Cyclodextrin-assisted latex polymerization

Abstract

A hydrophobic latex polymer having a small particle size is disclosed. Polymerized via a reaction mixture including a hydrophobic monomer, a macromolecular organic compound having a hydrophobic cavity such as a cyclodextrin, a surfactant that is sterically hindered from complexing with the macromolecular compound, and an initiator, the resulting latex polymer has a small polymer size, lacks grit, and is producible without undesirable reactor deposits.

Description

23134P1CYCLODEXTRIN-ASSISTED LATEX POLYMERIZATIONCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 U. S. C. 119(e) to U. S. Provisional Patent Application 63 / 723,923 filed November 22, 2024. The contents of the aforementioned application is incorporated herein.FIELD

[0002] This application generally relates to methods of producing a hydrophobic acrylic polymer by latex polymerization, latex dispersions including the hydrophobic acrylic polymer, and a paint or stain composition including the latex dispersions.BACKGROUND

[0003] Latex, or emulsion polymerization is carried out in a heterogeneous reaction medium in which the monomers diffuse from monomer droplets to growing polymer particles. This process occurs when monomer(s), initiator, dispersion medium, and surfactant constitute initially an inhomogeneous system resulting in a colloidal mixture containing the formed polymer. This system restricts the list of useful monomers to more hydrophilic ones that have a finite solubility in water, as these can diffuse through the dispersion medium from the monomer droplets to the polymer particles.

[0004] Cyclodextrin has been used to improve transport of hydrophobic monomers and / or chain transfer agents in emulsion polymerization to overcome the inhomogeneity problem. Having an annular or cup-like shape, cyclodextrin and other cavitands have been reported to have an inner portion having hydrophobic affinity, and an outer portion having hydrophilic affinity. Consequently, the technology allows the transport of hydrophobic monomers from a monomer drop to a growing latex particle. Latex polymerization requires the use of a surfactant to stabilize the polymer particles in water, however, and cyclodextrin-assisted polymerization with conventional ethoxylated surfactants having a hydrophobic portion that includes a linear saturated hydrocarbon chain has been unsuccessful in supporting polymerization of hydrophobic monomers. More specifically, polymerization with such conventional surfactants have yielded polymeric dispersions that are undesirable in some application, having a large particle size, a gritty latex (caused by crosslinking of the monomers) and / or leaving deposits on thePage 1 of 4662821089 123134P1polymerization reactor. Thus, what is needed is a method for producing hydrophobic acrylic latex dispersions by cyclodextrin-assisted emulsion polymerization which has a sufficiently small particle size, provides a high quality, low grit dispersion, and leaves little to no deposits on the reactor.SUMMARY

[0005] Disclosed is a method of producing a hydrophobic acrylic polymer by latex dispersion polymerization, the method comprising: mixing a reactant mixture including a (meth)acrylate monomer including a linear or branched saturated aliphatic group having at least 8 carbons; a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin or a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof; a surfactant having a structure hindered from complexing with the macromolecular organic compound; and an initiator.

[0006] In some embodiments, the surfactant hindered from complexing with the macromolecular organic compound is a compound of formula (I):whereinRi is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched C1to C6alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;R3is selected from the group consisting of H, linear or branched Ci to Ce alkyl, and C4 to C7 cycloalkyl, aryl, and heteroaryl;R4 is optionally present and selected from the group consisting of linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4 are independently selected for each Ri;Page 2 of 4662821089 123134P1Rs is H, S04’A+, or PO4'A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.

[0007] Also disclosed is an aqueous latex dispersion comprising: a hydrophobic polymer wherein at least 10 weight percent, at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 50 weight percent, or at least 75 weight percent of monomer units in the hydrophobic polymer are derived from a (meth)acrylate monomer having a linear or branched, saturated hydrocarbon chain of at least 8 carbons; and a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin and a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof; and a surfactant hindered from complexing with the macromolecular organic compound; wherein the latex polymer dispersion has a peak particle size of not greater than about 200 nm.

[0008] Also disclosed is a paint or stain composition comprising a film-forming amount of the disclosed aqueous latex dispersions, and at least one additive or an opacifying pigment.

[0009] These features may be combined with one or more optional aspects as disclosed herein.

[0010] The foregoing summary is not intended to describe each and every aspect of the present disclosure and present inventions. Further aspects of the present disclosure are described herein.FIGURES

[0011] FIG. 1 is a structure of an exemplary surfactant according to the description with a measurement of the hydrophobic end.DETAILED DESCRIPTION

[0012] Prior use of cyclodextrin to aid in latex polymerization of hydrophobic monomers tended to produce latex dispersions having polymers having an undesirably large particle size for some applications. The cyclodextrin aided in the transport of hydrophobic monomers and / or hydrophobic chain transfer agents by binding to such compounds. However, prior cyclodextrin-Page 3 of 4662821089 123134P1assisted latex polymerization using conventional long chain fatty alcohol ether sulfate surfactants combined with hydrophobic monomers generally resulted in latex particles with large particle sizes over about 200 nm. Without wishing to be limited by theory, it is believed that linear surfactants having C 12 to C 16 alkyl chains as a hydrophobic tail compete with monomers having a similar length alkyl chain, such as lauryl and / or stearyl (meth)acrylate monomers in the context of binding to the cyclodextrin cavity. Thus, the affinity of the surfactant alkyl chain with the cyclodextrin cavity often resulted in less cyclodextrin available for the transport of the monomers and / or less available surfactant and, as a result, larger particle sizes of the formed latex dispersion. In addition, surfactant binding with the cyclodextrin may remove usable surfactant that can stabilize the latex particles during polymerization. Prior use of conventional long chain linear surfactants, cyclodextrin, and hydrophobic monomers thus has the shortcoming that particle sizes below about 200 nm were difficult to obtain and / or the reaction left deposits on the reactor.

