(Met)acrylate functional dispersant

Abstract

(Meth)acrylate functional copolymers are useful as dispersants for solid particulates in paints, inks, and coatings. The copolymers have (meth)acrylate functional groups located as pendants on the polymer chains. Additionally, non-(meth)acrylate-functional hydrophobic and / or hydrophilic pendant groups are located as pendants on the polymer backbone chains. The copolymers are useful as dispersants in dispersions of particulate solids in organic and aqueous media, such as paints and printing inks.

Description

Technology Field

[0001] The present invention relates to a (meth)acrylate-functional polymer having (meth)acrylate functional groups located as pendants on the polymer chain. Additionally, non-(meth)acrylate-functional hydrophobic and / or hydrophilic pendant groups are located as pendants on the polymer backbone chain. The polymer is useful as a dispersant in dispersions of particulate solids and organic media, such as paints and printing inks. Background Technology

[0002] Paints, inks, and coatings often contain dispersions of solid pigments in organic or aqueous media. These dispersions need to be uniform so that a uniform coating of particles remains on the substrate when the ink or paint dries. These dispersions must also be stable for long storage times over a wide range of temperatures. Dispersants are used in the fields of paints, inks, and coatings to ensure the uniform and stable separation of solid pigments in these compositions. A desirable property of these dispersants is their ability to interact with various possible types of pigments as well as the media in which they are dispersed. Since inks and paints often contain more than one type of pigment particles, each of which can have different surface characteristics, the ability to interact with various pigment types is particularly desirable. Therefore, useful dispersants are compatible with a wide range of organic and organic pigment types. Dispersants capable of compatibilizing and stabilizing these pigments with both organic and aqueous media are much more desirable. Another desirable property is that the dispersant does not interfere with the curing of ethylenically unsaturated species other than (meth)acrylate groups that may be present in the ink, coating, or paint.

[0003] outline

[0004] The present disclosure provides a (meth)acrylate-functional polymer having a (meth)acrylate functional group located as a pendant on the polymer chain and a hydrophobic and / or hydrophilic pendant group also located as a pendant on the polymer chain. The disclosed polymer is useful as a dispersant in coloring systems and as a filler in coatings or inks. The polymer can be used as an adhesion promoter. The novel polymer structures disclosed herein enable various functionalizations for the dispersion of organic and / or inorganic pigments in ink, coating, or paint formulations. Ink, coating, or paint formulations may include various types of pigments dispersed in an organic or aqueous medium. Additionally, a synthesis method used to produce such a (meth)acrylate-functional polymer having pendant hydrophobic and / or hydrophilic moiety is disclosed.

[0005] Accordingly, a (meth)acrylate-functionalized polymer is provided that comprises, is composed of, or consists of the repeating unit of structure [A], the repeating unit of structure [B], and the repeating unit of structure [C] as essential elements.

[0006] The repeating unit [A] has the following structure:

[0007]

[0008] In structure [A], R1 and R3 are the same or different and are H or alkyl, and R2 and R4 are different from each other and are an organic moiety or H having at least one (meth)acrylate functional group. Thus, structure [A] has a (meth)acrylate functional group of the (meth)acrylate-functionalized polymer disclosed herein.

[0009] The repeating unit [B] has the following structure:

[0010]

[0011] In structure [B], R7 and R9 are the same or different and are H or alkyl. R8 and R 10Both are either H or different from each other, and are independently selected from the following:

[0012] -(R 11 O) n R 12 (here, R 11 is a divalent alkylene moiety, and R 12 is H or C1-C26, particularly C8-C26 alkyl, and n is an integer greater than or equal to 1);

[0013] R 19 (here, R 19 is a branched or straight-chain alkyl of C2-C34, particularly C2-C30, more particularly C8-C26, and even more particularly C8-C22;

[0014] -R 20 -(C=O)OH(where, R 20 is a C2-C26, particularly C8-C26 alkylene); or

[0015] H.

[0016] Preferably, R8 and R 10 If one of them is H, R8 and R 10 The other one is one of the other choices.

[0017] The repetition unit [C] is as follows:

[0018]

[0019] In the structure [C], R 13 , R 14 , R 15 , and R 16 It is selected from a group consisting of identical or different H and organic moieties independently.

[0020] A (meth)acrylate-functional copolymer comprising, composed of, or composed of structures [A], [B], and [C] as essential elements is conditioned that structure [C] is different from structures [A] and [B]. The (meth)acrylate-functional copolymer is also conditioned that one or more units of structure [C] are located between at least one of i) two units of structure [A], ii) two units of structure [B], or iii) one unit of structure [A] and one unit of structure [B]. To avoid doubt, this means that the chain of the (meth)acrylate-functionalized polymer of the present invention has at least one of the following repeating units: [A][C][A], [B][C][B], or [A][C][B]. Structure [A] is understood to have a (meth)acrylate functional group of the (meth)acrylate-functionalized polymer.

