Comb polymers

Abstract

Disclosed is a dispersant polymer having the following formula (I) and useful for stabilizing various formulations, in particular suspension concentrate. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 416,236, filed on October 14, 2022, and U.S. Provisional Application No. 63 / 498,296, filed on April 26, 2023, each of which is expressly incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to polymers useful as dispersants and preparations (formulations) comprising the polymers. Background Art

[0004] Dispersants can be used to stabilize a wide variety of formulations. For example, so-called "comb polymers" are used for this purpose and are able to stabilize agrochemical formulations by adsorption to particles or droplets in suspension concentrates (SC), suspoemulsions (SE) and oil-in-water formulations.

[0005] 4913, available from Croda, is a methyl methacrylate polyethylene glycol grafted comb copolymer used as a dispersant in such agrochemical formulations. The copolymer is typically prepared by transesterification of a methyl methacrylate polymer with a methoxy polyethylene glycol.

[0006] 755, available from Nouryon, is another methyl methacrylate polyethylene glycol grafted comb copolymer used as a dispersant in agrochemical formulations.

[0007] Despite the availability of these materials, there remains a need for better performance in suspending and dispersing actives in agrochemical and other formulations, particularly suspension concentrate formulations. Summary of the invention

[0008] In one embodiment, the present disclosure relates to a polymer having formula (I):

[0009]

[0010] in

[0011] a is 1-25 mol %;

[0012] b is 50-95 mol%;

[0013] c is 0-25 mol%;

[0014] a+b+c=100 mol%;

[0015] n is 1-100, wherein when n>1, each -O-CH 2-CHR 7 - the groups may be identical or different;

[0016] X is O or NH, and is usually O;

[0017] R 0 For -C=OOR 6 or aryl, wherein aryl is usually -C 6 H 5 ;

[0018] R 1 It is the end group derived from the water-soluble initiator system;

[0019] R 2 H, C 1 -C 10 Hydrocarbon groups, or end groups derived from water-soluble initiator systems or chain transfer agents;

[0020] R 3 H or C 1 -C 22 Hydrocarbon;

[0021] R 4 H or CH 3 ;

[0022] R 5 H or CH 3 ;

[0023] R 6 H or C 1 -C 22 a hydrocarbon group; and

[0024] R 7 H or C 1 -C 10 Hydrocarbon.

[0025] A second embodiment of the present disclosure is directed to a method for preparing a polymer having formula (I):

[0026] in

[0027] a is 1-25 mol %;

[0028] b is 50-95 mol%;

[0029] c is 0-25 mol%;

[0030] a+b+c=100 mol%;

[0031] n is 1-100, wherein when n>1, each -O-CH 2 -CHR 7 - the groups may be identical or different;

[0032] X is O or NH, and is usually O;

[0033] R 0 For -C=OOR 6 or aryl, wherein aryl is usually -C 6 H 5 ;

[0034] R 1 It is the end group derived from the water-soluble initiator system;

[0035] R 2 H, C 1 -C 10 Hydrocarbon groups, or end groups derived from water-soluble initiator systems or chain transfer agents;

[0036] R 3 H or C 1 -C 22 Hydrocarbon;

[0037] R 4 H or CH 3 ;

[0038] R 5 H or CH 3 ;

[0039] R 6 H or C 1 -C 22 a hydrocarbon group; and

[0040] R 7 H or C 1 -C 10 Hydrocarbon;

[0041] The method comprises:

[0042] (a) introducing monomers a, b and c into a reactor under starve-fed conditions, wherein monomer a has the formula:

[0043]

[0044] Monomer b has the following formula:

[0045]

[0046] And monomer c has the formula:

[0047]

[0048] wherein monomer a, monomer b and monomer c are introduced into the reactor in a molar ratio of a:b:c of 1-25:50-95:0-25, wherein the molar ratio remains substantially constant throughout the process and the total molar ratio a+b+c=100 mol %; and

[0049] (b) obtaining a polymer of formula (I) from (a).

[0050] In a third embodiment, the present disclosure is directed to polymers prepared according to the disclosed methods.

[0051] In a fourth embodiment, the present disclosure is directed to a formulation comprising at least one active ingredient dispersed in an effective dispersing amount of at least one disclosed polymer.

[0052] In a fifth embodiment, the method is directed to a method of combating fungi comprising applying a fungicidally effective amount of a formulation as described herein to the fungi or to a locus from which fungi need to be eliminated.

[0053] In a sixth embodiment, the method is directed to a method of combating insects comprising applying an insecticidally effective amount of a formulation as described herein to the insects or to a locus from which the insects are to be eliminated.

[0054] In a seventh embodiment, the method is directed to a method for combating plants comprising applying a herbicidally effective amount of a formulation as described herein to the plants or to a locus from which the plants are to be removed.

[0055] In an eighth embodiment, the method is directed to a method of coating a surface comprising applying to the surface an effective amount of a formulation as described herein for coating the surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] The present disclosure will now be described in more detail with reference to the accompanying drawings, in which:

[0057] Figure 1 The phase separation of formulations incorporating various dispersant polymers as described in the Examples is illustrated. DETAILED DESCRIPTION

[0058] The following detailed description is illustrative only and is not intended to limit the present invention. Furthermore, the present invention is not intended to be bound by any theory presented in the preceding background or the following detailed description.

[0059] Embodiments of the present disclosure generally relate to polymers, compositions comprising the polymers, and methods for forming the polymers. For the sake of brevity, conventional techniques associated with manufacturing polymers and such compositions may not be described in detail herein. In addition, the various tasks and process steps described herein may be incorporated into a more comprehensive program or process with additional steps or functions not described in detail herein. Specifically, the various steps in the manufacture of polymers and related compositions are well-known, and therefore, for the sake of brevity, many conventional steps will only be briefly described herein, or will be omitted entirely without providing well-known process details.

[0060] In the present disclosure, in various embodiments, the term "about" can describe each value ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%. In addition, it should be considered that in various non-limiting embodiments, except for the actual examples, all numerical values ​​provided herein are endpoints or specific values ​​that are intended to be interpreted as approximate values ​​of "about" or "approximately" the stated value. It should also be considered that all isomers and chiral options of each compound described herein are expressly contemplated for use in various non-limiting embodiments.

[0061] Throughout this disclosure, the term "active" percentage is well known in the art and refers to the percentage of active or actual compound or molecule present compared to the total weight of, for example, solvents and dilute solutions of such compounds. Some compounds, such as solvents, do not have an active percentage because it is well known that their active content is approximately 100%. It will be understood by those skilled in the art that any one or more of the values ​​described herein may alternatively be described as an active percentage.

[0062] In various embodiments, the term "free of" describes an embodiment comprising less than about 5, 4, 3, 2, 1, 0.5 or 0.1 weight percent (or active weight percent) of the compound or element involved, the percentage using an appropriate weight basis understood by those skilled in the art. In other embodiments, the term "free of" describes an embodiment wherein the weight percent of the compound or element involved is zero.

[0063] The term "consisting essentially of" may describe various non-limiting embodiments that are free of one or more optional compounds described herein and / or free of one or more polymers, surfactants, additives, solvents, and the like.

[0064] It should be understood that polymer subscripts are often described as average values ​​because the synthesis of polymers often results in a distribution of individual molecules.

[0065] The polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process descriptions described herein. The embodiments exemplarily disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

[0066] An object of the present disclosure is to provide polymers that offer improved performance in suspending and dispersing actives, particularly in suspension concentrate formulations.

[0067] It is also an object of the present disclosure to provide polymers with improved properties, such as extended open time in waterborne coating formulations.

[0068] The present invention provides a polymer having formula (I):

[0069]

[0070] in

[0071] a is 1-25 mol %;

[0072] b is 50-95 mol%;

[0073] c is 0-25 mol%;

[0074] a+b+c=100 mol%;

[0075] n is 1-100, wherein when n>1, each -O-CH 2 -CHR 7 - the groups may be identical or different;

[0076] X is O or NH, and is usually O;

[0077] R 0 For -C=OOR 6 or aryl, wherein aryl is usually -C 6 H 5 ;

[0078] R 1 It is the end group derived from the water-soluble initiator system;

[0079] R 2 H, C 1 -C 10 Hydrocarbon groups, or end groups derived from water-soluble initiating systems or chain transfer agents;

[0080] R 3 H or C 1 -C 22 Hydrocarbon;

[0081] R 4 H or CH 3;

[0082] R 5 H or CH 3 ;

[0083] R 6 H or C 1 -C 22 a hydrocarbon group; and

[0084] R 7 H or C 1 -C 10 Hydrocarbon.

[0085] The present disclosure also provides a method for preparing the polymer, which comprises the following steps:

[0086] (a) introducing monomers a, b and c into a reactor under starvation feed conditions, wherein monomer a has the formula:

[0087]

[0088] Monomer b has the following formula:

[0089]

[0090] And monomer c has the formula:

[0091]

[0092] wherein monomer a, monomer b and monomer c are introduced into the reactor in a molar ratio of a:b:c of 1-25:50-95:0-25, wherein the molar ratio remains substantially constant throughout the process and the total molar ratio a+b+c=100 mol %; and

[0093] (b) obtaining a polymer of formula (I) from (a).