[0013] The particle size of a hydrophobic latex can be reduced by further processing following polymerization in the form of high-shear mixing such as sonication, microfluidization, homogenization, colloid mixing, mini-emulsification, micro-fluidization, and the like. However, this processing requires investment in additional capital equipment and extends processing time beyond that required for polymerization.

[0014] In one approach or embodiment, the present application relates to methods of producing a hydrophobic acrylic polymer by latex emulsion polymerization or latex dispersion polymerization through a reactant mixture of one or more hydrophobic (meth)acrylate monomers, such as (meth)acrylate monomers having a linear or branched saturated aliphatic group having at least 8 carbons; optionally short chain (meth)acrylate monomers; a macromolecular organic compound having a hydrophobic cavity, such as cyclodextrin or a cyclodextrin derivative, cyclic oligosaccharides having a hydrophobic cavity such as cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene, and cavitand, or combinations thereof; a surfactant hindered from complexing with the macromolecular organic compound; and an initiator. (As used herein, latex emulsion and latex dispersion (or a polymer latex emulsion or polymer latex dispersion) can be used interchangeably.) Surprisingly, when such macromolecular organic compound is combined with surfactants hindered from complexing with the macromolecular organic compound during polymerization, the resultantPage 4 of 4662821089 123134P1polymer latex dispersions can be formed with a peak particle size of less than about 200 nm and such peak particle size of the polymer latex dispersions can be produced in embodiments without using any of the high shear mixing as noted above.

[0015] In one embodiment, an in-situ seed preparation process is the first stage of a continuous or batch polymerization process including water, surfactants that are hindered from complexing with the macromolecular organic compound, and a small portion of the recipe's monomers, are polymerized with an initiator to form the desired number of seed polymer particles. The amount of monomer and reaction conditions used for seed polymerization determines the number and size of seed particles formed, which, upon addition of the remaining monomers, grows to the particle size of the final latex dispersion. The seed, once formed, is followed by a second stage of successive addition of the remaining recipe monomers to form the final product. The macromolecular organic compound having a hydrophobic cavity may be added prior to seed polymerization, or after. Selection of the monomers used for the first stage, seed-polymerization and the remaining monomers later added can be used to generate a two-phase polymer particle.

[0016] Alternatively, a seeded polymerization process may be utilized, wherein a previously polymerized seed polymer is added with water, monomers, a macromolecular organic compound, surfactants that are hindered from complexing with the macromolecular organic compound, and initiator are added to a reaction vessel. Seed polymer particles having a molecular weight of, e.g., about 100,000 or more of weight average molecular weight are generally utilized. After addition of the seed polymer, water, surfactants that are hindered from complexing with the macromolecular organic compound, and monomers are added with a water-soluble initiator to polymerize around the seed particles. The macromolecular organic compound having a hydrophobic cavity may be added before or after the initiator. As with in-situ seed preparation, selection of the monomers used to prepare the polymerized seed polymer and the remaining monomers later added can be used to generate a two-phase polymer particle.

[0017] Thus, during the polymerization process, the ingredients are monomer, surfactant, water, macromolecular organic compound noted above, and a water-soluble initiator. Typically, the monomer is dispersed in the aqueous phase by the surfactant or emulsifying agent and / or the macromolecular organic compound. The reaction is initiated by the water-soluble initiator. During polymerization, the macromolecular hydrophobic having a hydrophobic cavityPage 5 of 4662821089 123134P1transports hydrophobic monomers from monomer droplets to the polymerizing latex polymer dispersed particles.

[0018] In embodiments, suitable polymerization temperatures of the aqueous dispersion may be at least about 30°C, at least about 60°C or at least about 70°C. In some embodiments, the polymerization temperature of the aqueous dispersion may be at most about 95° C, or at most about 90° C, or at most about 85° C.

[0019] Hydrophobic Monomers:

[0020] The methods and polymers herein include one or more hydrophobic monomers. Such monomers can provide a low surface energy to aid in stain resistance and / or dirt pick-up resistance to the formed coatings. In an embodiment, hydrophobic monomers suitable for the polymer latex dispersions and polymerization methods herein may include, but are not limited to, hydrophobic a, P-ethylenically unsaturated monomers such as vinyl esters of C8 toC30 carboxylic acids, such as vinyl 2-ethylhexanoate, vinyl neodecanoate and the like; N-alkyl substituted (meth)acrylamide such as octyl acrylamide and maleic acid amide; vinyl alkyl or aryl ethers with (C8 to C30) alkyl groups such as stearyl vinyl ether; (C8 to C30) alkyl esters of (meth)acrylic acid, such as 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate; multifunctional monomers such as pentaerythritol triacrylate; and the like. The hydrophobic monomers herein may also contain other functionalities, such as hydroxy, amido, aldehyde, ureido, polyether and the like functionalities as needed for particular application.