[0021] A curable composition comprising, composed of, or composed of a (meth)acrylate-functional copolymer as an essential element is also provided.

[0022] According to an embodiment, the (meth)acrylate-functionalized polymer may be a reaction product of at least i) an anhydride-functionalized base (meth)acrylate-functionalized polymer, ii) hydroxyl-functionalized (meth)acrylate, and iii) alkoxylated long-chain aliphatic alcohol. Brief explanation of the drawing

[0023] FIG. 1 illustrates a dispersion of titanium dioxide pigment in monomers comprising an exemplary embodiment of the present invention. Figure 2 shows a dispersion of titanium dioxide pigment among monomers without an embodiment of the dispersant of the present invention. Specific details for implementing the invention

[0024] details

[0025] The following description is by nature merely illustrative and is not intended in any way to limit the disclosure, its application, or its use.

[0026] In a preferred embodiment, the structure of the polymer is alternating. In another embodiment, the structure [C] is repeated.

[0027] The term "polymer" as used herein means comprising organic molecules having a number average molecular weight greater than 1,000 Da, or greater than 1,500 Da, or greater than 2,000 Da, or greater than 2,500 Da, or greater than 5,000 Da, or greater than 50,000 Da when measured by gel permeation chromatography using tetrahydrofuran as a solvent and polystyrene of known molecular weight as a correction standard.

[0028] The term "(meth)acrylate" is understood to include one or both of an acrylate moiety and a methacrylate functional group.

[0029] A (meth)acrylate-functionalized polymer is provided. According to some embodiments, the functionalized polymer can be conveniently prepared by reacting a hydroxyl-functionalized reactant with a polymer comprising an anhydride functionalized unit along its backbone. According to some embodiments, such a polymer may comprise, for example, a styrene-maleic anhydride (SMA) copolymer. According to another embodiment, a poly(ethylene-maleic anhydride) copolymer may be functionalized with a (meth)acrylate functional group. According to another embodiment, such a polymer may comprise a copolymer of maleic anhydride and vinyl methyl ether functionalized with a (meth)acrylate functional group. According to a further embodiment, the polymer may comprise a copolymer of maleic anhydride and octadecene functionalized with a (meth)acrylate functional group. The hydroxyl functional group on the hydroxyl-functionalized (meth)acrylate reacts with the anhydride functional group on the polymer backbone to produce a (meth)acrylate functionalized polymer, wherein the (meth)acrylate functional group is pendant to the polymer backbone and connected thereto by an ester linkage. According to a specific embodiment, at least 25-50 mol% of the backbone units in the copolymer contain anhydride functional groups prior to reaction with one or more hydroxyl functionalized reactants. For example, 30-45%, 35-50%, 25-40%, and 45-50% of the molar basis of the SMA copolymer may contain maleic anhydride units prior to reaction with the hydroxyl functionalized reactants. Prior to functionalization, the number average molecular weight of the base SMA backbone may be 1,000 to 50,000 daltons. The SMA base polymer may be a random copolymer or a block copolymer. A random copolymer is preferred. According to some embodiments, the molar ratio of styrene or ethylene or vinyl methyl ether or C3-C22 alkene or other comonomer to maleic anhydride monomer in the base SMA copolymer (or other copolymer) is 1:1 to 4:1, preferably about 1:1.According to a specific embodiment, a maleic anhydride-styrene copolymer base resin containing an approximate molar ratio of 1.3 moles of styrene to 1 mole of maleic anhydride having a weight average molecular weight (Mn) of about 2000 daltons in the backbone can be functionalized with (meth)acrylate. Thus, the base copolymer can have 8 moles of anhydride per chain. According to a specific embodiment, 1 mole of this styrene maleic anhydride resin can react with 2 to 4 moles of hydroxyl-functional (meth)acrylate, e.g., 2-hydroxyethyl acrylate, and 1 to 3 moles of hydroxyl-functional hydrophilic and / or hydrophobic pendant groups as disclosed in more detail herein.

[0030] The term "organic moiety" as used herein is used to denote the organic part of a molecule, for example, ester R 1 In COOR2, the alcohol moiety is R2O. The organic moiety is understood to refer to a moiety based on a carbon chain or ring that also contains hydrogen, regardless of the presence or absence of oxygen, nitrogen, or other molecules.

[0031] Accordingly, a (meth)acrylate-functionalized polymer is provided. The polymer comprises, is composed of, or consists of a repeating unit of structure [A], a repeating unit of structure [B], and a repeating unit of structure [C] as essential elements.

[0032] Structure [A] is the following:

[0033]

[0034] R1 and R3 are the same or different and are H or alkyl. The alkyl groups R1 or R3 are not particularly limited and, for example, include, are composed of, or consist of straight-chain or branched saturated or unsaturated hydrocarbons as essential elements. Non-limiting examples include, for example, C1-C6 hydrocarbons. Structure [A] provides a (meth)acrylate functional group for a (meth)acrylate functionalized copolymer.