[0094] 4913 is available from Croda and is a methyl methacrylate polyethylene glycol grafted comb copolymer believed to be prepared by transesterification of a methyl methacrylate polymer with methoxy polyethylene glycol. Without wishing to be bound by theory, it is believed that a significant amount of unbound methoxy polyethylene glycol is present in the product. Therefore, the disclosed polymers of formula (I) are generally prepared in a manner that avoids significant amounts of this and other similar impurities.

[0095] Thus, in a typical embodiment, the polymer of formula (I) is substantially free of monomers of formula (II):

[0096]

[0097] in

[0098] n is 1-100;

[0099] R 3 H or C 1 -C 22 a hydrocarbon group; and

[0100] R 7 H or C 1 -C 10 Hydrocarbon.

[0101] When the phrase "substantially free" as used herein is related to a compound of formula (II), the phrase means that the polymer contains less than 20% by weight of the compound of formula (II), based on the total weight of the polymer. Typically, the polymer contains less than 19% by weight, or less than 18% by weight, or less than 17% by weight, or less than 16% by weight, or less than 15% by weight, or less than 14% by weight, or less than 13% by weight, or less than 12% by weight, or less than 11% by weight, or less than 10% by weight, or less than 9% by weight, or less than 8% by weight, or less than 7% by weight, or less than 6% by weight, or less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1.5% by weight, or less than 1% by weight of the compound of formula (II), or is completely free of the compound of formula (II). When the compound of formula (II) is methoxypolyethylene glycol, this means that the polymer contains less than 20% by weight, or less than 19% by weight, or less than 18% by weight, or less than 17% by weight, or less than 16% by weight, or less than 15% by weight, or less than 14% by weight, or less than 13% by weight, or less than 12% by weight, or less than 11% by weight, or less than 10% by weight, or less than 9% by weight, or less than 8% by weight, or less than 7% by weight, or less than 6% by weight, or less than 5% by weight, or less than 4% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1.5% by weight, or less than 1% by weight of methoxypolyethylene glycol, or is completely free of methoxypolyethylene glycol.

[0102] The polymer composition is usually prepared from the polymerization mixture in an aqueous medium under the reaction conditions adopted in the presence of any initiator or initiation system capable of releasing free radicals. Based on the total moles of monomers, the free radical initiator is present in an amount of about 0.01% to about 10 mol%. In a typical embodiment, the initiation system can be dissolved in water at a solubility of at least 0.1% by weight, usually at least 1% by weight and most usually at least 10% by weight at 25°C. Suitable initiators include, but are not limited to, peroxides, azo initiators, and redox systems (such as isoascorbic acid) and initiation systems based on metal ions. Initiators can also include inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauroyl peroxide; organic hydroperoxides, such as cumene hydroperoxide and tert-butyl hydroperoxide. In one embodiment, inorganic peroxides such as sodium persulfate, potassium persulfate, and ammonium persulfate are typical. In another embodiment, the initiator includes an initiation system based on metal ions comprising Fe and hydrogen peroxide and a combination of Fe and other peroxides. Organic peracids such as peracetic acid can be used. Peroxides and peracids can be optionally activated with a reducing agent, such as sodium bisulfite, sodium formaldehyde or ascorbic acid, transition metals, hydrazine, etc. A typical system is a single persulfate such as sodium persulfate or ammonium persulfate, or a redox system with iron and persulfate and hydrogen peroxide. Azo initiators can also be used, especially water-soluble azo initiators. Water-soluble azo initiators include, but are not limited to, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis{2-[1-(2-hydroxy ... dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidinyl-2-ethylpropane) dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and the like.

[0103] The molecular weight of the polymer can be controlled by various compounds used in the art, including, for example, chain transfer agents such as mercaptans, iron and copper salts, bisulfites, and lower secondary alcohols, typically isopropanol. As the content of monomer b increases to more than 75 mol%, the polymer begins to become increasingly insoluble in water. Within this composition range, higher molecular weight polymers tend to reduce water solubility. Therefore, when b>75 mol% or 79 mol%, it is important to use a chain transfer agent to minimize the effect on water solubility by reducing the molecular weight, so R in this embodiment is preferably 1.5 mol%.2 Derived from chain transfer agents. For the purposes of this disclosure, a typical chain transfer agent is a mercaptan, such as 3-mercaptopropionic acid or 2-mercaptoethanol, or a lower secondary alcohol, usually isopropanol.

[0104] As used herein, the phrase "starved feed" means gradually introducing monomers into a reactor at a sufficiently slow rate that a majority of each monomer introduced is consumed by reaction before additional monomer is added. In a typical embodiment, at least 50% of the monomer is consumed by reaction before more monomer is added, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%, or at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, or at least 86%, or at least 87%, or at least 88%, or at least 89%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% of the monomer is consumed by reaction before more monomer is added to the reactor.

[0105] The feed mole ratio of monomers is "substantially constant" means that in each case, the difference between the feed mole number of each monomer and the expected mole number of that monomer in the final polymer is within 10%, usually within 5%, more usually within 2%, and most usually within 0.5%, all on a molar basis.

[0106] In a typical embodiment, the polymer of formula (I) is a polymer wherein

[0107] a is 3-18 mol %;

[0108] b is 60-90 mol%;

[0109] c is 2-20 mol%;

[0110] n is 2-25, wherein each -O-CH 2 -CHR 7 - the groups may be identical or different;

[0111] X is O;

[0112] R 1 is an end group derived from a peroxide, persulfate or azo initiator;

[0113] R 2 H, CH 3 or terminal groups derived from alcohols or diols;

[0114] R 3 H or CH3 ;

[0115] R 4 H or CH 3 ;

[0116] R 5 H or CH 3 ;

[0117] R 6 H or CH 3 ;and

[0118] R 7 H or CH 3 .

[0119] In a more typical embodiment, the polymer of formula (I) is a polymer wherein

[0120] a is 6-14 mol %;

[0121] b is 70-85 mol%;

[0122] c is 5-15 mol%;

[0123] n is 5-15, wherein each -O-CH 2 -CHR 7 - the groups may be identical or different;

[0124] X is O;

[0125] R 1 is an end group derived from sodium persulfate, ammonium persulfate or potassium persulfate;

[0126] R 2 H, CH 3 , or end groups derived from isopropanol, propylene glycol, or a mercaptan chain transfer agent such as 3-mercaptopropionic acid or 2-mercaptoethanol;

[0127] R 3 H or CH 3 ;

[0128] R 4 H or CH 3 ;

[0129] R 5 H or CH 3 ;

[0130] R 6 H or CH 3 ;and

[0131] R 7 H or CH 3 .

[0132] In one embodiment, the polymer of formula (I) is derived from methoxy polyethylene glycol methacrylate.

[0133] In a typical aspect of this embodiment, the compound of formula (II) is methoxypolyethylene glycol.

[0134] In a more typical aspect of this embodiment, the polymer of formula (I) comprises less than 20% or less than 15% or less than 10% or less than 5% by weight of methoxypolyethylene glycol, based on the total weight of the polymer.

[0135] In a particularly typical embodiment, the polymer comprises (a) 75-85 mol % of methyl methacrylate, (b) 10-15 mol % of methoxy polyethylene glycol methacrylate, and (c) 5-10 mol % of methacrylic acid, wherein (a) + (b) + (c) = 100 mol %.

[0136] In a particularly typical embodiment, the polymer comprises (a) 75-85 mol % of methyl methacrylate, (b) 10-15 mol % of methoxypolyethylene glycol methacrylate, and (c) 5-10 mol % of methacrylic acid, wherein (a) + (b) + (c) = 100 mol %, and based on the total weight of the polymer, contains less than 10% or less than 5% or less than 2% or less than 1.5% or less than 1% by weight of methoxypolyethylene glycol.

[0137] In the most typical embodiment, the polymer is a polymer prepared by the disclosed method under "starved feeding" conditions, comprising (a) 70-85 mol% methyl methacrylate, (b) 10-15 mol% methoxypolyethylene glycol methacrylate, and (c) 5-10 mol% methacrylic acid, wherein (a) + (b) + (c) = 100 mol%, and based on the total weight of the polymer, contains less than 10% or less than 5% or less than 2% or less than 1.5% or less than 1% by weight of methoxypolyethylene glycol.

[0138] In one embodiment, the present disclosure is directed to a formulation comprising a formulation carrier, at least one active ingredient effective for the intended end use, an effective dispersing amount of at least one disclosed polymer, and optionally one or more other ingredients conventionally included in formulations for said end use.

[0139] In one embodiment, the at least one active ingredient is a water-insoluble or immiscible material.

[0140] For the purposes of this disclosure, "water-insoluble or immiscible material" is defined as any active material having a solubility of less than 0.1% by weight in water.

[0141] In a typical embodiment, the disclosed formulation is an agrochemical formulation and the at least one active ingredient is an agrochemical active ingredient.

[0142] Agrochemical formulations disclosed herein include at least one agrochemical active ingredient and an effective dispersing amount of at least one disclosed polymer.