[0021] In another approach or embodiment, the hydrophobic monomers of the polymers and methods herein are preferably hydrophobic (meth)acrylate monomers and include (meth)acrylate monomers having a saturated aliphatic group with a linear chain of least 8 carbons, or at least 10 carbons, or at least 12 carbons, or at least 16 carbons, or at least 20 carbons, or more than 20 carbons. In another embodiment, the linear or branched saturated aliphatic group has at most 24 carbons, at most 20 carbons, at most 18 carbons, or at most 16 carbons. In an embodiment, the linear or branched saturated aliphatic group has at least 8 carbons, at least 10 carbons, or at least 12 carbons. In an embodiment, the linear or branched saturated aliphatic group has at least 10 carbons, at least 12 carbons, or at least 14 carbons. In other embodiment, the long chain linear or branched saturated aliphatic group of thePage 6 of 4662821089 123134P1(meth)acrylate monomers herein is a C8 to C24 group, a C8 to C20 group, a C8 to Cl 8 group, or other ranges between such end points. In yet another embodiment, the hydrophobic (meth)acrylate monomer may preferably include monomers of stearyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, isooctyl (meth)acrylate, isobomyl (meth)acrylate, isodecyl (meth)acrylate, ethylhexyl (meth)acrylate, or combinations thereof.

[0022] Hydrophobic monomers as disclosed herein have low water solubility. In an embodiment, the water solubility of the hydrophobic (meth)acrylate monomers herein is less than about 0.01 wt. %, or less than about 0.005 wt. %, or less than about 0.0025 wt. %, or less than about 0.001 wt. %, as measured according to the experimental procedure described in Chai, X.-S., et al., Measurement of the Solubilities of Vinylic Monomers in Water, Ind. Eng. Chem. Res. 2005, 44, 5256-5258. In some embodiments, the monomer mixture being reacted is substantially free, or free, of alkyd monomers.

[0023] Other Monomers:

[0024] In other embodiments, the polymers herein may also include other monomers as needed for a particular application. In one approach, such other monomers may include short chain (meth)acrylate monomers. In this optional approach, the short chain moiety of the (meth)acrylate monomers may include a linear or branched aliphatic group having less than 8 carbons, or no more than 6 carbons, or no more than 4 carbons, or no more than 2 carbons. In an embodiment, such short-chain (meth)acrylate monomer may include, but are not limited to, butyl (meth)acrylate, methyl (meth)acrylate, propyl (meth)acrylate, vinyl acetate, (meth)acrylic acids, and the like, and combination thereof.

[0025] In alternative approaches, the polymers and methods herein may include other optional monomers including, but not limited to, vinyl monomers selected from the group consisting of vinyl esters, vinyl aromatic hydrocarbons, vinyl aliphatic hydrocarbons, vinyl acetate, vinyl alkyl ethers and mixtures thereof. Examples of vinyl esters that may be used include vinyl acetate, vinyl propionate, vinyl laurate, vinyl pivalate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl butyrates, vinyl benzoates, and vinyl isopropyl acetates. Examples of vinyl aromatic hydrocarbons that may be used include styrene, methyl styrenes and other lower alkyl styrenes, chlorostyrene, vinyl toluene, vinyl naphthalene and divinyl benzene. Examples of vinyl aliphatic hydrocarbons that may be used include vinyl chloride andPage 7 of 4662821089 123134P1vinylidene chloride as well as alpha olefins such as ethylene, propylene, isobutylene, as well as conjugated dienes such as 1,3 butadiene, methyl-2 -butadiene, 1,3-piperylene, 2,3-dimethyl butadiene, isoprene, cyclohexene, cyclopentadiene, and dicyclopentadiene. Examples of vinyl alkyl ethers that may be used include methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether.

[0026] Optional acrylic monomers suitable for use in the present methods and compositions may include any compounds having acrylic functionality. Suitable acrylic monomers are selected from the group consisting of alkyl (meth)acrylates, acrylic acids, as well as aromatic derivatives of (meth)acrylic acid, acrylamides, acrylonitrile, or combinations thereof. Typically, the alkyl (meth)acrylate monomers (also referred to herein as "alkyl esters of (meth)acrylic acid") will have an alkyl ester portion containing from 1 to 6, in some approaches, 1 to 4, carbon atoms per molecule, or 1 to 2 carbon atoms, or methyl groups.

[0027] Suitable acrylic monomers may include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, neopentyl (meth)acrylate, 1-adamatyl methacrylate and various reaction products such as butyl, phenyl, and cresyl glycidyl ethers reacted with (meth)acrylic acid, hydroxyl alkyl (meth)acrylates, such as hydroxyethyl and hydroxypropyl (meth)acrylates, amino (meth)acrylates, as well as acrylic acids such as (meth)acrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cycanoacrylic acid, crotonic acid, beta-acryloxy propionic acid, and beta-styryl acrylic acid.

