165] Typically, at least 50% by weight, preferably at least 70% by weight, and more preferably at least 90% by weight of the agrochemical active ingredient, based on the total weight of the agrochemical active ingredient, can be present as solid particles in the agrochemical suspension.

[0166] The agrochemical suspension may contain an additional active ingredient, which may be selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biopesticides, nitrification inhibitors, urease inhibitors, and / or growth regulators. The additional active ingredient may be present in the agrochemical suspension in dissolved form or as suspended particles. The concentration of the additional active ingredient is typically 1 to 50% by weight, preferably 10 to 25% by weight, based on the total weight of the agrochemical suspension.

[0167] Agrochemical suspensions can be prepared at any pH value. Preferably, the pH of the agrochemical suspensions according to the invention is less than 9, more preferably between 4 and 8.

[0168] Agrochemical suspensions typically contain a thickener. The term "thickener" 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 ocide condensation products, polyvinyl acetate, maleic anhydride, polypropylene glycol, polyacrylonitrile block copolymers, proteins and carbohydrates.

[0169] The present invention also relates to the use of a graft polymer according to the present invention as a dispersant for an agrochemical active ingredient in an agrochemical composition, such as a suspension. It is understood that all embodiments herein relating to an agrochemical composition relate to both the agrochemical composition of the present invention and the use of a graft polymer according to the present invention as a dispersant for an agrochemical active ingredient in an agrochemical composition.

[0170] For the treatment of plant propagation material, particularly seeds, typically used are seed treatment solutions (LS), suspoemulsions (SE), seed treatment flowables (FS), dry seed treatment powders (DS), wettable seed treatment slurries (WS), water-soluble seed treatment dusts (SS), seed treatment emulsions (ES), emulsifiable concentrates (EC), and gel formulations (GF). These compositions can be diluted 2-10 times to obtain ready-to-use preparations with active substance concentrations 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, particularly seeds, include dressing, coating, pelleting, spraying, dipping, and in-furrow application to the propagation material. Preferably, the agrochemical compositions are applied to the plant propagation material in a manner that does not induce germination, such as by seed dressing, pelleting, coating and dusting.

[0171] The present invention also relates to 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 to phytopathogenic fungi, to unwanted plant growth or to unwanted insects or mites; and / or to the habitat of phytopathogenic fungi, to the habitat in which unwanted plants grow or to the habitat of unwanted insects or mites; and / or to the plants to be protected and / or to the soil of the plants to be protected; and / or to useful plants and / or their habitat.

[0172] In one embodiment, the method is for controlling phytopathogenic fungi. In another embodiment, the method is for controlling unwanted plant growth. In another embodiment, the method is for suppressing unwanted infestation by insects or mites. These methods typically involve treating the plant to be protected, the locus in which it grows, the phytopathogenic fungi and / or unwanted plant growth and / or unwanted insect or mite attack with an agrochemical composition.

[0173] Suitable treatment methods include, inter alia, soil treatment, seed treatment, furrow application, and foliar application. Soil treatment methods include soil drench, drip irrigation (drip application to the soil), root, tuber, or bulb immersion, or soil injection. Seed treatment methods include seed dressing, seed coating, seed spraying, seed soaking, and seed pelleting. Furrow application typically 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.

[0174] When used in plant protection, the application rates of the agrochemically active substances 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.

[0175] When used in the protection of materials or stored products, the application rates of the active substances vary depending on the area of ​​application and the type of effect desired. Amounts customarily used in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0176] For the treatment of plant propagation material such as seeds, for example by spraying, covering or drenching the seeds, 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) is generally required.

[0177] The present invention also relates to seeds containing the agrochemical composition of the present invention in an amount of 0.1 g to 10 kg per 100 kg of seeds.

[0178] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the agrochemical composition as a premix or, if appropriate, 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.

[0179] The user typically applies the agrochemical compositions according to the invention from a predosage device, a backpack sprayer, a spray tank, a spray aircraft or drone, or an irrigation system. Typically, the agrochemical composition is formulated to the desired application concentration with water, buffers, and / or further adjuvants, thereby obtaining a ready-to-use spray solution or agrochemical composition according to the invention. Typically, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray solution are applied per hectare of agriculturally useful area.

[0180] The present invention also relates to methods for eliminating or controlling invertebrate pests, comprising contacting the pests or their food source, habitat, or breeding grounds with a pesticidally effective amount of an agrochemical composition. The present invention also relates to 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 are grown with a pesticidally effective amount of an agrochemical composition. The present invention also relates to methods for treating or protecting animals from infestation or infection by invertebrate pests, comprising contacting the animals with a pesticidally effective amount of an agrochemical composition.

[0181] Invertebrate pests according to the present invention are typically arachnids, mollusks or insects, especially insects.

[0182] According to one embodiment, the individual components of the composition according to the invention, for example the components of a kit or the components of a two- or three-component mixture, can be mixed by the user himself in a spray tank, with further adjuvants being added if appropriate.

[0183] In a further embodiment, either the individual components or the partially premixed components of the composition according to the invention can be mixed by the user in a spray tank, and further adjuvants can be added if appropriate.

[0184] In a further embodiment, either the individual components or the partially premixed components of the compositions according to the present invention may be applied together (e.g. after mixing in a tank) or sequentially.

[0185] The present invention is further illustrated by the following examples. [Example]

[0186] Polymer Measurements The K value is a measure of the relative viscosity of a diluted polymer solution and is a relative measure of average molecular weight. As the average molecular weight of a particular polymer increases, the K value also tends to increase. The K value is determined at 23°C using a polymer concentration of 1% polymer in a 3% by weight NaCl solution according to the method of H. Fikentscher, "Cellulosechemie", 1932, 13, 58.

[0187] The number average molecular weight (M n ), weight average molecular weight (M w ) and polydispersity M w / M n was 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, and 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. The molecular weight M was used for calibration. n Poly(ethylene glycol) (PEG) standards (PL) with densities ranging from 106 to 1378000 g / mol were used.

[0188] polymer backbone Examples 13, 14, and 39 used commercially available EO / PO polyether products as backbone materials, such as those available from BASF under the Breox® trade name.