[0143] The term "effective dispersant amount" refers to an amount of the disclosed polymer that is effective to disperse the at least one active ingredient (eg, the at least one agrochemical ingredient) in a liquid carrier.

[0144] In a typical embodiment, the liquid carrier is usually water. However, if desired, an organic solvent may be added.

[0145] In another typical embodiment, the liquid carrier is water alone or optionally in combination with an organic solvent, and the disclosed polymer is used in an amount of 0.1 to 20 weight %, 0.1 to 10 weight %, 0.1 to 5 weight %, in each case based on the total weight of the formulation, and the amount is effective to disperse the at least one agrochemical ingredient in the liquid carrier.

[0146] In yet another typical embodiment, the agrochemical active ingredient is selected from the group consisting of herbicides, insecticides, fungicides, biocides, molluscicides, algaecides, plant growth regulators, insect repellents, rodenticides, nematicides, miticides, amebicides, protozoicides, crop safeners and adjuvants.

[0147] Typically, agrochemical active ingredients are water-insoluble or immiscible.

[0148] Specific examples of useful agrochemical active ingredients include, but are not limited to:

[0149] Herbicides: including triazines, such as atrazine {6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine, and prometryn {N,N'-bis(1-methylethyl)-6-(methylthio)-1,3,5-triazine)-2,4-diamine}; substituted ureas, such as diuron {N'-(3,4-dichlorophenyl)-N,N-dimethylurea}; sulfonylureas, such as metsulfuron-methyl {2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate}, triasulfuron {2-(2- chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide}, tribenuron-methyl {2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]benzoic acid methyl ester} and chlorsulfuron {2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide}; biscarbamates such as Phenmedipham {3-[(methoxycarbonyl)amino]phenyl(3-methylphenyl)carbamate}; triadimenes such as Sulfentrazone;

[0150] Fungicides: include thiocarbamates, particularly alkylenebis(dithiocarbamates), such as maneb {[1,2-ethanediylbis-[dithiocarbamate](2-)]manganese} and mancozeb {a mixture of [[1,2-ethanediyl-bis[dithiocarbamate]](2-)]manganese and [[1,2-ethanediyl-bis[dithiocarbamate]](2-)]zinc}; strobilurins, such as azoxystrobin {(E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-a-(methoxymethylene)phenylacetic acid methyl ester} and kresoxim-methyl {(E)-a-(methoxyimino)-2-[(2 1-[(1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole} and tebuconazole {(RS)-1-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol}; halogenated phthalonitriles such as chiorothalonil {2,4,5,6-tetrachloro-1,3-dicyanobenzene}; and inorganic fungicides such as copper hydroxide {Cu(OH) 2};

[0151] Insecticides: including benzoylureas, such as Difiubenzuron {N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide)}; and carbamates, such as carbaryl {1-naphthyl methylcarbamate}; and

[0152] Acaricides: include tetrazines, such as Clofentezine {3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine}.

[0153] Among the water-soluble active materials, non-selective herbicides, particularly N-(phosphonomethyl)glycine-type herbicides, such as glyphosate and glufosinate {isopropylamino and trimethylsulfonium salts of N-phosphonomethylglycine, respectively} and phosphinoamino acids, such as glufosinate-ammonium {2-amino-4-(hydroxymethylphosphino)butanoic acid}, particularly the ammonium salt. Such water-soluble actives may be used as the sole active material in water-dispersible granules, but more often they will be used in combination with water-insoluble or immiscible active materials in multi-active formulations.

[0154] In many agricultural applications, agrochemical actives are usually hydrophobic or water-insoluble, and are usually inevitably applied in the form of finely divided solids suspended in an aqueous medium. Most of these agrochemical actives are manufactured and sold in concentrated form, and other insoluble inert fillers may be added, and then diluted before application. For example, agrochemical actives are usually provided in the form of suspended concentrates (SC), wettable powders (WP), suspended emulsions (SE) or water-dispersible granules (WDG). However, since agrochemical actives are usually hydrophobic, it is necessary to add a suitable dispersant to achieve uniform dispersion under the condition of minimum mixing, such as can be easily achieved by manual or minimum mechanical mixing. Generally, this is a particularly challenging task, because the water used is extremely hard and may have a hardness (in terms of calcium carbonate) of up to 1000ppm. This requires that the dispersant has hard water resistance. Conventional dispersants cannot play a role under these harsh conditions. In addition, once uniform dispersion is achieved, the resulting suspension must remain stable for at least a long enough time so that it is applied by common techniques (such as spraying). Any settling, agglomeration or flocculation of finely divided solids may result in inconsistent and ineffective application and clogging of spray equipment. It is therefore desirable to provide a dispersant that provides easy and uniform dispersion and results in a suspension that maintains its stability during application of the aqueous dispersion, especially under hard water conditions.

[0155] In agrochemical applications, a wide variety of insoluble materials, such as agrochemical actives, are delivered in aqueous suspensions. Active ingredients, such as those used in WP, WDG, SE, and SC formulations, are generally insoluble in water at ambient temperature. Water-insoluble materials that can be advantageously used in WP, WDG, SE, and SC formulations include herbicides, insecticides, fungicides, biocides, molluscicides, algaecides, plant growth regulators, anthelmintics, rodenticides, nematicides, acaricides, amebicides, protozoicides, crop safeners, and adjuvants. Examples of such agrochemical actives, which are usually formulated as granules or powders in agriculture, include triazine herbicides, such as simazine, atrazine, terbuthylazine, terbutryn, prometryn, and ametryn; urea herbicides, such as diuron and fluoromethron; sulfonylurea herbicides, such as chlorsulfuron, metsulfuron, and chlorsulfuron; methyl), nicosulfuron, and triasulfuron; sulfonanilide herbicides such as fiumetsulam; triazolone herbicides such as sulfentrazone; organophosphate insecticides such as azinphosmethyl, chlorpyrifos, sulprofos, and azamethiphos; carbamate insecticides such as aldicarb; The pesticides used in the treatment of a variety of diseases include, for example, benzylpyrene, bendiol, bendiol, benzylpyrene ...In addition, by adding an inert carrier to facilitate processing or to help control the release of the formulation, some fertilizers and water-soluble active principles can use water-dispersible formulations. Various other insoluble materials are used in agricultural applications, including fillers and carriers, such as but not limited to natural and synthetic silicates and silicate minerals, mineral oxides and hydroxides and organic materials derived from natural and synthetic. Such materials can be used as porous carriers, added as moisture-proofing agents, to help the bonding or agglomeration properties of the formulation, or simply the formulation is filled to a convenient weight. The example of such filler can include natural silicates (such as diatomaceous earth), synthetic precipitated silica, clay (such as kaolin, attapulgite and bentonite), zeolite, titanium dioxide, iron oxides and hydroxides, aluminum oxides and hydroxides or organic materials (such as bagasse, charcoal or synthetic organic polymers). These other insoluble materials can be easily dispersed according to the disclosure.

[0156] In addition to the disclosed dispersant polymers, the disclosed formulations may also contain a surfactant wetting agent. In the case of SC formulations, the role of the wetting agent is to help remove air from the particle surface during manufacturing and to aid dilution in water. In the case of WP formulations, the role of the wetting agent may aid penetration of the solid into the water, while in the case of WDG formulations, the wetting agent may aid penetration of the particles into the water and aid disintegration of the particles back to the original particle size. In some cases, the dispersant itself may act as a suitable wetting agent, while in other cases, the dispersant may exhibit an antagonistic effect on the wetting agent.

[0157] The wetting agent may be anionic, cationic, nonionic or amphoteric, but is typically nonionic. Each of these types of wetting agents is well known in the art.

[0158] The surfactant wetting agent can be an alkyl or alkylaryl sulfonate, such as alkylbenzene sulfonate, α-olefin sulfonate and alkylnaphthalene sulfonate. These surfactant wetting agents can be alkyl sulfates, wherein the hydrophobe can be a linear or branched alcohol, such as sodium dodecyl sulfate. They can also be ethoxylated or non-ethoxylated alkyl or alkylaryl carboxylates and alkyl or alkylaryl phosphates. The surfactant wetting agent can be an alkyl polysaccharide; a dialkyl or monoalkyl sulfosuccinate derivative; a nonionic surfactant supported on an inert silicate carrier; and a nonionic surfactant provided in the form of a urea surfactant complex. The surfactant wetting agent can also include a nonionic surfactant supported on a soluble organic or inorganic carrier or an anionic surfactant such as sulfosuccinate using sodium benzoate as a carrier. Typical wetting agents are α-olefin sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates and combinations thereof.

[0159] Suitable wetting nonionic agents include Ethylan TM NS-500LQ and Ethylan TM 324, both available from Nouryon; and Atlox TM 4894、Terwet TM 1116 and Terwet TM 1118.

[0160] In addition to the disclosed dispersant polymers, the disclosed formulations may also contain one or more additional dispersants. These additional dispersants may be anionic, cationic, nonionic or amphoteric, but are typically anionic.

[0161] In a typical embodiment, the formulation further comprises at least one anionic dispersant.