[0035] R2 and R4 are different from each other and are organic moiety or H having at least one (meth)acrylate functional group. For example, if not H, R2 or R4 may be derived from 2-hydroxyethyl acrylate. For example, in addition to 2-hydroxyethyl acrylate, R2 or R4 may be derived from hydroxyl propyl acrylate, OH-terminated polycaprolactone containing terminal (meth)acrylate groups, or other hydroxyl functionalized (meth)acrylates and combinations thereof. According to a specific embodiment, one of R2 or R4 may conform to the following structure (1):

[0036]

[0037] In some embodiments of the present invention, R5 may be a divalent alkylene, an oligooxyalkylene, or a poly(ester) moiety. The oligooxyalkylene may correspond to a linker comprising one or more oxyalkylene moietys, in particular one or more moietyes selected from oxyethylene, oxypropylene, oxybutylene, and mixtures thereof. The oligooxyalkylene has the following chemical formula -[(CR a R b ) p -O] q -(CR a R b ) p It can be expressed as -, where R a and R bis independently H or alkyl, p is 2 to 4, and q is at least 1. The poly(ester) moiety may be a moiety having at least one ester bond. The poly(ester) moiety has the following chemical formula -[(CR c R d ) r -C(=O)-O] s -(CR c R d ) t It can be expressed as -*, where R c and R d is independently H or alkyl, r is 3 to 6, s is at least 1, t is 1 to 10, and the symbol * indicates an attachment point to the (meth)acrylate group of structure (1).

[0038] According to a specific embodiment, R5 may be a poly(ester) moiety containing a caprolactone residue. According to an embodiment, R6 may be H or CH3. According to a specific embodiment, R6 is H. According to another embodiment, R5 may be ethylene or oligooxyethylene.

[0039] Structure [B] is the following:

[0040]

[0041] R7 and R9 are the same or different, and are H or alkyl.

[0042] R8 and R 10 They are different from each other. R8 and R 10 It does not contain (meth)acrylate functional groups and is independently selected from H or the following:

[0043] ● -(R 11 O) n R 12 (here, R 11 is a divalent alkylene moiety, and R 12 is H or C1-C26, particularly C8-C26 alkyl, and n is an integer greater than or equal to 1). For example, R 12is R8 or R 10 This may be a C1 alkyl so as to be a polyalkylene oxide. This moiety may be derived from hydroxyl-terminated polyalkoxylates, e.g., polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1450, polyethylene glycol 3350, polyethylene glycol 8000, polyethylene glycol 350 methyl ether, polyethylene glycol 550 methyl ether, polytetrahydrofuran, and mixtures thereof. In the foregoing, the numbers are understood to refer to the average molecular weight of each individual moiety. According to some embodiments, R8 or R 10 It may include, be composed of, or have as essential elements polyethylene oxide, or polypropylene oxide or poly(ethylene oxide / propylene oxide) blocks, or may include an ethylene oxide / propylene oxide / hydrocarbon block.

[0044] ● R 19 (here, R 19 is a branched or straight-chain alkyl of C2-C34, particularly C2-C30, more particularly C8-C26, and even more particularly C8-C22). For example, in some embodiments, R8 or R 10It can be derived from fatty alcohols. Non-limiting examples of such branched or straight-chain fatty alcohols include tertiary-butyl alcohol, tertiary-amyl alcohol, 3-methyl-3-pentanol, 1-heptanol (enantic alcohol), 1-octanol (capryl alcohol), pelargon alcohol (1-nonanol), 1-decanol (decyl alcohol, capric alcohol), undecyl alcohol (1-undecanol, undecanol, hendecanol), lauryl alcohol (dodecanol, 1-dodecanol), tridecyl alcohol (1-tridecanol, tridecanol, isotridecanol), myristyl alcohol (1-tridecanol), pentadecyl alcohol (1-pentadecanol, pentadecanol), cetyl alcohol (1-hexadecanol), palmitoleyl alcohol (cis-9-hexadecen-1-ol), and heptadecyl alcohol (1-n-heptadecanol). Includes heptadecanol), stearyl alcohol (1-octadecanol), oleyl alcohol (1-octadesenol), nonadecyl alcohol (1-nonadecanol), arachidyl alcohol (1-eicosanol), heneicosyl alcohol (1-heneicosanol), behenyl alcohol (1-docosanol), erucyl alcohol (cis-13-docosen-1-ol), lignoceryl alcohol (1-tetracosanol), cetyl alcohol (1-hexacosanol), 1-heptacosanol, montanyl alcohol, cruityl alcohol, 1-octacosanol, 1-nonacosanolmyricyl alcohol, 1-triacontanol, 1-dotriacontanol, or gedyl alcohol (1-tetratriacontanol). Any mixture of two or more of these is considered.