[0189] Polymer backbone of Example 26 For Example 26, the EO / PO block copolymer backbone was synthesized as follows.

[0190] Step 26a: Propylene glycol + 2.6 mol PO 228.3 g of propylene glycol and 1.36 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was purged with nitrogen three times and heated to 140°C. Within 8 hours, 453.0 g of propylene oxide was added. The mixture was further stirred at 140°C for 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 680.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0191] Step 26b: EO / PO block copolymer (propylene glycol + 2.6 mol PO + 17.7 mol EO, 80 wt% EO, molecular weight 1000 g / mol) 209.6 g of the product from Step 26a and 1.39 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was flushed with nitrogen three times and heated to 140°C. Within 12 hours, 693.8 g of ethylene oxide was added. The mixture was further stirred at 140°C for 5 hours to complete the reaction. After cooling to 80°C, the reaction mixture was neutralized with 0.96 g of acetic acid. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to yield 901.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0192] Polymer backbone of Example 27 EO / PO block copolymer backbone for Example 27 (polyethylene glycol + 4.2 mol EO + 7.2 mol PO, 80 wt % EO, M n 2100 g / mol) was synthesized as follows: In a 2 L autoclave, polyethylene glycol (M n499.9 g of Pluriol E1500 (1500 g / mol) and 1.42 g of potassium tert-butylate were mixed. The autoclave was flushed with nitrogen three times and heated to 140°C. 61.7 g of ethylene oxide was added within 1 hour and stirred for an additional 2 hours. 139.4 g of propylene oxide was added within 3 hours. The mixture was stirred at 140°C for an additional 6 hours to complete the reaction. After cooling to 80°C, the reaction mixture was neutralized with 0.75 g of acetic acid. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 700.0 g of a light brown solid. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0193] Polymer backbone of Example 32 For Example 32, a statistical EO / PO polyether backbone was synthesized as follows.

[0194] Step 32a: Diethylene glycol + 5.3 mol EO + 8.3 mol PO 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 233.9 g of ethylene oxide and 482.6 g of propylene oxide was added within 13 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 820.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0195] Step 32b: Statistical EO / PO copolymer (diethylene glycol + 17.7 mol EO + 27.7 mol PO, 35 wt% EO, molecular weight 2500 g / mol) In a 2 L autoclave, 370.2 g of the product from Step 32a and 1.51 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 245.6 g of ethylene oxide and 506.7 g of propylene oxide was added within 15 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to yield 1119.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0196] Polymer backbone of Example 33 The statistical EO / PO polyether backbone for Example 33 was synthesized as follows.

[0197] Step 33a: Diethylene glycol + 12.1 mol EO + 3.2 mol PO 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 532.6 g of ethylene oxide and 186.4 g of propylene oxide was added within 13 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 825.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0198] Step 33b: Statistical EO / PO copolymer (diethylene glycol + 40.3 mol EO + 10.7 mol PO, 75 wt% EO, molecular weight 2500 g / mol) In a 2 L autoclave, 370.1 g of the product from Step 33a and 1.50 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 559.2 g of ethylene oxide and 195.8 g of propylene oxide was added within 15 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to give 1130.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0199] Polymer backbone of Example 34 For Example 34, a statistical EO / PO polyether backbone was synthesized as follows.

[0200] Step 34a: Diethylene glycol + 8.7 mol EO + 5.8 mol PO 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 381.9 g of ethylene oxide and 334.5 g of propylene oxide was added within 13 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 822.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0201] Step 34b: Statistical EO / PO copolymer (diethylene glycol + 28.9 mol EO + 19.2 mol PO, 55 wt% EO, molecular weight 2500 g / mol) In a 2 L autoclave, 370.1 g of the product from Step 34a and 1.50 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 370.2 g of ethylene oxide and 351.6 g of propylene oxide was added within 15 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to give 1128.0 g of a light brown oil. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0202] Polymer backbone of Example 35 For Example 35, a statistical EO / PO polyether backbone was synthesized as follows.

[0203] Step 35a: Diethylene glycol + 14.4 mol EO + 1.26 mol PO 106.1 g of diethylene glycol and 1.63 g of potassium tert-butylate were mixed in a 2 L autoclave. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 634.4 g of ethylene oxide and 73.2 g of propylene oxide was added within 13 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to obtain 815.0 g of a light brown wax. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0204] Step 35b: Statistical EO / PO Copolymer (Diethylene Glycol + 48.0 mol EO + 4.2 mol PO, 90 wt% EO, Molecular Weight 2500 g / mol) In a 2 L autoclave, 366.1 g of the product from Step 35a and 1.49 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 661.1 g of ethylene oxide and 76.8 g of propylene oxide was added within 15 hours. The mixture was stirred at 140°C for an additional 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. This was filtered to yield 1105.0 g of a light brown wax. 1 H-NMR was measured in CDCl3 and confirmed the predicted structure.

[0205] For Examples 51 and 52, an EO / PO polyether product commercially available from BASF under the trade name Lupranol® was used. Specifically, Lupranol® 2048 was used in Example 51, and Lupranol® 6000 / 1 was used in Example 52. Lupranol® 2048 is a polymer obtained from glycerin, PO, and EO, and has the structure glycerin[2.25]-PO[5.54]-PO[19.72] / EO[67.49]-EO[5.0] (M n 3550 g / mol). Lupranol® 6000 / 1 is a polymer derived from diethylene glycol, PO and EO, with the structure DEG[4.9]-EO[12.4]-PO[20.9] / EO[47.5]-EO[14.3] (M n 2220 g / mol).

[0206] All other examples used commercially available polyether products as backbone materials, such as those available from BASF under the trade names Pluriol® and Pluronic®.

[0207] Graft polymer The graft polymerizations shown below were carried out using the materials and ratios and amounts shown below and in Table 1.

[0208] Example 1: Graft polymerization of vinyl acetate (40 wt%) onto a PO-EO-PO block copolymer (60 wt%) First, a PO-EO-PO block copolymer (M n Six hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed 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 rate within 56 minutes at 95°C. After the feed addition was complete, 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 hour.