[0162] In a more typical embodiment, the at least one anionic dispersant is selected from D-360 / D-390, D-425, 789, Agrilan 785, Agrilan 788 and Agrilan 700, all from Nouryon; and Atlox TM 4913、Atlox TM 4915、Atlox TM 4917、Atlox TM 4919(Croda), Tersperse TM 2500(Indorama), Tersperse TM 2020 and Tersperse TM 2100.

[0163] The present disclosure is described with reference to WP, WDG, SE and SC formulations. In each case, the formulation provides a stable aqueous dispersion of finely divided insoluble hydrophobic particles. The stability characteristics of the dispersion, and therefore the effectiveness of the dispersion, can be determined by using the suspension rate test described in CIPAC tests MT 15.1, 161 and 168. In this test, the volume fraction of suspended material is compared to the volume fraction that settles out due to gravity after 30 minutes. Generally, for WDG and WP formulations, a suspension rate of about 70% is considered to be an effective dispersant, while for SC formulations, a suspension rate of over 90% is expected to be considered an effective dispersant. For the WDG formulation, a typical metric is to use a suspension rate of 1000 ppm (as CaCO) in a suspension containing ... 3Another measure of dispersion stability is the degree to which the particles remain unaggregated. This can also be a characteristic of the uniform distribution of the dispersant in the formulation. The degree of particle aggregation is often measured by the wet sieve retention test described in CIPAC test MT 59.3. In this test, the dispersed solids are poured through a series of fine sieves and sieved, and the material retained is measured as the fraction of the total amount of dispersed material. This formation of aggregates is the main problem observed in WDG formulations and is less common in WP formulations.

[0164] Typically, WP formulations are made by grinding the agrochemical active alone or with fillers, dispersants and / or surfactant wetting agents to a suitable particle size (usually in the range of 5-15 μm). The ground material is then dry mixed with a surfactant wetting agent and / or dispersant (if not already present) or with additional dispersants and / or surfactant wetting agents to obtain a uniform composition. Powder formulations are evaluated for wettability according to methods such as CIPAC MT 53.5.1 and for suspension rate according to CIPAC MT 15.1. It is desirable that the wettability of the formulation is less than 1 minute and the suspension rate is greater than 80%. It is generally considered unacceptable to be less than 60%. Commercially acceptable results are either determined by local registration agencies or by standards set by the formulators themselves.

[0165] In the case of WDG formulations, the appropriately ground active ingredient can be mixed with one or more surfactant wetting agents and one or more dispersants with or without other fillers whose particle size is usually 5 to 15 μm. Typically, excess water is added to form agglomerates so that the particles are bonded together. Excess water is then reduced to an optimal level by appropriate air drying techniques. Agglomerates are usually granulated using one of a variety of techniques well known to those skilled in the art, including pan granulation, drum granulation, fluidized bed granulation, spray drying, tableting or extrusion techniques. Wetting agents and dispersants can be powders blended with active ingredients, or alternatively can be mixed with water for aiding agglomeration as aqueous solutions in water. Active ingredients, fillers, wetting agents and dispersants can also be ground together in one operation before adding water.

[0166] In order for a WDG formulation to be acceptable, an additional requirement needs to be met, namely that the particles should be easily dispersed back to the initial dispersed particle size in water within a short period of time. This property is called dispersibility, and when describing the current disclosure, dispersibility is measured as the time required to disperse the particles in water back to the initial particle size under standard stirring. Dispersion times of less than one minute are ideal, 20 seconds are excellent, and 2 minutes are poor. Ideally, the particles should also have good suspension rate. Suspension rate is usually tested using CIPAC MT 15.1. Results above 70% are ideal, and results below 60% are generally considered unsatisfactory. In many cases, when testing particles, a so-called maximum surface coverage result is usually obtained. This is where the suspension rate result reaches a maximum level and then levels off. Adding more dispersant does not usually improve the result. It is believed that this phenomenon is due to the particle size distribution of the material. Generally, there is a certain number of particles whose size is such that they will settle regardless of the type and concentration of dispersant. Ideally, the particles should have a low wet sieve retention rate. Wet sieve retention rate is usually tested using CIPAC MT59.3. For a 150 micron sieve, less than 0.1% of the retained material is ideal. Less than 0.02% is more ideal. Likewise, for a 53 micron sieve, less than 0.6% is ideal, with anything less than that being more ideal.

[0167] Another desirable property of a WDG formulation is that the particles should be dust-free and resistant to abrasion. This is generally a property of the granulation method used and the level of compaction obtained thereby. Generally, it is found that there is a trade-off between the dispersibility properties of a WDG formulation and the level of compaction and abrasion resistance. Abrasion resistance can be measured by subjecting the particles to a certain degree of agitation and measuring the level of smaller particles produced through sieves of various sizes. Storage stability can be tested by storing at 50 degrees Celsius and testing at intervals of 1 month and 3 months in the manner described above to determine if any of the properties have changed significantly.

[0168] As a further embodiment of the present disclosure, in the case of WP and WDG formulations, the dispersants described herein can be combined with a surfactant wetting agent selected from the following categories: α-olefin sulfonates and salts thereof, alkylnaphthalene sulfonates and salts thereof, alkylbenzene sulfonates and salts thereof, alcohol sulfates and salts thereof, alkyl polysaccharides, nonionic surfactants supported on porous silicate carriers, and urea surfactant complexes of nonionic surfactants. The wetting agent can be mixed in such formulations at a ratio exceeding 1% w / w and generally less than 5% w / w. Typical wetting agents are α-olefin sulfonates and salts thereof, alkylnaphthalene sulfonates and salts thereof, alkylbenzene sulfonates and salts thereof, and alcohol sulfates and salts thereof. Examples of these wetting agents include α-olefin sulfonates and salts thereof, such as Terwet 1004 from Huntsman and Witconate AOK from AkzoNobel Surface Chemistry, the most typical of which is C 14 -C 16 Alkyl hydroxyl and C 14 -C 16 Sodium or potassium salts of olefin sulfonates, alkylnaphthalene sulfonates and their salts such as Morwet DB from AkzoNobel Surface Chemistry or Agnique ANS 3DNP-R from Cognis. The most typical are butyl, dibutyl, isopropyl and diisopropylnaphthalene sulfonates. Examples of alkylbenzene sulfonates and their salts are Witconate 90 from AkzoNobel Surface Chemistry or Stepwet DF90 from Stepan. The most typical is C 12 Alkylbenzene sulfonate or C 10 -C 16 Salts of alkylbenzenesulfonates. Examples of alcohol sulfates and their salts are Stepwet DF-95 from Stepan or Agnique SLS1295P from Cognis. The most typical is lauryl sulfate, i.e., dodecyl sulfate.

[0169] Suspoemulsions (SE) consist of at least three phases: an aqueous phase, which contains the agrochemical active in solid dispersed form; an organic phase, which contains the second agrochemical active in liquid form or dissolved in an organic hydrophobic solvent. Usually, the aqueous phase is the continuous phase. The second agrochemical active is usually water-insoluble or immiscible. Liquid means that the melting point of the active is below 30°C. The second agrochemical active that is liquid or soluble in a hydrophobic organic solvent is an acetanilide derivative, such as alachlor, metolachlor or S-metolachlor (the S-enantiomer of racemic metolachlor); typical ones are metolachlor and S-metolachlor. Suitable fungicides which can be used as the second agrochemical active substance are, for example, benomyl, cyprodinil, dimethomorph, edifenphos, fenpropimorph, metalaxyl, (R)-metalaxyl ((R)-metalaxyl)) (enantiomers), oxadixyl, pyrifenox, thiabendazol, tridemorph, azoxystrobin, kresoxim-methyl or triazoles such as propiconazol, difenoconazol, bromoconazol, cyproconazole, epoxyconazol, hexamethylenetetracycline, oxadiazole ... hexaconazol, ipconazol, fenbuconazol, myclobutanil, penconazol, tebuconazol, triadimefon, triadimenol, tetraconazol, triticonazol or uniconazol; also famoxadone, quinoxyfen, spiroxamin, fludioxonil, fenpiclonil, famoxadone, fenhexamid and 2-[a-{[(a-methyl-3-trifluoromethylbenzyl)imino]-oxy}-o-tolyl]-glycolic acid methyl ester-O-methyl oxime.Suitable hydrophobic organic solvents in which the pesticide can be dissolved are aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosene, mixtures or substituted naphthalenes, mixtures of mono- and polyalkylated aromatic compounds, halogenated hydrocarbons (such as dichloromethane, chloroform and o-dichlorobenzene; phthalates such as dibutyl phthalate or dioctyl phthalate; ethers and esters such as ethylene glycol monomethyl ether or monoethyl ether, fatty acid esters; pyrrolidones such as N-octylpyrrolidone, ketones such as cyclohexanone; vegetable oils such as castor oil, soybean oil, cottonseed oil and possible methyl esters thereof; and epoxidized coconut oil or soybean oil.

[0170] In the most typical embodiment, the formulation is a suspension concentrate.

[0171] In one embodiment, the suspension concentrate comprises: (a) one or more active ingredients, (b) one or more dispersant polymers of the present invention, (c) one or more wetting agents, and (d) a liquid carrier. In addition, the suspension concentrate may optionally contain antifreeze agents, defoamers, rheology modifiers and preservatives.