[0028] In yet other approaches, the methods and polymers herein may also include optional ketone-functional vinyl monomer units. In some approaches, these monomer units may be derived from diacetone acrylamide, diacetone (meth)acrylamide, acetoacetoxyethyl (meth)acrylate, acrolein, methacrolein, vinylacetoacetate, crotonaldehyde, 4-vinylbenzaldehyde, vinyl alkyl ketones, acrylamide-pivalaldehyde, methacrylamidopivalaldehyde, 3-acryl amidomethyl-anisaldehyde, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, acetoacetoxyethylmethacrylate, 2-hydroxypropylacrylate acetylacetate, and butanediol acrylate acetylacetate and the like, and combinations thereof.

[0029] The methods and polymers herein may also include other optional monomers polymerized into the polymer backbone as needed for a particular application. For instance, thePage 8 of 4662821089 123134P1copolymer may further include ureido monomers, amino monomers, sulfonate monomers or surfactants, silane monomers, phosphate monomers or surfactants, carboxyl monomers or surfactants, and combinations thereof. In some approaches, the copolymer may further include vinyl monomers such as allyl imidazolidinone, allyl acetoacetates, allyl epoxies, epoxy acrylates, carbonyl monomers, other sulfonates, other phosphonates, vinyl phosphonate, allyl hydroxypopyl sodium sulfonate, allyloxy hydroxypropyl sodium sulfonate, and combinations thereof as needed for a particular application. In some approaches, for instance, any other monomers may each be present in the acrylic copolymer in amounts up to about 10 weight percent, and in other approaches, about 0.1 to about 5 weight percent, in other approaches, about 0.5 to about 2 weight percent, but the amounts may vary depending on the particular application. In yet other approaches, the other or additional monomers may each be included in the polymer backbone in amounts less than about 1 weight percent.

[0030] Macromolecular Organic Compound with a Hydrophobic Cavity:

[0031] In another aspect of the polymer latex dispersions and polymerization methods herein, the methods include the use of a macromolecular organic compound having a hydrophobic cavity configured to complex with the hydrophobic monomers in a first stage of the polymerization. In embodiments, the macromolecular organic compound having a hydrophobic cavity may be selected from the group consisting of cyclodextrin or a cyclodextrin derivative; or cyclic oligosaccharides having a hydrophobic cavity such as a cycloinulohexose, a cycloinuloheptose, a cycloinuloctose, a calyxarene and a cavitand, and the like; or combinations thereof. Such compounds have a cavity, often in the form of a hollow cylinder, bucket, cup, or other cavity shape, with an inner surface providing a hydrophobic cavity, and an outer surface that is more hydrophilic, making the macromolecular compound stable, and soluble, in water, but able to complex with hydrophobic molecules.

[0032] Cyclodextrin is preferred as the organic macromolecular compound, and suitable examples of cyclodextrins include a-cyclodextrin, 0-cyclodextrin, and y-cyclodextrin with 0-cyclodextrin being most preferred. In other embodiments, examples of cyclodextrin derivatives include partially or fully methylated cyclodextrins, partially or fully acetylated cyclodextrins, and / or partially or fully hydroxylpropylated cyclodextrins. Suitable cyclodextrin derivatives may include, but are not limited to, methyl, triacetyl hydroxypropyl and hydroxyethylPage 9 of 4662821089 123134P1derivatives of a-cyclodextrin, P-cyclodextrin and y-cyclodextrin. Suitable cyclic oligosaccharides having a hydrophobic cavity, such as cycloinulohexose, cycloinuloheptose, that may be used are described, or instance, by Takai et al., Journal of Organic Chemistry, 1994, volume 59, number 11, pages 2967-2975, which is incorporated herein by reference. Suitable calyxarenes are those described in US 4,699,966, WO 89 / 08092, JP 1988 / 197544, and JP 1989 / 007837, which are all incorporated herein by reference. Suitable cavitands are those described in IT 22522 A / 89 and Moran et al., Journal of the American Chemical Society, volume 184, 1982, pages 5826-5828, which are both incorporated herein by reference.

[0033] Exemplary alpha, beta, and gamma cyclodextrins suitable for the organic macromolecular compounds herein have a hydrophobic cavity configured to interact with the hydrophobic portion of the monomers described herein. The hydrophobic cavity has been reported1to have the following dimensions.Table 1: Hydrophobic Cavity Dimensions_ of Exemplary Cyclodextrins _Molecule Hydrophobic cavity diameter(angstroms)oc-cyclodextrin 4.5 - 5.3P-cyclodextrin 6.0 - 7.0Y-cyclodextrin 7.5 - 8.5

[0034] In some approaches, the hydrophobic cavity is about 4 to about 10 angstroms wide (at the broadest end) by about 5 to about 10 angstroms deep. In one embodiment, suitable hydrophobic cavities have a cross-sectional area (at the larger end) of about 16 to about 56 square angstroms, or more preferably about 28 to about 39 square angstroms. In other embodiments, suitable hydrophobic cavities have a volume of about 120 to 450 cubic angstroms, and more preferably about 220 to about 315 cubic angstroms.