[0209] Example 2: Graft polymerization of vinyl acetate (30 wt%) onto PO-EO-PO block copolymer (70 wt%) First, a PO-EO-PO block copolymer (M n770 g of vinyl acetate (6500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 7.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (330 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0210] Example 3: Graft polymerization of vinyl acetate (20 wt%) onto PEG (80 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n Eight hundred grams of vinyl acetate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0211] Example 4: Graft polymerization of vinyl acetate (30 wt%) onto PO-EO-PO block copolymer (70 wt%) First, a PO-EO-PO block copolymer (M n Seven hundred grams of vinyl acetate (1950 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0212] Example 5: Graft polymerization of vinyl acetate (50 wt%) onto PO-EO-PO block copolymer (50 wt%) First, a PO-EO-PO block copolymer (M n500 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (500 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0213] Example 6: Graft polymerization of vinyl acetate (20 wt%) and vinyl laurate (20 wt%) onto PEG (60 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n A total of 640 g of vinyl peroxy-2-ethylhexanoate (4000 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.11 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 36.16 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (213.33 g of vinyl acetate) and Feed 3 (213.33 g of vinyl laurate) were started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.72 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.89 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred for 1 hour at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0214] Example 7: Graft polymerization of vinyl acetate (40 wt%) onto PO-EO-PO block copolymer (60 wt%) First, a PO-EO-PO block copolymer (M n Six hundred grams of vinyl acetate (1950 g / mol) was charged and melted at 90°C. Feed 1, consisting of 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0215] Example 8: Graft polymerization of vinyl acetate (40 wt%) onto PEG (60 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nSix hundred grams of vinyl acetate (4000 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.90 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0216] Example 9: Graft polymerization of vinyl acetate (40 wt%) onto PO-EO-PO block copolymer (60 wt%) First, a PO-EO-PO block copolymer (M nSix hundred grams of vinyl acetate (5900 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed at a constant 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 rate within 56 minutes at 95°C. After the feed addition was complete, 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 hour. The resulting graft polymer (Example 9) had an average molecular weight Mw of 5190 g / mol and a polydispersity of 1.5.

[0217] Example 10: Graft polymerization of vinyl acetate (30 wt%) onto PEG (70 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n595 g of vinyl acetate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 10.41 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 42.76 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (255 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.75 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0218] Example 11: Graft polymerization of vinyl acetate (25 wt%) onto PEG (75 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n 750 g of vinyl acetate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (250 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0219] Example 12: Graft polymerization of vinyl acetate (25 wt%) onto PO-EO-PO block copolymer (75 wt%) First, a PO-EO-PO block copolymer (M n 750 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.90 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (250 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0220] Example 13: Grafting of vinyl acetate (50 wt%) onto an EO / PO backbone (50 wt%) First, an EO / PO statistical copolymer (M n500 g of vinyl acetate (2500 g / mol; 60% EO) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.91 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (500 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.85 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0221] Example 14: Grafting of vinyl acetate (70 wt%) onto an EO / PO backbone (30 wt%) First, an EO / PO statistical copolymer (M n 300 g of vinyl acetate (2500 g / mol; 60% EO) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.91 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (700 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.85 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0222] Example 15: Graft polymerization of vinyl acetate (20 wt%) and vinyl laurate (5 wt%) onto PEG (75 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n 750 g of vinyl peroxy-2-ethylhexanoate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.50 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) and Feed 3 (50 g of vinyl laurate) were started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.48 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0223] Example 16: Graft polymerization of vinyl acetate (30 wt%) onto PEG (70 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA mixture of 700 g of vinyl acetate (600 g / mol) was charged and heated to 90°C. Feed 1, consisting of 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was dosed and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0224] Example 17: PO-EO-PO block copolymer of vinyl acetate (35 wt%) (M n Graft polymerization on 2650 g / mol; 65 wt.% First, a PO-EO-PO block copolymer (M n650 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.91 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (350 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.85 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0225] Example 18: Graft polymerization of vinyl acetate (20 wt%) onto EO-PO-EO block copolymer (80 wt%) First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n 880 g of vinyl acetate (2900 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.42 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 37.33 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (220 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.70 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0226] Example 19: Graft polymerization of vinyl acetate (60 wt%) onto PEG (40 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n 400 g of peroxy-2-ethylhexanoate (6000 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (600 g of vinyl acetate) was dosed 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 rate within 56 minutes at 95°C. After the feed addition was complete, 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 hour.

[0227] Example 20: PEG (M) of vinyl acetate (30% by weight) and vinylpyrrolidone (20% by weight) n Graft polymerization on 6000 g / mol; 50 wt.% The experimental procedure was carried out according to Example 1K of US Patent Application Publication No. 2019 / 0390142A1.

[0228] Example 21: Graft polymerization of vinyl acetate (30 wt%) onto PPG (70 wt%) First, PPG (M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA mixture of 700 g of vinyl acetate (2000 g / mol) was charged and heated to 90°C. Feed 1, consisting of 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was dosed and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0229] Example 22: Graft polymerization of vinyl acetate (40 wt%) onto PO-EO-PO block copolymer (60 wt%) First, a PO-EO-PO block copolymer (M nSix hundred grams of vinyl acetate (3100 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed at a constant 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 rate within 56 minutes at 95°C. After the feed addition was complete, 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 hour. The resulting graft polymer (Example 7) had an average molecular weight Mw of 5190 g / mol and a polydispersity of 1.5.