[0045] ● -R 20 -(C=O)OH(where, R 20 is a C2-C26, particularly C8-C26 alkylene). For example, R8 or R 10 It can be derived from long-chain carboxylic acids containing terminal hydroxyl groups. Non-limiting examples of such reactants are C2-C26, or C2-C22, or C8-C26 carboxylic aliphatic alcohols, e.g., 12-hydroxylauric acid.

[0046] According to a specific embodiment of the (meth)acrylate-functionalized polymer, R1, R3, R7, and R9 are each H. According to another embodiment, R8 or R 10 is R 10 or R8 = -(R 11 O) n R 12 and R 11 This is CH2CH2, and R 12 α is a C13 straight-chain saturated alkyl and can be derived from an alkoxylated fatty alcohol such as 12 moles of ethoxylated tridecyl alcohol so that n = 12.

[0047] R 10Alternatively, non-limiting examples of R8 include fatty alcohol alkoxylates. The alkoxylate moiety may include, be composed of, or consist of ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO) units or a mixture thereof as an essential element. The alkoxylate moiety may also exist in the form of an ethylene oxide / propylene oxide block copolymer. The fatty alcohol oxyalkylate may also include polyglycerolized fatty alcohols. The ethoxylated fatty alcohol may be a primary alcohol having 8 to 22 carbon atoms, for example, coconut, palm fat, palm kernel, tallow fat, lauryl, stearyl, or oleyl alcohol. These may contain 1 to 80 EO (ethylene oxide) units per mole of alcohol, and the alcohol radicals may be linear or methyl-branched at the 2-position, or may contain linear and methyl-branched radicals in the mixture, typically as in the case of oxo alcohol radicals. Ethoxylated alcohols may include, for example, C11 alcohols having 3, 5, 7, 8, and 11 EO units; (C12-C15) alcohols having 3, 6, 7, 8, 10, and 13 EO units; (C14-C15) alcohols having 4, 7, and 8 EO units; (C16-C18) alcohols having 8, 11, 15, 20, 25, 50, and 80 EO units; and mixtures thereof. The specified degree of ethoxylation constitutes a statistical average that can be an integer or a fraction for a specific product.

[0048] According to a specific embodiment of a (meth)acrylate functionalized polymer, R 11 can be a divalent ethylene or propylene moiety. In some embodiments, R of the (meth)acrylate functionalized polymer 12is a C8-C26 straight-chain saturated alkyl. In some embodiments of the (meth)acrylate-functionalized polymer, n may be an integer from 3 to 30. For example, n may be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30. According to some embodiments of the (meth)acrylate-functionalized polymer, R 19 It can be a branched saturated alkyl moiety.

[0049] Structure [C] is the following:

[0050]

[0051] R 13 , R 14 , R 15 , and R 16 is the same or different and is independently selected from the group consisting of H and organic moiety. Suitable organic moiety includes, but is not limited to, aromatic groups (e.g., phenyl groups), alkyl groups (e.g., methyl groups), or alkoxy groups. According to a specific embodiment of the (meth)acrylate-functionalized polymer, R 13 can be phenyl, alpha-methylphenyl, methyl or methoxy, or ethoxy, or any C2-C20 alkyl, and R 14 , R 15 and R 16 Each can be H. According to a specific embodiment, R 13 , R 14 , R 15 , and R 16All of them may be H. For example, the (meth)acrylate functionalized polymer disclosed herein may be derived from a methyl vinyl ether co-maleic anhydride polymer, e.g., Gantrez™ copolymer available from Ashland Chemical. According to a specific embodiment, the (meth)acrylate functionalized copolymer provided herein comprises a base polymer chain that may be derived from a copolymer of maleic anhydride and styrene or methyl vinyl ether or C2-C22 alkenes. For example, other comonomers suitable for copolymerization with maleic anhydride or other anhydride functionalized comonomers may be selected from ethylene, propylene, butene, pentene, hexene, heptene, octane, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, icocene, henicosene, dococene, styrene, alpha-methyl styrene, methyl vinyl ether, isomers thereof, and mixtures thereof.

[0052] The provided (meth)acrylate-functionalized polymer is conditioned such that structure [C] is different from structure [A] and structure [B], and additionally, one or more repeating units of structure [C] are located between at least one of i) two structure [A] units, ii) two structure [B] units, or iii) one structure [A] unit and one structure [B] unit.

[0053] According to another embodiment, the (meth)acrylate-functionalized polymer may further comprise, be composed of, or be composed of repeating units of structure [D] as an essential element. Structure [D] is as follows:

[0054]

[0055] R 17 and R 18 may be the same or different, may be selected from H, and may be selected from H or C1 to C4 alkyl groups. Preferably, R17 and R 18 Both are H.

[0056] According to an embodiment of a (meth)acrylate functionalized polymer comprising structural units [A], [B], [C], and [D], one or more structural units [C] may be located between at least one of the following:

[0057] i) 2 structural [A] units,

[0058] ii) 2 structural [B] units,

[0059] iii) 2 structural [D] units,

[0060] iv) 1 structure [A] unit and 1 structure [B] unit,

[0061] v) 1 structure [A] unit and 1 structure [D] unit, or

[0062] vi) 1 structure [B] unit and 1 structure [D] unit.