[0172] For SC formulations in the present disclosure, active ingredients are typically added to water containing a dispersant, typically with a surfactant wetting agent and a conventional nonionic dispersant. A humectant may also be included. A dispersion is formed using high shear mixing. The dispersion is then ground by any of several wet grinding techniques so that the average particle size of the dispersed solids is less than 5 mm, more typically in the range of 1 to 3 mm. The resulting product is called millbase and may be modified with additives such as antifreeze, rheology modifiers, and anti-settling agents, and biocides and colorants may be added. In order for SC formulations to be acceptable, a high degree of thickening, settling, or aggregate growth should not be exhibited over time. These physical properties can be assessed by visual observation. SCs generally require good viscosity and storage stability. Storage stability is generally assessed by the degree of top settling or syneresis, precipitation, or "claying," i.e., the tendency to form a viscous layer at the bottom and "ooze out," which is a tendency for the dispersion to separate and not necessarily exhibit uniform settling. Redispersibility is also important. These can also be assessed visually.

[0173] Suspensions of insoluble materials in aqueous media are generally used to treat substrates, such as plants or other agricultural media. The application of the suspension on the substrate can be achieved by any convenient technology, including spraying, etc. Usually the particles are dispersed in water before the farmer sprays. The agricultural sprayer can be a small backpack hand sprayer or a large boom sprayer or other convenient technology. Aerial spraying is also sometimes used. The preparation of the present disclosure can also be directly applied to the substrate before dispersion. Rainwater or other aqueous media are subsequently applied to configure the suspension of particulate matter.

[0174] The step of dispersing the preparation in the aqueous medium can be achieved by any convenient technique, depending on the nature of the preparation. Ideally, the dispersion of the preparation in the aqueous solution can be carried out by manual or minimal mechanical agitation. Mechanical agitation can include stirring, mixing, blending and other similar processes.

[0175] Additional Implementations

[0176] In another typical embodiment, the formulation is a paint dispersion and the at least one active ingredient is a pigment.

[0177] Suitable pigments include inorganic pigments such as titanium dioxide, coated titanium dioxide, titanium dioxide (titania, titanium dioxide), iron oxides (red, yellow, brown and black), zinc oxide, chromium pigments, ultramarine pigments, cobalt pigments (cobalt blue) and organic pigments such as azo pigments. In a typical embodiment, the polymers of the present disclosure disperse titanium dioxide, thereby having a better hiding effect than traditional dispersants, or using less titanium dioxide in the formulation to achieve the same hiding effect.

[0178] Examples of suitable organic colored pigments are: monoazo pigments: CI Pigment Brown 25; CI Pigment Orange 5, 13, 36, 38, 64 and 67; CI Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:, 53, 53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191:1, 208, 210, 245, 247 and 251; CI Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; CI Pigment Violet 32; Diazo Pigments: CI Pigment Orange 16, 34, 44, 72; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180 and 188; Diazo Condensation Pigments: CI Pigment Yellow 93, 95 and 128; CI Pigment Red 144, 166, 214, 220, 221, 242 and 262; CI Pigment Brown 23 and 41; Anthrone Pigments: CI Pigment Red 168; Anthraquinone Pigments: CI Pigment Yellow 147, 177 and 199; CI Pigment Violet 31; Anthraquinone Pigments: CI Pigment Yellow 108; Quinacridone Pigments: Pigment Orange 48 and 49; CI Pigment Red 122, 202, 206 and 209; CI Pigment Violet 19; Quinophthalone Pigments: CI Pigment Yellow 138; Diketopyrrolopyrrole Pigments: CI Pigment Orange 71, 73 and 81; CI Pigment Red 254, 255, 264, 270 and 272; Dioxazine Pigments: CI Pigment Violet 23 and 37; CI Pigment Blue 80; Flavanthrene Pigments: CI Pigment Yellow 24; Indanthrene Pigments: CI Pigment Blue 60 and 64; Isoindoline Pigments: CI Pigment Orange 61 and 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185; Isoindolinone pigments: CI Pigment Yellow 109, 110 and 173; Isoviolanthrone pigments: CI Pigment Violet 31; Metal complex pigments: CI Pigment Red 257; CI Pigment Yellow 117, 129, 150, 153 and 177; CI Pigment Green 8; Violinone pigments: CI Pigment Orange 43; CI Pigment Red 194; Perylene pigments: CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179, 190 and 224; CI Pigment Violet 29; Phthalocyanine pigments: CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; CI Pigment Green 7 and 36; Pyranthrone pigments: CI Pigment Orange 51; C.I. Pigment Red 216; Pyrazolone pigments: CI Pigment Orange 67; CI Pigment Red 251; Thioindigo pigments: CI Pigment Red 88 and 181; CI Pigment Violet 38; Triarylcarbonium pigments: CI Pigment Blue 1, 61 and 62; CI Pigment Green 1; CI Pigment Red 81, 81:1 and 169; CI Pigment Violet 1, 2, 3 and 27; CI Pigment Black 1 (Aniline Black); CI Pigment Yellow 101 (Aldazine Yellow); CI Pigment Brown 22. .

[0179] Examples of suitable inorganic colored pigments are: white pigments: titanium dioxide (CI Pigment White 6), zinc white, pigment grade zinc oxide; zinc sulfide, lithopone; black pigments: iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); carbon black (CI Pigment Black 7); colored pigments: chromium oxide, hydrated chromium oxide green; chrome green (CI Pigment Green 48); cobalt green (CI Pigment Green 50); ultramarine green; cobalt blue (CI Pigment Blue 28 and 36; CI Pigment Blue 72); ultramarine; manganese blue; ultramarine violet; cobalt violet; manganese violet; iron oxide red (CI Pigment Red 101); cadmium sulfoselenide (CI Pigment Red 108); cerium sulfide (CI Pigment Red 265); molybdate red (CI Pigment Red 266); =CI Pigment Red 104); Ultramarine Red; Iron Oxide Brown (CI Pigment Brown 6 and 7), Mixed Brown, Spinel Phase and Corundum Phase (CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40), Chrome Titanium Yellow (CI Pigment Brown 24), Chrome Orange; Cerium Sulfide (CI Pigment Orange 75); Iron Oxide Yellow (CI Pigment Yellow 42); Nickel Titanium Yellow (CI Pigment Yellow 53; CI Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chrome Titanium Yellow; Spinel Phase (CI Pigment Yellow 119); Cadmium Sulfide and Cadmium Zinc Sulfide (CI Pigment Yellow 37 and 35); Chrome Yellow (CI Pigment Yellow 34); Bismuth Vanadate (CI Pigment Yellow 184).

[0180] Formulations containing a high proportion of pigment (i.e. pigment concentrates) are typical because such formulations are particularly effective in providing color and hiding power to paints. Based on the total weight of the pigment concentrate, the pigment concentrate typically contains 5 to 85% by weight, typically 20 to 75% by weight, of pigment.

[0181] Typically, the pigment is added in an amount of 5 to 40 weight percent, most typically 10 to 25 weight percent, based on the total weight of the dispersion.

[0182] The formulation suitably comprises up to 100% by weight, typically 0.01 to 10% and most typically 0.1 to 5% by weight of a dispersant of the present disclosure, calculated on the weight of the pigment. The most suitable amount of dispersant depends, among other things, on the specific type of pigment to be dispersed.

[0183] In a typical embodiment, the disclosed formulation is a paint comprising (a) one or more pigments, (b) one or more binders, (c) one or more rheology modifiers, (d) one or more dispersant polymers of the present invention, and (e) a liquid carrier.

[0184] The polymers disclosed herein can be used as dispersants in decorative paint compositions as well as in waterborne paper coating compositions. These polymers can be used in paint formulations of waterborne flat, semi-flat, semi-gloss and gloss paint compositions.

[0185] The components of a paint composition are usually solvents (usually water for latex paints), binders, pigments and extenders, and additives. These binders are usually latex binders, such as polyvinyl acetate; copolymers of vinyl acetate and acrylates; copolymers of vinyl acetate and ethylene; copolymers of vinyl acetate, ethylene and vinyl chloride; and copolymers of styrene and acrylates. Latex binders are usually stabilized with anionic surfactants.

[0186] Extenders are paint additives that are insoluble in binder and water. Extenders are added to change the fluidity and mechanical properties of the paint as well as the permeability, gloss and leveling of the paint film. White extender pigments are added to paint to reduce its cost or improve its properties. Such extenders include calcium carbonate, calcium sulfate, diatomaceous earth and china clay.

[0187] Additives include rheology modifiers and opaque polymers. Rheology modifiers include cellulose derivatives, hydrophobically modified alkali swellable polymers, inorganic materials such as clays and nonionic polyurethane associative thickeners (HEUR) and similar materials.

[0188] The formulations may optionally contain other known additives such as additional dispersants, defoamers, biocides, pH control agents, wetting agents, materials to improve freeze-thaw stability, leveling aids, coalescing agents and / or polymeric or oligomeric binders.