[0230] Example 23: Graft polymerization of vinyl acetate (15 wt%) onto PEG (85 wt%) First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n850 g of vinyl acetate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (150 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0231] Example 24: Graft polymerization of vinyl acetate (30 wt%) and vinyl laurate (10 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 60 wt%) First, a PO-EO-PO block copolymer (M nSix hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.03 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) and Feed 3 (100 g of vinyl laurate) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0232] Example 25: Graft polymerization of vinyl acetate (15 wt%) and vinyl laurate (15 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 70 wt%) First, a PO-EO-PO block copolymer (M nSeven hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.03 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (150 g of vinyl acetate) and Feed 3 (150 g of vinyl laurate) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0233] Example 26: Graft polymerization of vinyl acetate (45 wt%) onto EO-PO-EO block copolymer (Mn 1043 g / mol; 55 wt%) First, an EO / PO statistical copolymer (M nA mixture of 350 g of vinyl acetate (1043 g / mol; 80% EO) was charged and melted at 90°C. Feed 1, consisting of 2.56 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.00 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (286.36 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 1.62 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.33 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0234] Example 27: PO-EO-PO block copolymer of vinyl acetate (60 wt%) (M n Graft polymerization on 2103 g / mol; 40 wt.% First, an EO / PO statistical copolymer (M nA mixture of 350 g of vinyl acetate (2103 g / mol; 80% EO) was charged and melted at 90°C. Feed 1, consisting of 3.52 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 28.88 g of 1,2-propanediol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (525 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.23 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.33 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0235] Example 28: PO-EO-PO block copolymer of vinyl acetate (5 wt%) and vinyl laurate (15 wt%) (M n Graft polymerization on 2650 g / mol; 80 wt.% First, a PO-EO-PO block copolymer (M n800 g of peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.01 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (50 g of vinyl acetate) and Feed 3 (150 g of vinyl laurate) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0236] Example 29: Graft polymerization of vinyl acetate (45 wt%) and vinyl propionate (5 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 50 wt%) First, a PO-EO-PO block copolymer (M n500 g of vinyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.01 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (450 g of vinyl acetate) and Feed 3 (50 g of vinyl propionate) were dosed and dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0237] Example 30: PO-EO-PO block copolymer of vinyl acetate (15 wt%) and vinyl propionate (15 wt%) (M n Graft polymerization on 2650 g / mol; 70 wt.% First, a PO-EO-PO block copolymer (M nSeven hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.01 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (150 g of vinyl acetate) and Feed 3 (150 g of vinyl propionate) were started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0238] Example 31: PO-EO-PO block copolymer of vinyl acetate (5 wt%) and vinyl propionate (15 wt%) (M n Graft polymerization on 2650 g / mol; 80 wt.% First, a PO-EO-PO block copolymer (M nEight hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.01 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (50 g of vinyl acetate) and Feed 3 (150 g of vinyl propionate) were dosed and dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.46 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0239] Example 32: Vinyl acetate (40 wt%) EO / PO backbone (M n Graft polymerization on 2500 g / mol; 60 wt.% First, an EO / PO statistical copolymer (M n480 g of vinyl acetate (2500 g / mol; 35% EO) was charged and melted at 90°C. Feed 1, consisting of 4.48 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 34.30 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (320 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.83 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.69 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0240] Example 33: Vinyl acetate (40 wt%) EO / PO backbone (M n Graft polymerization on 2500 g / mol; 60 wt.% First, an EO / PO statistical copolymer (M n420 g of vinyl acetate (2500 g / mol; 75% EO) was charged and melted at 90°C. Feed 1, consisting of 3.49 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (280 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0241] Example 34: Vinyl acetate (40 wt%) EO / PO backbone (M n Graft polymerization on 2500 g / mol; 60 wt.% First, an EO / PO statistical copolymer (M n420 g of vinyl acetate (2500 g / mol; 55% EO) was charged and melted at 90°C. Feed 1, consisting of 3.70 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (280 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.34 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0242] Example 35: Vinyl acetate (40 wt%) EO / PO backbone (M n Graft polymerization on 2500 g / mol; 60 wt.% First, an EO / PO statistical copolymer (M n420 g of vinyl acetate (2500 g / mol; 90% EO) was charged and melted at 90°C. Feed 1, consisting of 3.05 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (280 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 1.93 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0243] Example 36: Graft polymerization of vinyl acetate (40 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 60 wt%) First, a PO-EO-PO block copolymer (M n Six hundred grams of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.00 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed at a constant rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 20.95 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0244] Example 37: Graft polymerization of vinyl acetate (40 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 60 wt%) First, a PO-EO-PO block copolymer (M n Six hundred grams of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 11.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 53.18 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed at a constant rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.81 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0245] Example 38: Graft polymerization of vinyl acetate (40 wt%) onto a PO-EO-PO block copolymer (Mn 2650 g / mol; 60 wt%) First, a PO-EO-PO block copolymer (M nSix hundred grams of vinyl acetate (2650 g / mol) was charged and melted at 100°C. Feed 1, consisting of 11.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 53.18 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 100°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was dosed at a constant rate over 6 hours at 100°C. Upon completion of this feed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.81 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 100°C. After the feed addition was complete, the mixture was stirred at 100°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0246] Example 39: Vinyl acetate (30 wt%) EO / PO backbone (M n Graft polymerization on 2500 g / mol; 70 wt.% First, an EO / PO statistical copolymer (M n A mixture of 420 g of vinyl acetate (2500 g / mol; 40% EO) was charged and melted at 90°C. Feed 1, consisting of 2.99 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (180 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 1.89 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0247] Example 40: PO-EO-PO block copolymer of vinyl acetate (5 wt%) and vinyl laurate (25 wt%) (M n Graft polymerization on 2650 g / mol; 70 wt.% First, a PO-EO-PO block copolymer (M n Seven hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.50 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (250 g of vinyl acetate + 50 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.48 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0248] Example 41: PO-EO-PO block copolymer of vinyl acetate (25 wt%) (M n Graft polymerization on 2900 g / mol; 75 wt.% First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n750 g of vinyl acetate (2900 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.90 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (250 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0249] Example 42: PO-EO-PO block copolymer of vinyl acetate (25 wt%) (M n Graft polymerization on 1950 g / mol; 75 wt.% First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n937.50 g of vinyl acetate (1950 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.46 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 37.38 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (312.50 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 6.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 51.25 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0250] Example 43: PO-EO-PO block copolymer of vinyl acetate (20 wt%) and vinyl laurate (5 wt%) (M n Graft polymerization on 1950 g / mol; 75 wt.