[0063] To eliminate any doubt, this means that the chain of the (meth)acrylate-functionalized polymer of the present invention has at least one of the following repeating units: [A][C][A], [B][C][B], [D][C][D], [A][C][B], [A][C][D], or [B][C][D]. Structure [A] is understood to have a (meth)acrylate functional group of the (meth)acrylate-functionalized polymer.

[0064] The (meth)acrylate-functionalized polymer may be a reaction product of at least i) an anhydride-functionalized base (meth)acrylate-functionalized polymer, ii) hydroxyl-functionalized (meth)acrylate, and iii) alkoxylated long-chain aliphatic alcohol. The anhydride-functionalized base (meth)acrylate-functionalized polymer may be a co(meth)acrylate-functionalized polymer of maleic anhydride and at least one comonomer. At least one comonomer may be styrene. ii) The hydroxyl-functionalized (meth)acrylate may be selected from the group consisting of hydroxyalkyl (meth)acrylate and alkoxylated hydroxyalkyl (meth)acrylate. iii) The alkoxylated long-chain aliphatic alcohol may be an ethoxylate of a C8-C26 aliphatic alcohol.

[0065] The (meth)acrylate-functionalized polymer may have a number average molecular weight of 1,000 to 75,000 daltons. For example, the number average molecular weight may be 1,000 to 50,000 daltons.

[0066] Curable compositions comprising the (meth)acrylate-functionalized polymer disclosed herein are provided. The curable composition may comprise the (meth)acrylate-functionalized polymer and ethylenically unsaturated curable species other than the (meth)acrylate-functionalized polymer. Non-limiting examples of such ethylenically unsaturated curable species may be selected from one or more free radical polymerizable, radiation-curable, substantially non-volatile, liquid monomers or oligomers with a molecular weight of up to about 2000, selected from monoethylenically unsaturated materials, polyethyleneally unsaturated materials, and mixtures thereof. Suitable non-limiting examples of such materials include lower alkyl esters of acrylic acid or methacrylic acid, including methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, and isobutyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride and vinylidene chloride; and particularly include highly soluble monomers such as 2,2-ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate, isodecyl acrylate, isooctyl acrylate, etc. Other non-limiting examples of monoethylene unsaturated reactive diluents include vinyl aromatics, e.g., styrene, alpha-methylstyrene, vinyl toluene, indene, and p-tert-butyl styrene; ethylenically unsaturated acids, e.g., fumaric acid, maleic anhydride, and esters thereof; and nitrogen-containing monomers, e.g., acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidine, N-vinylcaprolactam, etc.Non-limiting examples of polyethylene-based unsaturated reactive diluents include polyol polyacrylates and polymethacrylates, e.g., alkane (C2-C16) diol diacrylates, aliphatic (C2-C16) polyacrylates, alkoxylated aliphatic polyacrylates, polyether glycol diacrylates, etc. Other non-limiting examples are 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol 200 diacrylate, and tetraethylene glycol diacrylate. Other polyunsaturated reactive diluents include allyl acrylates, e.g., allyl methacrylates and diallyl methacrylates; acrylated epoxy, aminoplast acrylates, and unsaturated polyesters; Trimethylolpropane-based polyacrylates, e.g., trimethylolpropane triacrylate; pentaerythritol-based polyacrylates or polymethacrylates; acrylic oligomers; acrylated polymers or oils, e.g., acrylated epoxy-dry-type oils, acrylated bisphenol A / epoxy resins, ethoxylated bisphenol A diacrylates, acrylated urethane prepolymers (also known as "acrylated polyurethane"), polyethers, silicones, etc.

[0067] The curable composition may further comprise a matrix that is liquid at 25°C in which solid particles of the material are dispersed. Non-limiting examples of such a matrix include water, organic solvents, and mixtures thereof. The solid particles of the material may be selected from the group consisting of fillers, pigments, and inorganic pigments. Non-limiting examples of such fillers, pigments, and inorganic pigments include metal oxides, e.g., titanium dioxide, zinc oxide, or iron oxide, as well as organic pigments or combinations thereof. Non-limiting examples of pigments include precipitated salts of pigments containing sulfonic acid and / or carboxylic acid groups precipitated with alkaline earth metals or manganese. These pigments are beta-naphthol pigment lakes, e.g., pigments Red 49 (Red 49:1 and Red 49:2), Red 50:1, Red 51, Red 53 (Red 53:1 and Red 53:3), Red 68, Orange 16, Orange 17:1, Orange 46; BONA pigment lakes, e.g., Red 48:1, Red 48:2, Red 48:3, Red 48:4, Red 48:5, Red 52:1, Red 52:2, Red 57:1, Red 58:2, Red 58:4, Red 63:1, Red 63:2, Red 64, Red 64:1, Red 200, Brown 5; Naphthol AS pigment lakes, e.g., Red 151, Red 237, Red 239, Red 240, Red 243, Red 247, and naphthalene sulfonic acid pigment lakes, e.g., Yellow 104, Orange 19, Red 60, Red 66, Red 67, are included but not limited thereto. Examples of fillers may include, but are not limited to, calcium carbonate, nepheline rock, feldspar, diatomaceous earth, talc, aluminosilicate, silica, alumina, clay, kaolin, mica, pyrophyllite, perlite, barite, or wollastonite.