[0189] The pigment particles in the formulation are usually present in finely divided form. Therefore, the average particle size of the pigment is usually in the range of 50nm to 5,000nm. Usually, the average particle size is at least 80nm, more usually at least 100nm. Preferably, the average particle size is at most 3,000nm, more usually at most 1,500nm, and most usually at most 1,000nm.

[0190] The average particle size of the pigment particles in the formulation can be determined, for example, by electron microscopy. Since the average particle size of the pigment in the formulation is essentially the same as the average particle size of the pigment after stirring into a liquid, the pigment formulation can also be mixed with a liquid medium and the average particle size of the pigment determined by dynamic light scattering.

[0191] In various embodiments, the polymers of the present disclosure are used in waterborne coatings, adhesives and sealants, and related formulations.

[0192] Waterborne coatings should have an acceptable balance of properties during storage, application and drying. During application, if irregularities occur, there is a limited period of time in which they can be repaired without visible brush marks. This time is known in the art as open time. Unfortunately, waterborne coatings typically use dispersed high molecular weight polymers as binders, which tend to shorten the open time because the dispersed polymer particles tend to quickly fix to the edges of the applied coating. As a result, the viscosity of the coating increases rapidly, which results in a limited operable window, i.e., a short open time.

[0193] In typical coatings, open time is increased by adding solvents and coalescing agents. However, this results in an increase in the volatile organic content (VOC) of the coating, which is undesirable. The polymers of the present disclosure can be added to the paint formulation in the grind, or as an additive in the letdown, especially when used to control the open time. In various embodiments, the polymers of the present disclosure are additives that are non-volatile but still extend the workable time of the coating after application without interfering with other properties.

[0194] The polymers of the present disclosure can also be used as dispersants in paint formulations, which increase open time and improve freeze-thaw stability. These polymers can be used to prepare zero VOC architectural paints because these polymers can eliminate the need for ethylene glycol solvents used as open time extenders and coalescing agents. In some embodiments, these polymers can also reduce the amount of rheology modifiers required for anionic dispersants. In other embodiments, these polymers can also eliminate the need for defoamers in formulations. In other embodiments, these polymers can also be used with most types of binders, such as acrylic acid, vinyl acrylate and styrene acrylate. In addition, the polymers of the present disclosure can improve the scrub resistance in certain formulations.

[0195] Additionally, the polymers of the present disclosure can be used as colloidal stabilizers during emulsion polymerization, especially for producing emulsion binders used in coatings.

[0196] The present disclosure will now be described in more detail with reference to the following non-limiting examples.

[0197] Example

[0198] Preparation of polymers by starvation feeding method

[0199] Embodiment 1:

[0200] An initial charge of 155.6 g of deionized water and 73.2 g of propylene glycol was added to a 2-liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adding adapters for monomer and initiator solutions. The reactor contents were heated to 80°C. A solution of 100 g of methoxypolyethylene glycol 750 methacrylate (Komerate A750M from Green Chemical, Korea) dissolved in 100 g of water was fed to the reactor over 1 hour. At the same time, a well-mixed solution of 76.8 g of methyl methacrylate, 6 g of methacrylic acid, and 1.5 g of 3-mercaptopropionic acid was added to the reactor over the same period of 1 hour. An initiator solution of 2.3 g of sodium persulfate dissolved in 34.8 g of water was added simultaneously with the above two solutions for 75 minutes. The reaction product was then kept at 80°C for 60 minutes. The reactor contents were then cooled to 65°C, and 6.3 g of 50% aqueous sodium hydroxide solution was then added. The final polymer had 80 mole % methyl methacrylate, 12.75 mole % methoxy polyethylene glycol 750 methacrylate (where n is approximately 15), and 7.25 mole % methacrylic acid.

[0201] Embodiment 2:

[0202] An initial charge of 180 g of deionized water and 100 g of isopropanol was added to a 2 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 59 g of Komerate A750M, 46.2 g of methyl methacrylate, and 3.7 g of methacrylic acid was added to the reactor over 2 hours. An initiator solution of 2.1 g of sodium persulfate dissolved in 60 g of water was added simultaneously with the mixed monomer solution for 135 minutes. The reaction product was then kept at 80°C for 60 minutes. 2.1 g of 50% aqueous sodium hydroxide solution dissolved in 100 g of water was then added. The reactor was then set up for distillation, and 195 g of an azeotrope of a mixture of water and isopropanol was then distilled out. The final polymer has 80 mole % methyl methacrylate, 12.5 mole % methoxy polyethylene glycol 750 methacrylate (where n is about 15) and 7.5 mole % methacrylic acid. The residual methoxy polyethylene glycol 750 is measured by NMR to be 3.8% by weight of the polymer. In comparison, Atlox 4931 has 31.6% by weight of unreacted methoxy polyethylene glycol 750 based on the weight of the polymer using the same method.

[0203] Embodiment 3:

[0204] Analogously to Examples 1 and 2, another copolymer can be prepared comprising 80 mol % methyl methacrylate, 12.5 mol % methoxy polyethylene glycol methacrylate, and 7.5 mol % methacrylic acid.

[0205] The methoxypolyethylene glycol content of different batches of this particular polymer ranged from 1.3 to 3.5% by weight, based on the total weight of the polymer. In contrast, the methoxypolyethylene glycol content of different batches of Atlox 4931 ranged from 22.9 to 28.3% by weight, also based on the total weight of the polymer.

[0206] Embodiment 4:

[0207] An initial charge of 210 g of deionized water, 90 g of propylene glycol, 9.6 g of methyl methacrylate and 89.6 g of methoxy polyethylene glycol 750 methacrylate was added to a 1 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 90° C. 81 g of methyl methacrylate was fed into the reactor over 50 minutes. An initiator solution of 7.2 g of sodium persulfate dissolved in 90 g of water was added simultaneously with the methyl methacrylate monomer and continued for 60 minutes. The reaction product was then held at 90° C. for 300 minutes. 8.7 g of 50% aqueous sodium hydroxide solution was then added. The final polymer had 78.8 mole % of methyl methacrylate, 10.4 mole % of methoxy polyethylene glycol 750 methacrylate (where n is approximately 15) and 10.8 mole % of methacrylic acid.

[0208] Embodiment 5:

[0209] An initial charge of 54 g of propylene glycol was added to a 1 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 85°C. A well-mixed homogeneous solution of 54 g of methoxypolyethylene glycol 750 methacrylate, 48.5 g of methyl methacrylate, and 6 g of methacrylic acid, 18.2 g of methyl ethyl ketone, and 140 g of water was added to the reactor over 50 minutes. An initiator solution of 2 g of sodium persulfate dissolved in 25 g of water was added simultaneously with the mixed monomer solution and continued for 60 minutes. The reaction product was then held at 85°C for 60 minutes. 5.5 g of a 50% aqueous sodium hydroxide solution dissolved in 100 g of water was then added. The final polymer had 78.3 mol % of methyl methacrylate, 10.4 mol % of methoxypolyethylene glycol 750 methacrylate (where n is approximately 15), and 11.3 mol % of methacrylic acid.

[0210] Embodiment 6:

[0211] An initial charge of 176 g of deionized water and 96 g of isopropanol was added to a 2-liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adding adapters for monomer and initiator solutions. The reactor contents were heated to 82 ° C. 405 g of methoxypolyethylene glycol 750 methacrylate (Komerate A750M) was added to the reactor over 2 hours. A well-mixed homogeneous solution of 25.8 g of styrene and 1.8 g of 3-mercaptopropionic acid dissolved in 37.6 g of isopropanol was fed to the reactor simultaneously with the previous feed over 2 hours. An initiator solution of 6 g of ammonium persulfate dissolved in 48 g of water was added simultaneously with the above solution for 2.5 hours. The reaction product was then kept at 85 ° C for 60 minutes. The reactor was then set for distillation, and an azeotrope of 265 g of water and isopropanol mixture was then distilled out. The final polymer had 50 mole % styrene and 50 mole % methoxy polyethylene glycol 750 methacrylate (where n is approximately 15).

[0212] Polymer Evaluation

[0213] Example 7: Suspension rate test

[0214] Various dispersant polymers were introduced into a 25% tebuconazole suspension concentrate formulation and the suspension rate of tebuconazole was measured.

[0215] A 25 wt% tebuconazole suspension concentrate was prepared using the ingredients listed in the table. The suspension rate was determined according to CIPAC MT 184, where the suspension concentrate was diluted 20 times in 1000 ppm hard water at 25°C, placed in a 250-liter measuring cylinder, and allowed to stand for 30 minutes. The top 9 / 10 was taken out, and the remaining 1 / 10 was then measured gravimetrically, and the suspension rate was calculated.

[0216] %weight Active ingredient: Tebuconazole 25.00％ Wetting agent: Morwet EFW 2.00％ Defoamer: Agnique DFM 111S 0.15％ Dispersants 3.00％ Carrier: Water 69.85％

[0217]

[0218] Example 8: Preparation stability test

[0219] Various dispersant polymers were incorporated into 25 wt % tebuconazole suspension concentrate formulations and the resulting formulations were aged at 54°C for two weeks. Figure 1 Phase separation is shown for various formulations. Figure 1 A series of experiments 10 are shown, carried out in five bottles 11, each of which is provided with a cap 12, each of which contains a sample formulation, which in each case contains a dispersant as indicated above each cap 11. The formulation is found to have separated into a liquid phase 13 and a solid phase 14. The degree of separation is indicative of the dispersing and stabilizing power of the dispersant. It can be clearly seen that the dispersion of the solid phase is not as good as that of the solid phase 14. 755 or The disclosed polymers exhibited significantly less formulation separation compared to 4913.