% First, a PO-EO-PO block copolymer (M n750 g of vinyl peroxy-2-ethylhexanoate (1950 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.50 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate + 50 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.48 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0251] Example 44: PO-EO-PO block copolymer of vinyl acetate (40 wt%) (M n Graft polymerization on 2900 g / mol; 60 wt.% First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n600.00 g of vinyl acetate (2900 g / mol) was charged and melted at 90°C. Feed 1, consisting of 11.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.21 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400.00 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.79 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0252] Example 45: PO-EO-PO block copolymer of vinyl acetate (15 wt%) and vinyl laurate (5 wt%) (M n Graft polymerization on 2650 g / mol; 80 wt.% First, a PO-EO-PO block copolymer (M nEight hundred grams of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 11.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 53.18 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (150 g of vinyl acetate + 50 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.81 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0253] Example 46: PO-EO-PO block copolymer of vinyl acetate (20 wt%) and vinyl laurate (5 wt%) (M n Graft polymerization on 2650 g / mol; 75 wt.% First, a PO-EO-PO block copolymer (M n750 g of vinyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 11.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 53.18 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate + 50 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.81 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0254] Example 47: PO-EO-PO block copolymer of vinyl laurate (10 wt%) (M n Graft polymerization on 2650 g / mol; 90 wt.% First, a PO-EO-PO block copolymer (M n900 g of tert-butyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 20.41 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 59.60 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (100 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 10.43 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0255] Example 48: PEG (M) with vinyl acetate (20 wt%) n Graft polymerization on 600 g / mol; 80 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n Eight hundred grams of vinyl acetate (600 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.08 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 31.82 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 38.18 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0256] Example 49: PO-EO-PO block copolymer of vinyl acetate (20 wt%) and vinyl laurate (5 wt%) (M n Graft polymerization on 2650 g / mol; 75 wt.% First, a PO-EO-PO block copolymer (M n 750 g of vinyl peroxy-2-ethylhexanoate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 4.08 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 37.33 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate + 50 g of vinyl laurate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 32.67 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0257] Example 50: PEG (M) of vinyl acetate (10 wt%) and vinylpyrrolidone (30 wt%) n Graft polymerization on 4000 g / mol; 60 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA total of 420 g of peroxy-2-ethylhexanoate (4000 g / mol) was charged and melted at 90°C. Feed 1, consisting of 2.50 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 20.66 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (70.0 g of vinyl acetate) and Feed 3 (210.0 g of vinylpyrrolidone) were dosed and dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 3.43 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 28.34 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred for 1 hour at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0258] Example 51: Lupranol® 2048 (M) with vinyl acetate (40% by weight) n Graft polymerization on 3550 g / mol; 60 wt.% A polymerization reactor equipped with a stirrer and reflux condenser was first charged with Lupranol® 2048 (M nSix hundred grams of vinyl acetate (3550 g / mol) was charged and melted at 90°C. Feed 1, consisting of 5.60 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 42.88 g of tripropylene glycol, was dosed over a period of 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.11 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0259] Example 52: Lupranol® 6000 / 1 (M) with vinyl acetate (40% by weight) n Graft polymerization on 2200 g / mol; 60 wt.% A polymerization reactor equipped with a stirrer and a reflux condenser was first filled with Lupranol® 6000 / 1 (M n360 g of vinyl acetate (2200 g / mol) was charged and melted at 90°C. Feed 1, consisting of 3.36 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (240 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 2.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0260] Example 53: PEG (M) of vinyl acetate (20 wt%) and isobutyl vinyl ether (5 wt%) n Graft polymerization on 1500 g / mol; 75 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA mixture of 675 g of tert-butyl peroxy-2-ethylhexanoate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 18.37 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 56.45 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (180 g of vinyl acetate) and Feed 3 (45.92 g of isobutyl vinyl ether) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 4.41 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.55 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred for 1 hour at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0261] Example 54: PEG (M) of vinyl acetate (20 wt%) and isobutyl vinyl ether (5 wt%) n Graft polymerization on 1500 g / mol; 75 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA mixture of 675 g of tert-butyl peroxy-2-ethylhexanoate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 27.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 60.34 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (180 g of vinyl acetate) and Feed 3 (45.92 g of isobutyl vinyl ether) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 4.41 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 9.66 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0262] Example 55: PEG (M) of vinyl acetate (15 wt%) and isobutyl vinyl ether (10 wt%) n Graft polymerization on 1500 g / mol; 75 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA mixture of 675 g of tert-butyl peroxy-2-ethylhexanoate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 10.10 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.53 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (135 g of vinyl acetate) and Feed 3 (91.84 g of isobutyl vinyl ether) were dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 7.35 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.47 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred for 1 hour at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0263] Example 56: PEG (M) with vinyl acetate (40 wt%) n Graft polymerization on 1500 g / mol; 60 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n560.40 g of vinyl acetate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 5.23 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.05 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (373.60 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 3.31 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.32 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0264] Example 57: PEG (M) of vinyl acetate (10 wt%) and vinylpyrrolidone (30 wt%) n Graft polymerization on 1500 g / mol; 60 wt.% First, PEG(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. nA total of 420 g of peroxy-2-ethylhexanoate (1500 g / mol) was charged and melted at 90°C. Feed 1, consisting of 2.50 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 20.66 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (70.0 g of vinyl acetate) and Feed 3 (210.0 g of vinylpyrrolidone) were dosed and dosed into the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of these feeds, Feed 4, consisting of 3.43 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 28.34 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred for 1 hour at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0265] Example 58: PO-EO-PO block copolymer of vinyl acetate (40 wt%) (M n Graft polymerization onto 2650 g / mol (60 wt%) and subsequent hydrolysis of 10% vinyl acetate First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n125.19 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 0.84 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.89 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (83.46 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 0.53 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.37 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour. The mixture was stirred at 80° C. and Feed 4, consisting of 7.76 g of sodium hydroxide dissolved in 78.71 g of water, was added slowly while maintaining the temperature below 85° C. Once the feed addition was complete, the mixture was stirred at 80° C. for 1 hour and cooled to room temperature.