[0068] A method for dispersing solid particles of a material in a liquid matrix comprising one or more ethylenically unsaturated curable species is provided. The method comprises incorporating an effective amount of at least one (meth)acrylate-functionalized polymer disclosed herein into a liquid matrix and grinding the mixture with a grinding device (three roll mill, media mill, cowles blade).

[0069] Exemplary aspects of the present invention can be summarized as follows:

[0070] Embodiment 1: A (meth)acrylate-functionalized polymer comprising at least one structural [A] unit, at least one structural [B] unit, and at least one structural [C] unit,

[0071] Structure [A] is

[0072]

[0073] (wherein R1 and R3 are the same or different and are H or alkyl, and R2 and R4 are different and are an organic moiety or H having at least one (meth)acrylate functional group) and;

[0074] Structure [B] is

[0075]

[0076] (Here, R7 and R9 are the same or different, are H or alkyl, and R8 and R 10 is different and independently

[0077] (R 11 O) n R 12 (here, R 11 is a divalent alkylene moiety, and R 12 is a C8-C26 alkyl, and n is an integer greater than or equal to 1;

[0078] R 19 (here, R 19 is a C2-C30 branched or straight-chain alkyl;

[0079] R 20 (C=O)OH(where, R 20 is a C8-C26 branched or straight-chain alkyl); or

[0080] (Selected from H) and;

[0081] The structure [C] is

[0082]

[0083] (here, R 13 , R 14 , R 15 , and R 16 is identical or different and is independently selected from the group consisting of H and organic moiety;

[0084] However, structure [C] is different from structure [A] and structure [B];

[0085] A (meth)acrylate-functionalized polymer in which one or more repeating units of structure [C] are located between at least one of i) two structure [A] units, ii) two structure [B] units, or iii) one structure [A] unit and one structure [B] unit.

[0086] Embodiment 2: In Embodiment 1, the (meth)acrylate-functionalized polymer further comprises repeating units of structure [D], and structure [D] is

[0087]

[0088] (here, R 17 and R 18 A (meth)acrylate-functionalized polymer, which may be the same or different and may be selected from H or C1 to C4 alkyl groups.

[0089] Embodiment 3: In either Embodiment 1 or Embodiment 2, the (meth)acrylate-functionalized polymer, wherein one or more repeating units of the structure [C] are located between at least one of the following:

[0090] i) 2 structural [A] units,

[0091] ii) 2 structural [B] units,

[0092] iii) 2 structural [D] units,

[0093] iv) 1 structure [A] unit and 1 structure [B] unit,

[0094] v) 1 structure [A] unit and 1 structure [D] unit, or

[0095] vi) 1 structure [B] unit and 1 structure [D] unit.

[0096] Mode 4: In any one of Modes 1 to 3, one of R2 or R4 A (meth)acrylate-functionalized polymer, wherein R5 is a divalent alkylene or oligooxyalkylene or poly(ester) moiety and R6 is H or CH3.

[0097] Embodiment 5: In Embodiment 4, R5 is a (meth)acrylate-functionalized polymer, which is a poly(ester) moiety containing caprolactone residues.

[0098] Embodiment 6: An (meth)acrylate-functionalized polymer, wherein R6 is H in Embodiment 4 or Embodiment 5.

[0099] Embodiment 7: A (meth)acrylate-functionalized polymer in any one of Embodiments 1 to 6, wherein R1, R3, R7, and R9 are each H.

[0100] Embodiment 8: In any one of Embodiment 4, Embodiment 6 or Embodiment 7, R5 is a (meth)acrylate-functionalized polymer, wherein R5 is ethylene or oligooxyethylene.

[0101] Mode 9: In any one of Modes 1 to 8, R 13 is phenyl, methoxy, or C16 alkyl, and R 14 , R 15 and R 16(meth)acrylate-functionalized polymers, each H.

[0102] Mode 10: In any one of Modes 1 to 9, R 11 (Meth)acrylate-functionalized polymer, which is a divalent ethylene or propylene moiety.

[0103] Mode 11: In any one of Modes 1 to 10, R 12 is a (meth)acrylate-functionalized polymer that is a C8-C26 straight-chain saturated alkyl.

[0104] Embodiment 12: A (meth)acrylate-functionalized polymer, wherein in any one of Embodiments 1 to 11, n is an integer from 3 to 30.

[0105] Mode 13: In any one of Modes 1 to 12, R 19 is a (meth)acrylate-functionalized polymer that is a branched saturated alkyl.