[0035] The amount of the macromolecular compound added to the reaction mixture depends on the type of macromolecular compound and the type of monomers in the reaction mixture. As a general matter, the ratio, on a molar basis, of the macromolecular compound to hydrophobic monomer is from about 5: 1 to 1: 5000. Preferably, the molar ratio is about 1: 1 to 1: 1000, and most preferably from 1:1 to 1:500.1Das, S., Cavity Size Dependent Stoichiometry of Probe-cyclodextrin Complexation: Experimental and Molecular Docking Demonstration. J. Photochem. & Photobiol. A: Chemistry 388 (2020).Page 10 of 4662821089 123134P1

[0036] As noted in the background, such the hydrophobic cavity is believed to have an affinity to the hydrophobic portion of the hydrophobic monomers. The hydrophobic cavity is further believed to also have an affinity to the hydrophobic portion of conventional surfactants, which include a long aliphatic chain. When utilized with conventional surfactants having a long chain aliphatic hydrophobic portion, latex dispersion polymerization of hydrophobic monomers in the presence of cyclodextrin or cyclodextrin derivatives as disclosed herein tend to have a large particle size or impart undesirable deposits on reactor components.

[0037] Surfactant Hindered From Complexing with Macromolecular Compound

[0038] In approaches or embodiments, the surfactant suitable for the polymers and methods herein is structurally configured to be sterically hindered from complexing with the organic macromolecular compound. In an aspect, the surfactant has one or more hydrocarbon hydrophobic groups, e.g., a benzene ring, cyclic group, or preferably more than one benzene ring or cyclic group. In this aspect, one or more benzene rings is preferred and may be substituted or unsubstituted. In an embodiment, the surfactant lacks a linear hydrocarbon hydrophobic group, e.g., a C6-C16 alkyl group. In another embodiment, the surfactant is preferably an ethoxylated tristyryl phenol.

[0039] In another approach or embodiment, the surfactant is a compound having a structure of Formula I:whereinRi is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched Ci to C6alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;R3is selected from the group consisting of H, linear or branched Ci to Ce alkyl, and C4 to C7 cycloalkyl, aryl, and heteroaryl;Page 11 of 4662821089 123134P1R.4 is optionally present and selected from the group consisting of linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4 are independently selected for each Ri;Rs is H, SO4’A+, or P04'A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.In an embodiment, the reactant mixture is essentially free of, or free of, an ethoxylated surfactant lacking a benzene ring. In optional embodiments, R2 is Ci to Ce alkyl; R3 is Ci to Ce alkyl or H; and / or R4 is an aryl group.

[0040] In further embodiments, the surfactant compound of Formula I above is a compound of Formula II and / or a compound of Formula III:R5 R5R-i R-|(II) (HI)wherein Ri, A+, and n are defined as above, or in another embodiment, Ri is

[0041] Thus, in some embodiments, the surfactant may be nonionic, as when Rs is H. In other embodiments, the surfactant may be ionic, as when Rs is a sulphate or phosphate anion, partially or wholly neutralized with an alkali cation such as Li+, Na+, K+, an ammonium cation, or a trialkylammonium cation.

[0042] Without being bound by theory, it is believed that the smaller cross-sectional area of conventional ethoxylated surfactants having a long-chain aliphatic hydrophobic portion as compared to the size of the hydrophobic cavity of the macromolecular compound allows the aliphatic, hydrophobic end to complex with the hydrophobic cavity of the macromolecular compound. In such circumstances, the hydrophobic cavity of the macromolecular compound is unavailable, or less available, for complexing with hydrophobic monomers, resulting in poorlyPage 12 of 4662821089 123134P1developed latex polymer dispersions such as those having a large particle size, gels, or deposits on reactor vessels.

[0043] In contrast, surfactants that are sterically hindered from complexing with the hydrophobic cavity of the macromolecular compound are available to stabilize the hydrophobic monomer droplets and latex dispersion particles, without competing with the hydrophobic monomers for complexing with the macromolecular compound.

[0044] This theory of mechanism for the discovered effects is supported by comparative calculation of the cross-sectional area of conventional long-chain aliphatic surfactants as compared to the sterically hindered surfactants as disclosed herein. With reference to FIG. 1, suitable surfactants have a cross sectional area of the hydrophobic end of about 40 square angstroms, or at least about 60 square angstroms, or at least about 65 square angstroms.

[0045] In some embodiments, the cross-sectional area of the surfactant hydrophobic end is about 40 to about 90 square angstroms.

[0046] The cross sectional area of the hydrophobic end of a surfactant may be estimated by a computer-assisted analysis of the molecular size of the hydrophobic end of a surfactant as viewed from the axis on which it is the narrowest. FIG. 1. shows an exemplar geometric calculation of the cross section area of the hydrophobic end calculated using the software and methodology of Example 4. The cross-sectional radius of the hydrophobic end show in FIG 1 was calculated to 5.1 angstroms. Thus, the cross-sectional area of the hydrophobic end of this molecular is calculated based on the area of the radius’s circle: for this molecule is π x (5.1 angstroms)2= 82.2 angstroms2.

[0047] In contrast, a similar analysis of the cross-sectional area of a conventional ethoxylated surfactant having a hydrophobic end composed of a long-chain aliphatic group yields a molecular radius of the hydrophobic end of radius of 1.55 angstroms, and a cross-sectional area of 7.6 angstroms2.