[0266] Example 59: PO-EO-PO block copolymer of vinyl acetate (40 wt%) (M n Graft polymerization onto 2650 g / mol (60 wt%) and subsequent hydrolysis of 25% vinyl acetate First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n125.19 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 0.84 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.89 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (83.46 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 0.53 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.37 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour. The mixture was stirred at 80° C. and Feed 4, consisting of 19.39 g of sodium hydroxide dissolved in 78.71 g of water, was added slowly while maintaining the temperature below 85° C. Once the feed addition was complete, the mixture was stirred at 80° C. for 1 hour and cooled to room temperature.

[0267] Example 60: PO-EO-PO block copolymer of vinyl acetate (40 wt%) (M n Graft polymerization onto 2650 g / mol (60 wt%) and subsequent hydrolysis of 40% vinyl acetate First, EO-PO-EO(M) was added to a polymerization reactor equipped with a stirrer and a reflux condenser in a nitrogen atmosphere. n125.19 g of vinyl acetate (2650 g / mol) was charged and melted at 90°C. Feed 1, consisting of 0.84 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.89 g of tripropylene glycol, was dosed over 6 hours and 10 minutes at 90°C while the reactor was stirred. 5.56 wt% of Feed 1 was dosed in the first 10 minutes, with the remainder dosed at a constant feed rate over 6 hours. Ten minutes after the start of Feed 1, Feed 2 (83.46 g of vinyl acetate) was started and dosed to the reactor at a constant feed rate over 6 hours at 90°C. Upon completion of this feed, Feed 3, consisting of 0.53 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.37 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90°C. After the feed addition was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour. The mixture was stirred at 80° C. and Feed 4, consisting of 37.19 g of sodium hydroxide dissolved in 94.37 g of water, was added slowly while maintaining the temperature below 85° C. Once the feed addition was complete, the mixture was stirred at 80° C. for 1 hour and cooled to room temperature.

[0268] biodegradation Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance was inoculated into wastewater collected from the Mannheim Wastewater Treatment Plant and incubated in sealed flasks at 25°C for 28 days. The oxygen consumed during this period was measured as the pressure change inside the flask using an OxiTop C (WTW). The evolved CO2 was absorbed using NaOH solution. The amount of oxygen consumed by the microbial community during the biodegradation of the test substance is expressed as a percentage of the theoretical oxygen demand (ThOD) after correction using a blank.

[0269] The results are shown in the following table, and the following abbreviations are used: - Example = Example of the present invention - Ref.Ex.=Reference example - %EO = total EO content in the main chain A1, A2: a structure according to formula (A1) or (A2), respectively - VAc = vinyl acetate - VPr = vinyl propionate - VLau = vinyl laurate - VP = vinylpyrrolidone - IBVE = Isobutyl vinyl ether - VOH = hydrolyzed vinyl acetate

[0270] [Table 1]

[0271] [Table 2]

[0272] [Table 3]

[0273] [Table 4]

[0274] [Table 5]

[0275] Viscosity measurement The viscosity of the samples was measured using a Brookfield viscometer. To perform the measurements, the samples were diluted with tripropylene glycol to the solids content shown in Table 2. The samples were heated to 60°C and measured at 30 rpm using spindle 31.

[0276] [Table 6]

[0277] Formulation Example - Suspension Concentrate All references to fully demineralized water refer to water that has been completely demineralized and further purified by ion exchange, with a pH value of approximately 5.5.

[0278] Preparation: Suspension concentrates were prepared by grinding 40% by weight (ws) of the active ingredient, 2.5% or 5% by weight of the dispersant, and 0.3% by weight of Agnique DFM 111 S (a silicon emulsion antifoam) together with fully demineralized water in a Lau GmbH disperser "DAS200" using glass beads (diameter: 2 or 3 mm) so that the dispersed pesticide particles achieved a particle size distribution characterized by D90≦10 μm, D50≦3 μm, and D10≦1 μm. Particle analysis was carried out according to method (I). The stability over time was evaluated as described in method (II). Blooming and suspension ratios were measured according to methods (III) and (IV). The specific components and experimental results are shown in the table below.

[0279] Method (I): Particle size analysis according to CIPAC MT 187 Approximately 1.0 mL of sample (suspension) was gently shaken in 9 mL of fully demineralized water. This diluted sample was added dropwise to a Malvern Master Sizer Dispersing Unit (Hydro MV) until laser shadowing reached 6% (+ / - 1.5%). In the dispersing unit, the sample was diluted with 120 mL of fully demineralized water and pumped into the measuring cell of a Malvern Mastersizer 3000 (Malvern Pananalytical GmbH, Germany), which uses a 632.8 nm laser (4 mW He-Ne) for analysis. The sample and the fully demineralized water used for dilution were used at room temperature. Particle size distributions, including D10, D50, and D90 values, were calculated using the Fraunhofer model known in the art. See, for example, ISO 13320-1:1999(E).

[0280] Method (II): Accelerated storage test according to CIPAC MT 46.3 Approximately 10 mL of sample (suspension) was placed into 40 mL glass penicillin vials fitted with screw caps and polyethylene inserts and stored in a temperature-controlled cabinet at the specified temperature (+ / - 2°C) for the specified period. For swing tests, those indicated below as "-10 / +40°C," the temperature was switched between -10°C and 40°C every 12 hours. After the specified time, the vials were removed from the oven and allowed to return to room temperature before further analysis.

[0281] Method (III): Blooming 95 mL of CIPAC Standard Water D was placed in a 100 mL graduated cylinder. Four drops of the suspension concentrate were then added and the dispersion was assessed: 1: homogeneous, 3: distributed throughout the cylinder but not completely homogeneous (<20%), 5: the SC agent did not disperse and remained at either the top or bottom. Therefore, 2 and 4 are intermediate between these.

[0282] Method (IV): Suspension rate according to CIPAC MT 161 Using the cylinder filled with the sample from Method III, further suspension concentrate was added until the cylinder contained 5 g of suspension concentrate. The contents were then homogenized by inverting the cylinder 180° 10 times and allowed to stand for 30 minutes. The top nine-tenths of the contents were then removed, and the remaining one-tenth was dried (approximately 50°C / 500 mbar) and evaluated gravimetrically to determine the suspension ratio according to the following method: Formula 1: 1 - (weight of solids / weight of water in sample composition) = weight percent solids Formula 2: [(Starting sample weight) x (decimal value of formula 1)] = grams of dispersible solids Formula 3:

number

[0283] [Table 7]