[0106] Embodiment 14: A (meth)acrylate-functionalized polymer having a number average molecular weight of 1,000 to 50,000 daltons in any one of Embodiments 1 to 13.

[0107] Embodiment 15: A curable composition comprising an ethylenically unsaturated curable species other than a (meth)acrylate-functionalized polymer according to any one of Embodiments 1 to 14 and the (meth)acrylate-functionalized polymer according to Embodiment 1.

[0108] Embodiment 16: The curable composition of Embodiment 15, wherein the curable composition comprises a matrix that is liquid at 25°C in which solid particles of the material are dispersed.

[0109] Embodiment 17: Embodiment 15 or Embodiment 16, wherein the material is a curable composition selected from the group consisting of a filler, a pigment, and an inorganic pigment.

[0110] Embodiment 18: A method for dispersing solid particles of a material in a liquid matrix comprising one or more ethylenically unsaturated curable species, wherein the method comprises incorporating an effective amount of at least one (meth)acrylate-functionalized polymer according to any of Embodiments 1 to 14 into the liquid matrix.

[0111] Embodiment 19: A (meth)acrylate-functionalized polymer, wherein the (meth)acrylate-functionalized polymer is a reaction product of at least i) an anhydride-functionalized base (meth)acrylate-functionalized polymer, ii) a hydroxyl-functionalized (meth)acrylate, and iii) an alkoxylated long-chain aliphatic alcohol.

[0112] Embodiment 20: In Embodiment 19, the anhydride-functionalized base (meth)acrylate-functionalized polymer is a (meth)acrylate-functionalized polymer of maleic anhydride and at least one comonomer.

[0113] Embodiment 21: The (meth)acrylate-functionalized polymer in Embodiment 19 or Embodiment 20, wherein the hydroxyl-functionalized (meth)acrylate is selected from the group consisting of hydroxyalkyl (meth)acrylates and alkoxylated hydroxyalkyl (meth)acrylates.

[0114] Embodiment 22: In any of Embodiments 19 to 21, the alkoxylated long-chain aliphatic alcohol is an ethoxylate of a C8-C26 aliphatic alcohol, a (meth)acrylate-functionalized polymer.

[0115] In this specification, embodiments have been described in a manner that allows for a clear and concise specification; however, it is intended and understood that embodiments may be combined or separated in various ways without departing from the invention. For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0116] In some embodiments, the present invention may be interpreted as excluding any element or process step that does not substantially affect the basic and novel features of the curable composition, material, product and article produced therefrom and the method for producing and using such curable composition described herein. Additionally, in some embodiments, the present invention may be interpreted as excluding any element or process step not specified herein.

[0117] Although the present invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications in detail may be made within the scope and range of the equivalents of the claims and without departing from the invention.

[0118] Examples

[0119] Example 1: Preparation of an acrylate-functional dispersant:

[0120] The apparatus used for the synthesis was a 500 ml round-bottom flask with a bushing and stirrer shaft / blade inserted into the central joint, a condenser inserted into one side joint, a thermocouple inserted into the second side joint, and a dry air blower inserted into the third side joint. The stirrer shaft was attached to a stirrer motor. A heating mantle was placed beneath the flask and controlled by a temperature controller. 62.5 g of diethylene glycol diacrylate, 36.5 g of 2-hydroxyethyl acrylate, 74.6 g of 12 molar ethoxylated tridecyl alcohol, 0.25 g of 4-methoxyphenol, 0.25 g of BHT, and 0.23 g of tin octoate were added to the flask. The mixture was stirred and heated to 50°C. Subsequently, 138.2 g of SMA ® 1000 (styrene-maleic anhydride copolymer from Cray Valley) resin was slowly added. SMA ® After adding and dispersing the 1000 resin, the mixture was heated to 95°C. The temperature was maintained at 95°C for 6 hours, after which samples were taken every hour to determine the acid value. When the acid value was < 139 mg KOH / gm, the reaction mixture was cooled to 65°C, and stirring and air aeration were stopped. The resulting polymer had a structure of repeating units [A], [B], [C], and [D], where [A], [B], [C], and [D] are as described above and are as follows:

[0121] [A]: R1= R2= R3= H and R4= ethyl acrylate.

[0122] [B]: R7= R8= R9= H and; R 10 = -(R 11 O) n R 12 and R 11 is CH2CH2, and R 12 is a C13 straight-chain saturated alkyl, and n = 12.

[0123] [C]: R 14 = phenyl and; R13 = R 15 = R 16 = It is H.

[0124] [D]: R 17 = R 18 = It is H.