[0220] % (weight / weight) Active ingredient: Tebuconazole 25.00 Wetting agent: Morwet EFW 2.00 Defoamer: Agnique DFM 111S 0.15 Dispersants 3.00 Carrier: Water 69.55 Rheology modifier: Xanthan gum 0.3

[0221] Example 9: Particle size stability test

[0222] Various dispersant polymers were incorporated into the sulfentrazone suspension concentrate formulations listed in the table. The particle size of the suspension concentrates was measured by Malvern Mastersizer 3000 when the suspension concentrates (SC) were freshly prepared at 25°C and after aging them for 2 weeks at 54°C. The polymer of the invention (Example 3) showed no change in particle size after aging, while the particle size increase of Atlox 4913 was much more pronounced.

[0223] After aging for 2 weeks at 54°C, any change in particle size is considered a predictor of the stability of the formulation at room temperature for 1-2 years. Therefore, in this aging test, an increase in particle size of more than 10% indicates that the formulation will not be stable over a long period of time at room temperature, because the increase in particle size indicates that the original particles are agglomerating to form larger particles.

[0224] It is clear from the results for the inventive polymer of Example 3 that there is essentially no change in particle size during the aging test.

[0225]

[0226]

[0227] Example 10

[0228] An initial charge of 399.4 g of deionized water and 399.3 g of isopropanol was added to a 2 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 165.2 g of methoxypolyethylene glycol 750 methacrylate (Komerate A750M) was dissolved in 124.6 g of deionized water, and then 46.2 g of methyl methacrylate and 3.7 g of methacrylic acid were added and mixed to form a homogeneous solution, which was then fed into the reactor over 120 minutes. An initiator solution of 6.1 g of sodium persulfate dissolved in 60 g of water was added simultaneously with the mixed monomer solution and continued for 135 minutes. The reaction product was then kept at 80°C for 60 minutes. 6.0 g of 50% aqueous sodium hydroxide solution dissolved in 55 g of water was then added. The reactor was then set up for distillation and 718.7 g of an azeotrope of a mixture of water and isopropanol was then distilled off. 23.7 g of a 50% aqueous sodium hydroxide solution and 450 g of water were then added. The final polymer solution had 70 mole % of methyl methacrylate, 12.5 mole % of methoxypolyethylene glycol 750 methacrylate (where n is about 15) and 17.5 mole % of methacrylic acid, a pH of 7.4 and a solids content of 32.4%.

[0229] Embodiment 11

[0230] An initial charge of 399.4 g of deionized water and 399.3 g of isopropanol was added to a 2-liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adding adapters for monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 165.3 g of methoxypolyethylene glycol 750 methacrylate (Komerate A750M) was dissolved in 124.6 g of deionized water, and then 97 g of methyl methacrylate and 38.3 g of methacrylic acid were added and mixed to form a homogeneous solution, which was then fed into the reactor over 120 minutes. An initiator solution of 6.1 g of sodium persulfate dissolved in 55 g of water was added simultaneously with the mixed monomer solution for 135 minutes. The reaction product was then kept at 80°C for 60 minutes. The reactor was then set for distillation, and an azeotrope of 718.7 g of water and isopropanol mixture was then distilled out. Then 37.4 g of 50% aqueous sodium hydroxide solution and 450 g of water were added. The final polymer solution had 60 mol % methyl methacrylate, 12.5 mol % methoxypolyethylene glycol 750 methacrylate (where n is about 15) and 27.5 mol % methacrylic acid, a pH of 7.6 and a solids content of 30.4%.

[0231] Example 12

[0232] An initial charge of 399.4 g of deionized water and 399.3 g of isopropanol was added to a 2-liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adding adapters for monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 165.4 g of methoxypolyethylene glycol 750 methacrylate (Komerate A750M) was dissolved in 124.3 g of deionized water, and then 81 g of methyl methacrylate and 52.1 g of methacrylic acid were added and mixed to form a homogeneous solution, which was then fed into the reactor over 120 minutes. A 6.0 g sodium persulfate initiator solution dissolved in 55 g of water was added simultaneously with the mixed monomer solution for 135 minutes. The reaction product was then kept at 80°C for 60 minutes. The reactor was then set for distillation, and an azeotrope of 718.7 g of water and isopropanol mixture was then distilled out. 50.8 g of 50% aqueous sodium hydroxide and 395 g of water were then added. The final polymer solution had 50 mol% methyl methacrylate, 12.5 mol% methoxypolyethylene glycol 750 methacrylate (where n is about 15) and 37.5 mol% methacrylic acid, a pH of 8.1 and a solids content of 31.6%.

[0233] Embodiment 13

[0234] An initial charge of 199.6 g of deionized water and 199.3 g of isopropanol was added to a 2 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 217.7 g of methoxypolyethylene glycol 1000 methacrylate (50% soluble in water, Bisomer S10W) and 65 g of methyl methacrylate and 5.3 g of methacrylic acid was added and mixed to form a homogeneous solution, which was then fed into the reactor over 120 minutes. An initiator solution of 3.5 g of sodium persulfate dissolved in 51.3 g of water was added simultaneously with the mixed monomer solution and continued for 135 minutes. The reaction product was then held at 80°C for 60 minutes. The reactor was then set for distillation, and then 360 g of an azeotrope of a mixture of water and isopropanol was distilled out. 5.4 g of 50% aqueous sodium hydroxide solution and 230 g of water were then added. The final polymer solution had 80 mol % methyl methacrylate, 12.5 mol % methoxy polyethylene glycol 1000 methacrylate (where n is about 23), and 7.5 mol % methacrylic acid, a pH of 7.0, and a solids content of 30.6%.

[0235] Embodiment 14

[0236] An initial charge of 128.3 g of deionized water and 128.7 g of isopropanol was added to a 2 liter glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 80°C. A well-mixed homogeneous solution of 269.6 g of methoxypolyethylene glycol 1000 methacrylate (50% soluble in water, Bisomer S20W) and 41.6 g of methyl methacrylate and 3.4 g of methacrylic acid was added and mixed to form a homogeneous solution, which was then fed into the reactor over 120 minutes. An initiator solution of 3.5 g of sodium persulfate dissolved in 43.0 g of water was added simultaneously with the mixed monomer solution and continued for 135 minutes. The reaction product was then held at 80°C for 60 minutes. The reactor was then set for distillation, and then 231 g of an azeotrope of a mixture of water and isopropanol was distilled out. 3.4 g of 50% aqueous sodium hydroxide solution and 230 g of water were then added. The final polymer solution had 80 mol % methyl methacrylate, 12.5 mol % methoxy polyethylene glycol 2000 methacrylate (where n is about 46), and 7.5 mol % methacrylic acid, a pH of 6.1, and a solids content of 30.9%.

[0237] Embodiment 15

[0238] An initial charge of 100 g of deionized water and 130 g of isopropanol was added to a glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. The reactor contents were heated to 82°C. A well-mixed homogeneous solution of 168.75 g of methoxypolyethylene glycol 750 methacrylate mixed with 169 g of water was added to the reactor over 135 minutes. A mixture of 9.26 g of styrene dissolved in 69 g of isopropanol was added at the same time for the same period of time. An initiator solution of 5 g of ammonium persulfate dissolved in 40 g of water was added simultaneously with the mixed monomer solution for 165 minutes. The reaction product was then kept at 82°C for 60 minutes. The reactor was then set for distillation, and then 357 g of an azeotrope of a mixture of water and isopropanol was distilled out. The final polymer solution had 30 mol% styrene and 70 mol% methoxy polyethylene glycol 750 methacrylate (where n is approximately 17), a pH of 2.6, and a solids content of 29.3%. In this example, a=30, b=70, and c=0.

[0239] Example 16

[0240] The open time extension of the polymers of the present disclosure was tested in the following high gloss styrene acrylate paint formulations and compared to the commercial dispersant polymer Alcosperse 787 from Nouryon. The control formulation Example 15A has propylene glycol, which extends the open time but increases the VOC. The formulations containing the polymers of the present disclosure do not contain propylene glycol. However, the open time of these formulations is longer than the control formulations containing propylene glycol.

[0241]

[0242] Embodiment 17

[0243] The open time extension of the polymers of the present disclosure was tested in the following semi-gloss styrene acrylic paint formulations and compared to the commercial dispersant polymer Alcosperse 787 from Nouryon. The control formulation Example 16A has propylene glycol, which extends the open time but increases the VOC. The formulations containing the polymers of the present disclosure do not contain propylene glycol. However, the open time of these formulations is longer than the control formulations containing propylene glycol.