[0048] As shown in Table 1, the hydrophobic cavity of a-cyclodextrin, P-cyclodextrin, and y-cyclodextrin have a radius of 2.25-2.65, 3-3.5, and 3.75-4.25 angstroms, respectively. The cross-sectional radius of the hydrophobic end of a conventional ethoxylated surfactant having a linear aliphatic hydrophobic chain has a similar or smaller cross-sectional area, estimated to be about 1.4 Angstroms. In contrast, the cross-sectional radius of the hydrophobic end of a sterically hindered surfactant as disclosed herein is larger, for example, 5.5 angstroms.Page 13 of 4662821089 123134P1Surfactants with a larger hydrophobic end as disclosed herein are thus sterically hindered from complexing with cyclodextrin and related cyclodextrin derivatives in the reaction mixture.

[0049] In some aspects, the amount of surfactants in the reaction mixture is at least 0.1, 0.2, or 0.5 wt.% based on total monomer (BOTM). In some aspects, the amount of surfactants in the reaction mixture is at most 8, at most 4, or at least 1 wt.% based on total monomer (BOTM).

[0050] Initiator

[0051] In an embodiment, the initiator may be added before or after the cyclodextrin to the reaction mixture. In another embodiment, the initiator is preferably added before the cyclodextrin. Adding the initiator before addition of the cyclodextrin allows for polymerization of a two-phase polymer particle. The amount of initiator will typically vary from about 0.01 to 3 weight percent based on the weight of monomers charged. However, the concentration of the initiator is preferably from about 0.05 to about 2 weight percent and, more preferably, from about 0.1 to about 1 weight percent of the monomers charged. The particular amount used in any instance will depend upon the specific monomer mixture undergoing reaction and the specific initiator employed, which details are known to those skilled in the art.

[0052] Suitable initiators that may be used in the polymerizations herein include, but are not limited to, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl hydroperoxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dicholorbenzoyl peroxide, 2,5-dimethyl-2,5-bis(hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dicicosyl peroxydicarbonate, di-t-butyl perbenzoate, 2,2'-azobis-2,4-dimethylvaleronitrile, ammonium persulfate, potassium persulfate, sodium persulfate, sodium perphosphate, azobi si sobutyronitrile, as well as any of the other known initiators. Also useful are the redox catalyst systems such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulfite, hydrogen peroxideascorbic acid, and other known redox systems. Moreover, as known by those skilled in the art, traces of metal ions can be added as activators to improve the rate of polymerization, if desired.

[0053] Aqueous Latex Dispersion or Aqueous Latex EmulsionPage 14 of 4662821089 123134P1

[0054] In another aspect, the present description includes a latex emulsion or latex dispersion prepared according to the method hereinbefore described and includes a hydrophobic polymer prepared by the polymerization methods described above. In an embodiment, the aqueous latex dispersion includes a hydrophobic polymer wherein at least about 10 weight percent, at least about 15 weight percent, at least about 20 weight percent, at least about 25 percent, at least about 50 weight percent, or at least about 75 weight percent of monomer units in the hydrophobic polymer are derived from a hydrophobic (meth)acrylate monomer as discussed above having a linear or branched saturated hydrocarbon chain of at least 8 carbons, based on the total monomers present in the hydrophobic polymer. In other approaches, the aqueous latex dispersion includes less than about 80 weight percent of monomer units in the polymer derived from such hydrophobic (meth)acrylate monomers, less than about 60 weight percent, or less than about 30 weight percent based on the total monomers present in the hydrophobic polymer.

[0055] In another aspect, the latex polymer emulsion as prepared herein has a peak particle size of not greater than about 200 nm as measured by dynamic light scattering. In other embodiments, the latex polymer dispersions herein has a peak particle size of not greater than about 175 nm, or not greater than about 150 nm, or not greater than about 125 nm. In an embodiment, the peak particle size of the latex polymer dispersions herein may be from about 75 to about 200 nm, or from about 75 to about 150 nm, or from about 90 to about 125 nm, or about 90 to about 120 nm, or from about 90 to about 110 nm. Preferably, the latex emulsions or latex dispersions herein may include all the embodiments, in any combination, as previous described hereinabove during the polymerization such as the organic macromolecular compound, the surfactant, and the initiator. In another approach or embodiment, the aqueous latex dispersion or aqueous latex emulsion is obtained without any high-shear mixing such as sonication, high shear mixing via a mini-emulsifier or micro-fluidizer, or the like, or combinations thereof.

[0056] In other approaches or embodiments embodiment, the latex dispersions herein include a hydrophobic polymer having a glass transition temperature (Tg), in one embodiment, of less than about -30°C, or in other embodiments about -30°C to about 0°C, or in yet other embodiments about 0°C to about 30°C, or in yet further embodiments about 15°C to about 30°C.Page 15 of 4662821089 123134P1

[0057] In an embodiment, the aqueous latex emulsions prepared by the polymerization methods described herein is a hydrophobic polymer with a number average molecular weight of at least about 500,000, or at least about 200,000, or at least about 100,000. In other embodiments, the aqueous latex dispersions prepared by the methods herein has a hydrophobic polymer having a number average molecular weight of no more than 1,000,000, no more than 250,000, no more than 150,000, or no more than 50,000.

[0058] In an embodiment, the latex emulsion or latex dispersions as described herein may be used in a fdm-forming amount within a paint composition or stain composition, and optionally be combined with at least one other additive. The paint or stain composition may have about 10 to about 50 percent polymer solids from the polymer latex dispersions herein. The paint composition or stain composition may include an opacifying pigment as the at least one other additive.