[0125] Example 2: Efficacy of the acrylate-functional polymer of Example 1 as a dispersant

[0126] SR238B solvent (1,6-hexanediol diacrylate available from Sartom Americas) (8 gr) having a viscosity of 6 cPs and the polymer prepared in Example 1 (0.2 gr) as a dispersant were mixed together in a room temperature water sonicator for 3 minutes until the dispersant prepared in Example 1 was completely dissolved in the monomer SR238B. Afterward, TiO2 (2 gr) was added and sonicated for an additional 3 minutes. The mixture was placed in a grind gauge and visually inspected to see how uniformly the TiO2 was dispersed in the monomer without further grinding. The results are shown in Figures 1 and 2. As shown in Figure 1, the mixture containing about 2 wt% of the acrylate-functional polymer prepared in Example 1 did not affect the viscosity of the solution and exhibited superior dispersion of 20 wt% TiO2 compared to the control mixture shown in Figure 2, which does not contain the dispersant of the present invention.

Claims

Claim 1 (Meth)acrylate-functionalized polymer comprising at least one structure [A] unit, at least one structure [B] unit, and at least one structure [C] unit: structure [A] is as follows: Here, R1 and R3 are the same or different and are H or alkyl, R2 and R4 are different and are an organic moiety or H having at least one (meth)acrylate functional group; structure [B] is as follows: Here, R7 and R9 are the same or different, are H or alkyl, and R8 and R 10 One of them is H, and R8 and R 10 The other one is -(R 11 O) n R 12 and, here, R 11 is a divalent alkylene moiety, and R 12 is a C8-C26 alkyl, n is an integer greater than 1; the structure [C] is as follows: Here, R 13 , R 14 , R 15 , and R 16 The structure [C] is selected from the group consisting of H and organic moieties that are identical or different and independently; provided that the structure [C] is different from the structure [A] and the structure [B]; and one or more repeating units of the structure [C] are located between at least one of i) two structure [A] units, ii) two structure [B] units, or iii) one structure [A] unit and one structure [B] unit. Claim 2 In paragraph 1, one of R2 or R4 and, where R5 is a divalent alkylene, an oligooxyalkylene, or a poly(ester) moiety, R6 is H or CH3, and the oligooxyalkylene is of the following chemical formula -[(CR a R b ) p -O] q -(CR a R b ) p Expressed as -, where R a and R b A (meth)acrylate-functionalized polymer, wherein is independently H or alkyl, p is 2 to 4, and q is at least 1. Claim 3 In paragraph 2, R5 is a (meth)acrylate-functionalized polymer, which is a poly(ester) moiety containing caprolactone residues. Claim 4 In paragraph 2, R5 is ethylene or oligooxyethylene, and said oligooxyethylene is of the following chemical formula -[(CR a R b )2-O] q -(CR a R b It is expressed as )2-, where R a and R b A (meth)acrylate-functionalized polymer in which is H and q is at least 1. Claim 5 In paragraph 1, R 13 is phenyl, alpha-methylphenyl, methyl, methoxy, ethoxy, or C2-C20 alkyl, and R 14 , R 15 and R 16 (meth)acrylate-functionalized polymers, each H. Claim 6 In paragraph 1, R 12 is a (meth)acrylate-functionalized polymer that is a C8-C26 straight-chain saturated alkyl. Claim 7 A (meth)acrylate-functionalized polymer, wherein n is an integer from 3 to 30. Claim 8 A (meth)acrylate-functionalized polymer having a number average molecular weight of 1,000 to 50,000 daltons in claim 1. Claim 9 A curable composition, wherein the curable composition comprises an ethylenically unsaturated curable species other than a (meth)acrylate-functionalized polymer according to any one of claims 1 to 8 and a (meth)acrylate-functionalized polymer according to claim 1. Claim 10 In claim 9, the curable composition comprises a matrix that is liquid at 25°C in which solid particles of a material are dispersed, and said material is selected from the group consisting of fillers and pigments. Claim 11 A method for dispersing solid particles of a material in a liquid matrix comprising one or more ethylenically unsaturated curable species, wherein the method comprises incorporating an effective amount of at least one (meth)acrylate-functionalized polymer according to any one of claims 1 to 8 into the liquid matrix, and wherein the material is selected from the group consisting of fillers and pigments. Claim 12 A (meth)acrylate-functionalized polymer, wherein the (meth)acrylate-functionalized polymer is a reaction product of at least i) an anhydride-functionalized polymer, ii) a hydroxyl-functionalized (meth)acrylate, and iii) an alkoxylated C8-C26 aliphatic alcohol. Claim 13 In paragraph 12, the anhydride-functionalized polymer is a (meth)acrylate-functionalized polymer, which is a copolymer of maleic anhydride and at least one comonomer. Claim 14 In claim 12 or 13, the hydroxyl-functionalized (meth)acrylate is a (meth)acrylate-functionalized polymer selected from the group consisting of hydroxyalkyl (meth)acrylates and alkoxylated hydroxyalkyl (meth)acrylates. Claim 15 In claim 12 or 13, the alkoxylated C8-C26 aliphatic alcohol is a (meth)acrylate-functionalized polymer that is an ethoxylate of a C8-C26 aliphatic alcohol. Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete

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