[0244]

[0245]

[0246] Formulations 17B, D, E, and F also underwent 5 freeze-thaw cycles. One freeze-thaw cycle consisted of 17 hours of storage in a freezer followed by 7 hours of storage at room temperature. This is quite unique because these formulations contain latex binders, which do not form latex paints that are freeze-thaw stable. In addition, Formulations 17B, D, E, and F did not show any syneresis after storage at 60°C for 10 days, which is a very good performance because it indicates that the formulations have good stability over several months at room temperature.

[0247] Embodiment 18

[0248] The following high gloss formulations were tested for open time and compared to a commercial dispersant, Alcosperse 787.

[0249]

[0250]

[0251] As shown below, the open time results for the high gloss formulations show that the polymers of the present disclosure have significantly longer open times than these commercial dispersants. The semi-gloss formulations have even better improvement in open time and the freeze-thaw stability is also very good. Similar open time results are also obtained for formulations containing a vinyl acrylate binder system. This shows that the performance is independent of the binder type.

[0252]

[0253] Embodiment 19

[0254] An initial charge of 150.0 g of deionized water and 150.2 g of isopropanol was added to a glass reactor equipped with an agitator, a water-cooled condenser, a thermocouple, and an inlet for adapters for adding monomer and initiator solutions. 0.0490 g of ammonium ferrous sulfate hexahydrate dissolved in 10 g of water was then added to the reactor. The reactor contents were heated to reflux. A mixture of 59.2 g of acrylic acid and 72.1 g of styrene was added to the reactor over 210 minutes. A well-mixed homogeneous solution of 176.3 g of methoxypolyethylene glycol 750 methacrylate, 5.7 g of 3-mercaptopropionic acid dissolved in 140.3 g of water was added to the reactor over 195 minutes. An initiator solution of 6.65 g of sodium persulfate, 19.4 g of 35% hydrogen peroxide dissolved in 80 g of water was added simultaneously for 140 minutes. The reaction product was then kept at 85° C. for 60 minutes. The reactor was then set up for distillation, and then 300 g of an azeotrope of a mixture of water and isopropanol was distilled out. Before distillation, 0.1 g of Silicone S-100 was added. Before distillation, 140 g of a 50% aqueous solution of 2-amino-2-methyl-1-propanol and 300 g of water were added. The final product was an opaque white solution with a pH of 7.2 and a solids content of 37%.

[0255] The polymer can be used as a colloidal stabilizer in emulsion polymerization.

[0256] Embodiment 20:

[0257] The hiding performance of Example 19 was tested in the following acrylate-based paint formulation and compared to a commercial dispersant polymer, Tamol 165A from Dow. The grind and letdown materials are as follows:

[0258]

[0259] Its opacity is 100.6, while Tamol 165A in the same formulation has an opacity of 98.5. This shows that the polymers of the present disclosure improve the hiding power of the paint formulation.

[0260] Although at least one exemplary embodiment is proposed in the aforementioned specific embodiments, it should be understood that there are a large number of variations. It should also be understood that the exemplary embodiment or multiple exemplary embodiments are only examples and are not intended to limit the scope, applicability or configuration in any way. On the contrary, the aforementioned specific embodiments will provide a convenient roadmap for implementing the exemplary embodiments for those skilled in the art. It should be understood that various changes can be made to the functions and arrangements of the elements described in the exemplary embodiments without departing from the scope given in the attached claims.

Claims

1. A polymer having the formula (I): wherein a is 1 - 25 mol%; b is 50 - 95 mol%; c is 0 - 25 mol%; a + b + c = 100 mol%; n is from 1 to 100, and when n > 1, each -O-CH 2 -CHR 7 - group is the same or different; X is O or NH, and is typically O; R 0 is -C=OOR 6 or aryl, where aryl is typically -C 6 H 5 ; R 1 is a terminal group derived from a water-soluble initiation system; R 2 is H, C 1 -C 10 a hydrocarbyl group, or a terminal group derived from a water-soluble initiator system or a chain transfer agent; R 3 is H or C 1 -C 22 hydrocarbyl group; R 4 is H or CH 3 ; R 5 is H or CH 3 ; R 6 is H or C 1 -C 22 alkyl; and R 7 is H or C 1 -C 10 hydrocarbyl group.

2. The polymer according to claim 1, wherein a is 3 - 18 mol%; b is 60 - 90 mol%; c is 2 - 20 mol%; n is from 2 to 25, wherein each -O-CH 2 -CHR 7 - group is the same or different; X is O; R 1 is a terminal group derived from a peroxide, persulfate or azo initiator; R 2 is H, CH 3 or a terminal group derived from an alcohol or a diol; R 3 is H or CH 3 ; R 4 is H or CH 3 ; R 5 is H or CH 3 ; R 6 is H or CH 3 ; and R 7 is H or CH 3 .

3. The polymer according to claim 1, wherein a is 6 - 14 mol%; b is 70 - 85 mol%; c is 5 - 15 mol%; n is from 5 to 15, wherein each -O-CH 2 -CHR 7 - group is the same or different; X is O; R 1 is an end group derived from sodium persulfate, ammonium persulfate or potassium persulfate; R 2 is H, CH 3 or a terminal group derived from isopropanol or propylene glycol; R 3 is H or CH 3 ; R 4 is H or CH 3 ; R 5 is H or CH 3 ; R 6 is H or CH 3 ; and R 7 is H or CH 3 .

4. The polymer according to any one of claims 1 - 3, which is substantially free of the compound of formula (II): wherein n is 1 - 100; R 3 is H or C 1 -C 22 a hydrocarbyl group; and R 7 is H or C 1 -C 10 hydrocarbyl group.

5. The polymer according to claim 4, wherein the compound of formula (II) is methoxypolyethylene glycol methacrylate.

6. The polymer according to claim 5, which contains less than 10% by weight of methoxypolyethylene glycol methacrylate based on the total weight of the polymer.

7. The polymer according to claim 1, which contains (a) 75 - 85 mol% of methyl methacrylate, (b) 10 - 15 mol% of methoxypolyethylene glycol methacrylate, and (c) 5 - 10 mol% of methacrylic acid, where (a)+(b)+(c)=100 mol%, and contains less than 10% by weight of methoxypolyethylene glycol methacrylate based on the total weight of the polymer.

8. A method for preparing a polymer having the formula (I): wherein a is 1 - 25 mol%; b is 50 - 95 mol%; c is 0 - 25 mol%; a + b + c = 100 mol%; n is from 1 to 100, and when n > 1, each -O-CH 2 -CHR 7 - group is the same or different; X is O or NH, and is typically O; R 0 is -C=OOR 6 or aryl, where aryl is usually -C 6 H 5 ; R 1 is a terminal group derived from a water-soluble initiation system; R 2 is H, C 1 -C 10 a hydrocarbyl group, or a terminal group derived from a water-soluble initiation system or a chain transfer agent; R 3 is H or C 1 -C 22 hydrocarbyl group; R 4 is H or CH 3 ; R 5 is H or CH 3 ; R 6 is H or C 1 -C 22 a hydrocarbon group; and R 7 is H or C 1 -C 10 hydrocarbyl; The method comprises: (a) introducing monomers a, b, and c into a reactor under starved - feed conditions, wherein monomer a has the following formula: monomer b has the following formula: and monomer c has the following formula: wherein monomers a, b, and c are each introduced into the reactor in a molar ratio of a:b:c of 1 - 25:50 - 95:1 - 25, and in the method this molar ratio remains substantially constant throughout and the total molar ratio a + b + c = 100 mol%; and (b) obtaining the polymer of formula (I) from (a).

9. A polymer obtained by the method according to claim 8.

10. A formulation comprising at least one active ingredient, the active ingredient being dispersed in an effective dispersing amount of at least one polymer according to any one of claims 1 - 7 and 9.

11. The formulation according to claim 10, which is an agrochemical formulation and the at least one active ingredient is an agrochemical active ingredient.

12. The formulation according to claim 11, wherein the agrochemical active ingredient is selected from herbicides, insecticides, fungicides, biocides, molluscicides, algaecides, plant growth regulators, repellents, rodenticides, nematicides, acaricides, amoebicides, protozoicides, crop safeners, and adjuvants.

13. The formulation according to claim 10, which is a paint formulation and the at least one active ingredient is a pigment.

14. The preparation according to any one of claims 10 - 13, further comprising at least one anionic dispersant.

15. The preparation according to claim 14, wherein the at least one anionic dispersant is selected from D-360 / D-390, D-425 and 789.

16. The preparation according to any one of claims 10 - 15, further comprising at least one non - ionic dispersant.

17. The preparation according to claim 16, wherein the at least one non-ionic dispersant is selected from Ethylan TM NS-500LQ and Ethylan TM 324.

18. The preparation according to any one of claims 10 - 17, which is a suspension concentrate.

19. A method of combating fungi, which comprises applying a fungicidally effective amount of the preparation according to any one of claims 10 - 12 or 14 - 18 to fungi or to a locus from which fungi are to be removed.

20. A method of combating plants, which comprises applying a herbicidally effective amount of the preparation according to any one of claims 10 - 12 or 14 - 18 to plants or to a locus from which plants are to be removed.

21. A method of painting a surface, which comprises applying to the surface an amount of the preparation according to claim 13 sufficient to coat the surface.

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