[0059] Suitable opacifying pigments, if included in the paint or stain compositions herein, include pigment particles or inorganic particles such as titanium dioxide (TiCh), zinc oxide (ZnCh), calcium carbonate (CaCCh), talc, clay materials, aluminum oxide, silicon dioxide, magnesium oxide, zinc sulfate, combinations thereof, or other known pigment or inorganic particles suitable for paints and other coatings. In some approaches, the pigment or inorganic particle is titanium dioxide, which may comprise anatase titanium dioxide or rutile titanium dioxide, or a mixture of the two. In other approaches, the pigment or inorganic particle comprises rutile titanium dioxide, to the exclusion of anatase titanium dioxide. In some approaches, the rutile titanium dioxide is surface treated with an inorganic oxide, such as silica (SiCh). Generally, the opacifying pigments, such as titanium dioxide, have a particle size less than a micron, such as about 0.2 to about 0.3 microns in diameter and provided in powder form, or in an aqueous slurry. An example of a titanium dioxide that is suitable for use is Ti-Pure® R-706, which is commercially available from The Chemours Company. Ti-Pure® R-706 titanium dioxide is a rutile titanium dioxide that is surface treated with silica. In some approaches, the waterborne compositions herein may include about 10 to about 30 weight percent of titanium dioxide, about 15 to about 20 weight percent, or about 18 to about 25 weight percent of titanium dioxide. In other approaches, the at least one additive may also be inorganic or mineral extender matting agents such as calcium carbonate, silicates, diatomaceous earth, clay, asbestine, barytes, silica, mica, and microspheres (glass, ceramic, or polymeric, and can be fdled or hollow).Page 16 of 4662821089 123134P1

[0060] The compositions of the present disclosure may also include other optional additives as needed for typical applications. For instance, the compositions of the present disclosure may be produced using techniques known to those skilled in the art of manufacturing paint. In addition, the compositions herein may contain conventional additives such as thickeners, coalescing aids, biocides, anti-foaming agents, freeze-thaw additives, and the like. In other approaches, the at least one additive may also be inorganic or mineral extender matting agents such as calcium carbonate, silicates, diatomaceous earth, clay, asbestine, barytes, silica, mica, and microspheres (glass, ceramic, or polymeric, and can be filled or hollow). It should also be appreciated that in addition to the opacifying pigment, small amounts of other pigments or colorants may be used to provide desired coloration or to confer other optical effects.

[0061] Glossary of Terms

[0062] Additives refer to a general category of components or other raw materials that may be added to the coatings herein to promote various properties. Examples include, but are not limited to, surfactants, defoamers, biocides, mildewcides, algaecides, thickeners, anti-settling agents, pH buffers, corrosion inhibitors, coalescents, and / or anti-skinning agents.

[0063] As used herein, without the need for, without substantial levels of, in the absence of, or substantially free of, or free-of generally means (unless apparent from the context of the discussion) the coating compositions herein have less than about 1 weight percent, in other approaches, less than about 0.5 weight percent, in other approaches, less than about 0.2 weight percent, and in yet other approaches, none of the particular component or additive.

[0064] When referring to a polymer, oligomer, or copolymer, and a particular monomer or reactant is described, it is also intended that such discussion refers to the resulting monomer unit or associated repeating unit when polymerized within the polymer, oligomer, or copolymer. Likewise, when a monomer unit or repeating unit of a polymer, oligomer, or copolymer is described, the corresponding monomer or reactant is also contemplated by this disclosure. As used herein, the terms polymer or copolymer are interchangeable unless the context of discussion suggests otherwise. A polymer or copolymer typically have a weight average molecular weight above about 40,000. and an oligomer typically has a molecular weight below 500.

[0065] As used herein, (meth)acrylate monomer(s) or monomer unit(s) include both acrylate monomer(s) and monomer unit(s) and methacrylate monomer(s) and monomer unit(s) as well asPage 17 of 4662821089 123134P1functionalized (meth)acrylate monomer(s) or monomer unit(s) suitable for incorporation into the functionalized polymers or oligomers disclosed herein. Functional moieties may also bear other crosslinking groups, photo-reactive groups, anti-fouling agents, light absorbers, anti-corrosion agents, and the like as needed for a particular application or use.

[0066] Paint or coating refers to any mixture or composition including different types of raw materials, each with its own function, which generally is balanced to achieve the desired properties in the final product or film coating. The two functions of paint or coating are decoration and / or protection. A paint or coating may contain a solvent (which can include a volatile component derived from a petroleum distillate for a solvent-based paint, or a low VOC, or no-VOC, or water for a water-based paint or composition), a binder polymer, a pigment, fillers (such as an extender or a plurality of extenders of different sizes) and an additive, which may impart different functionality to the paint or final coating.

[0067] Coatings refer to compositions such as paint, stains, lacquers, etc.TEST METHODS

[0068] Unless otherwise identified herein, the following test methods were utilized in association with the Examples disclosed and apply to this patent application.