[0284] Table 8

[0285] Table 9

[0286] Table 10

[0287] Table 11

[0288] Table 12

[0289] Table 13

[0290] Table 14

[0291] Table 15

[0292] Table 16

[0293] Table 17

[0294] Table 18

[0295] Table 19

[0296] Table 20

[0297] Table 21

[0298] Table 22

[0299] Table 23

[0300] Table 24

[0301] Table 25

[0302] Table 26

[0303] Table 27

[0304] Table 28

[0305] Table 29

[0306] Table 30

[0307] Table 31

[0308] Table 32

[0309] Table 33

[0310] Table 34

[0311] Table 35

[0312] Table 36

[0313] Table 37

[0314] Table 38

[0315] Table 39

[0316] Table 40

[0317] Table 41

[0318] Table 42

[0319] Table 43

[0320] Table 44

[0321] Table 45

[0322] Table 46

[0323] Table 47

[0324] Table 48

[0325] Table 49

[0326] [Table 50]

[0327] [Table 51]

[0328] [Table 52]

[0329] [Table 53]

[0330] [Table 54]

[0331] [Table 55]

[0332] [Table 56]

[0333] [Table 57]

[0334] [Table 58]

[0335] Formulation Example - Suspension Concentrate with Co-Dispersant Preparation: Suspension concentrates were prepared by grinding 40% wt. of the active ingredient, 2.5% or 5% wt. of the dispersant, 2.5% wt. of the dispersing aid Pluronic PE 6400 (PO-EO block polymer), and 0.3% of Agnique DFM 111 S (silicone emulsion antifoam) together with fully demineralized water in a Lau GmbH "DAS200" disperser using glass beads (diameter: 2 or 3 mm) so that the dispersed pesticide particles achieved a particle size distribution characterized by D90 ≤ 10 μm and D50 ≤ 3 μm. Particle analysis was performed according to method (I). Temporal stability was evaluated as described in method (II). Blooming and suspension ratios were measured according to methods (III) and (IV). Methods (I) to (IV) are described in detail above. Specific components and experimental results are shown in the table below.

[0336] [Table 59]

[0337] [Table 60]

[0338] Composition example - Dispersible concentrate (DC) The following materials were added, in order, to a beaker with stirring at room temperature (approximately 23°C): 500 g of the polar, water-miscible solvent indicated below, 40 g of mefentrifluconazole, 32 g of methyltetraprole, 100 g of alcohol alkoxylate wetting agent (Adjuvant A), 197 g of the polymer of Example 1, and 50 g of ethoxylated castor oil (Surfactant A). The mixture was stirred until all active ingredients were dissolved and a homogeneous solution containing no crystals was obtained. This was transferred to a graduated cylinder and made up to 1 L with the polar, water-miscible solvent. The final solution was passed through a 150 μm sieve and poured into a storage bottle to obtain the dispersible concentrate (DC). The specific components and experimental results are shown in the table below.

[0339] Dilution Test 0.625 g of the DC obtained above was added to 99 g of CIPAC standard water D using a pipette. After the addition was complete, the tapered cylinder was capped and homogenized by inverting 30 times. The optical appearance was evaluated immediately and after standing for 24 hours.

[0340] Applicable Test To assess the ease of handling and application of the composition, the resulting composition was diluted with CIPAC standard water D to obtain an emulsion containing 0.625% by weight of the composition in water at a temperature of 10° C. Two liters of the diluted emulsion thus obtained were continuously pumped through a series of one 300 μm sieve and one 150 μm sieve at an initial flow rate of 100 liters / hour.

[0341] The circulating spray liquid was replaced with fresh composition five times: 1, 2, 2.5, and 4 hours after the first day, and at the beginning and 1 hour after the second day. The applicability characteristics of the composition were graded from "++" to "--" based on the flowability of the diluted emulsion through the sieve in the final filtration cycle and a visual assessment of the residue on the sieve. A grade of "--" indicates that the sieve contained a large amount of residue and the flow of the diluted emulsion through the sieve was slow, while a grade of "++" indicates that the flow of the diluted emulsion through the sieve remained essentially unchanged and little residue was collected on the sieve. To receive a "+" rating for handling, the flow at the end of the test must be 90% or greater than the initial flow rate (i.e., at least 90 L / h).

[0342] Polymer A: Example 1 Adjuvant A: Wettol LF 312 (alcohol alkoxylate) Surfactant A: Wettol EM 31 (polyethoxylated castor oil, 31 EO units) Solvent A: Solvesso 200 ND Solvent B: Cyclohexanone Solvent C: N-butylpyrrolidone

[0343] [Table 61]

[0344] It is apparent that the use of the present graft polymers reduces crystal formation in agrochemical compositions, thus increasing their applicability.

[0345] Composition example - Suspoemulsion (SE) Preparation: A SC formulation was prepared by grinding 50% ws of azoxystrobin, 2.5% ws of the dispersant (Example 3), and 0.3% ws of Agnique DFM 111 S (a silicon emulsion type antifoaming agent) in a Lau GmbH dispersing machine "DAS200" using glass beads (diameter: 2 or 3 mm) so that the dispersed pesticide particles reached a particle size distribution characterized by D90≦10 μm and D50≦3 μm. The particle analysis was carried out according to method (I). The stability over time was evaluated as described in method (II). Methods (I) and (II) are as detailed above.

[0346] To prepare the EC agent, 37% wt% of Agnique AE3-2EH (2-ethylhexyl lactate) and 25% wt% of Agnique AMD 12 (fatty acid dimethylamide) were mixed in a 100 mL bottle. Then, 8% wt% of a PO-EO block copolymer with a PO block of 1750 g / mol and containing 40% EO by weight, 4% wt% of a PO-EO block polymer with a PO block of 2750 g / mol and containing 20% ​​EO by weight, and Lutensol AO8 (ethoxylated C 13 ~C 15 6% ws of oxo alcohol was added with stirring. Once completely dissolved, 20% ws of tebuconazole was added and heated to 50°C until completely dissolved.

[0347] The SC and EC thus prepared were then combined (weight ratio 1:1) and homogenized using a torque-measuring stirrer (Hightech ViscoPakt Rheo X7) at 800 rpm for 15 minutes to obtain a suspoemulsion containing 25% ws azoxystrobin and 10% ws tebuconazole. The stability of the emulsion was evaluated as described in Method (V).

[0348] Specific components and experimental results are shown in the table below.

[0349] Method (V): Emulsion quality according to CIPAC 36.3 a) Initial quality of emulsion: Five grams of suspension concentrate was added to 95 mL of CIPAC standard water D in a 100 mL graduated cylinder. The graduated cylinder was then sealed with a glass or plastic stopper and homogenized by inverting 180° 10 times. The initial quality of the emulsion was then rated: 1: very good (homogeneous), 3: fair, 5: very poor (unable to emulsify). Thus, 2 and 4 are intermediate.

[0350] b) Emulsion stability after 24 hours: The filled graduated cylinder was then stored at room temperature for 24 hours, during which time any separation at the surface or bottom of the emulsion was recorded (recorded after 1 hour, 2 hours, 4 hours, and 24 hours).

[0351] c) Re-emulsification after 24 hours: After 24 hours of storage, the emulsion was homogenized by inverting the graduated cylinder 180° 10 times and evaluated for creaming and sedimentation after 30 minutes.

[0352] [Table 62]

[0353] [Table 63]

Claims

1. (i) an agrochemically active ingredient; (ii) a graft polymer; 1. An agrochemical composition comprising: The graft polymer is (A) a polymer backbone as a graft substrate, C ２ ~C １０ - alkylene oxide, preferably C ２ ~C ５ - alkylene oxide, for example at least one alkylene oxide selected from the group of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide; and optionally C ２ ~C １４ - at least one polyol selected from the group of polyols or C ２ ~C １４ and at least one polyamine selected from the group consisting of polyamines; (B) a polymer side chain grafted onto the polymer main chain (A), the polymer side chain (B) being obtainable by polymerizing a monomer containing at least one vinyl ester monomer (B1) in the presence of the polymer main chain (A); 1. An agrochemical composition comprising:

2. The graft polymer has a number average molecular weight M of 1,000 to 100,000 g / mol. ｎ 10. The agrochemical composition of claim 1, having

3. The polydispersity M of the graft polymer ｗ / M ｎ is less than 7, and M ｗ is the weight average molecular weight, and M ｎ 10. The agrochemical composition of claim 1, wherein is the number average molecular weight.

4. 2. The graft polymer of claim 1, wherein the graft polymer has a biodegradation according to OECD 301F of at least 30% by weight solids, preferably at least 40% by weight solids, and most preferably at least 50% by weight solids within 28 days.

5. 2. The agrochemical composition of claim 1, wherein the graft polymer comprises 25 to 90% by weight, in particular 45 to 70% by weight, of the polymer backbone (A) and 10 to 75% by weight, in particular 30 to 55% by weight, of the polymer side chains (B), based on the total weight of the graft polymer.

6. The polymer main chain (A) has a number average molecular weight M of 500 to 3,800 g / mol. ｎ 10. The agrochemical composition of claim 1, having

7. 2. The agrochemical composition of claim 1, wherein the polymer backbone (A) is obtainable by polymerizing ethylene oxide.

8. 2. The agrochemical composition according to claim 1, wherein the polymer backbone (A) is obtainable by polymerizing ethylene oxide and at least one alkylene oxide selected from 1,2-propylene oxide and / or 1,2-butylene oxide, preferably exclusively 1,2-propylene oxide.

9. 2. The agrochemical composition of claim 1, wherein the polymer backbone (A) is capped at one or both of its end groups.

10. 2. The agrochemical composition of claim 1, wherein the at least one vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate.

11. The polymer side chain (B) is At least one vinyl ester monomer (B1) is optionally present in an amount of 65 to 100% by weight, preferably 70 to 100% by weight, more preferably 75 to 100% by weight, most preferably 80 to 100% by weight, based on the total amount of monomers constituting the polymer side chain (B). At least one auxiliary monomer (B2) is present in an amount of 0 to 35% by weight, preferably 0 to 30% by weight, more preferably 0 to 25% by weight, and most preferably 0 to 20% by weight, based on the total amount of monomers constituting the polymer side chain (B).

2. The agrochemical composition according to claim 1, which is obtained by radical polymerization of the following in the presence of the polymer backbone (A).

12. The number average molecular weight M ｎ is 500 to 3,800 g / mol, and the polymer side chain (B) is 65 to 100% by weight, preferably 70 to 100% by weight, more preferably 75 to 100% by weight, most preferably 80 to 100% by weight of at least one vinyl ester monomer (B1), based on the total amount of monomers constituting the polymer side chain (B), and optionally At least one auxiliary monomer (B2) is present in an amount of 0 to 35% by weight, preferably 0 to 30% by weight, more preferably 0 to 25% by weight, and most preferably 0 to 20% by weight, based on the total amount of monomers constituting the polymer side chain (B).

2. The agrochemical composition according to claim 1, which is obtainable by radical polymerization of the following in the presence of the polymer backbone (A).

13. 13. The agrochemical composition of claim 12, wherein the graft polymer comprises 25 to 90% by weight, in particular 45 to 70% by weight, of the polymer backbone (A) and 10 to 75% by weight, in particular 30 to 55% by weight, of the polymer side chains (B), based on the total weight of the graft polymer.

14. 2. The agrochemical composition according to claim 1, wherein the agrochemical active ingredient is selected from pesticides, in particular herbicides, fungicides and insecticides.

15. 15. An agrochemical composition according to claim 14, wherein the agrochemical active ingredient is selected from azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, methyltetraprole, mefentrifluconazole, tebuconazole, atrazine, indaziflam, saflufenacil, pyroxasulfone, glufosinate, cinmethylin, terbuthylazine and metribuzin, preferably from azoxystrobin, fluxapyroxad, fludioxonil, prothioconazole, chlorothalonil, diflufenican, terbuthylazine and atrazine, in particular azoxystrobin.

16. 10. The agrochemical composition of claim 1, wherein the weight ratio of said agrochemical active ingredient to said graft polymer in said agrochemical composition is in the range of 1:1 to 30:

1.

17. 2. The agrochemical composition according to claim 1, wherein the agrochemical composition is a suspension, emulsifiable concentrate, wettable powder, water-dispersible dust or granule, in particular a suspension such as a suspension concentrate, suspoemulsion or dispersible concentrate, most preferably a suspension concentrate.

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