[0069] Latex Polymer Particle Size. Latex dispersions may be evaluated for particle size by dynamic light scattering using a Nanotrac Wave from Microtrac Inc. A latex sample is diluted by 5x in water and gently manually agitated before being placed in a clean sample cell. Grit level, and observable quality of formed dispersions were also evaluated. Residue present on the reaction vessel was evaluated by visual inspection. Dn, the number average particle size, is reported.

[0070] Latex Polymer Grit. Grit is a phenomena wherein a latex emulsion includes larger, crosslinked polymeric particles which are larger than the apertures in a 200 mesh stainless steel screen (74 microns). Grit level is determined using a 200 mesh stainless steel screen as follows: (1) weigh the screen to the nearest 0.001 grams; (b) weigh approximately 200 grams of latex sample; (c) dilute sample with about 200 grams of water; (c) pour the diluted latex sample through the screen; (d) slowly pour 200 grams of additional water through the screen to rinse away the free latex; (e) with a squeeze bottle rinse off excess liquid latex without washing away the grit; (f) dry the screen in a circulating oven at about 230°F for about 15 minutes; (g) remove the screen from the oven and weigh the dried screen; and (h) calculate level of grit (ppm), usingPage 18 of 4662821089 123134P1the formula grit (ppm) = (W2-W1) / S * 1,000,000 where W1 is weight of initial screen, W2 is weight of screen plus sample after drying, S is the weight of the latex sample.

[0071] Glass transition temperature. Tg is the midpoint of the temperature at which a polymer transitions from a glassy state to an amorphous state. Tg may be determined by Differential Scanning Calorimetry (DSC) according to the following method. A latex emulsion is drawn down using a 10 mil drawdown bar onto a plate glass substrate. After drying at room tmperature until clear, the sample is dried under vacuum at 70°C for 2 hours to remove all water. After cooling to room temperature, a 10 mg sample is scraped, placed in a sample pan, and weighed. The sample is analyzed using the standard DSC heat-cool -heat method. The samples are equilibrated at -60° C., then heated at 20° C. per minute to 200° C., cooled to -60° C., and then heated again at 20° C. per minute to 200° C. Glass transitions are calculated from the thermogram of the last heat cycle. The glass transition is measured at the inflection point of the transition.

[0072] Net-Volatile Matter (NVM) or Percent Solids, is the amount of solids, generally polymeric material, in a latex emulsion. Percent solids is determined by drying a weighed sample of latex emulsion which has been dilluted in MIBK on a weighing dish in an oven for 30 minutes in a 300°F oven. Thereafter the sample is cooled and again weighed. The percentage weight remaining is reported as NVM.

[0073] Volatile Organic Compound or VOC generally refers to organic compounds that have a high vapor pressure at room temperature. In many cases, VOCs are compounds with a vapor pressure of greater than about 0.1 mm of Hg. VOC as reported herein is measured according to ASTM D2369-90 and is the weight of the VOC per volume of the coating solids in grams / L. As used herein, low VOC or substantially free of VOCs means less than about 50 g / L, in other approaches, less than about 10 g / L, in yet other approaches, less than about 5 g / L, and in yet other approaches, no VOCsEXAMPLES

[0074] The following examples demonstrate the preparation of copolymers and waterborne compositions such as those described herein above, as well as non-inventive examples for comparison. The examples are intended to be representative of the polymers that can be made and are not intended to limit the scope of the present disclosure to the specific illustrative examples disclosed below. Reference to any percentages, ratios, and amounts in this disclosurePage 19 of 4662821089 123134P1and the Examples are by weight unless the context of discussion herein suggests otherwise. Any reference to a standardized test method, unless apparent from the context of its use in the specification, claims, or these Examples, refers to the version of the test method publically available at the time of this disclosure.

[0075] EXAMPLE 1:

[0076] Emulsion polymerization using cyclodextrin before initiator:

[0077] The emulsion polymerization was earned out in a round-bottom vessel with four necks equipped with a mechanical stirrer, temperature control device, condenser, monomer mixture feed line, initiator feed lines, and chaser feed lines, and a nitrogen inlet. A monomer mixture containing the monomers shown in Table 2 or Table 3 was mixed, together with 9 g ionic and 64 g of nonionic surfactant as shown in Table 3 in amounts to total 1000 g of monomer mixture. Following preparation of the monomer mixture, the vessel was charged with deionized water and heated to about 81 °C. Approximately 3% of the monomer mixture was added to the vessel with an additional 4.1 g of ionic surfactant. Thereafter, 14.14 g of Cavasol-W7-M, a methyl-beta-cyclodextrin, from Wacker Chemie AG, Munich Germany, was diluted with an approximately equal mass of water and added to the vessel. The vessel was held with low shear mixing for about 10 minutes. Next, 2.25 g ammonium persulfate initiator dissolved in water was added to the reactor and the reaction mixture was held with mixing for about 10 to about 20 minutes. Next, over three hours, the remaining monomer mixture and an additional 0.3 g ammonium persulfate initiator in 70 g water were added to the reaction, and the vessel was held at about 81 °C The vessel was cooled to about 65°C, and a cleanup containing tert-butyl hydrogen peroxide 0.65 g in 10 g water and the a reducer, Bruggolite FF6, 0.65 g in 12 g water were added over 30 minutes and the vessel was held at 65°C for 30 min. After cooling to 35°C, the precipitate was filtered in a 0.75 micron nylon mesh.

[0078] T 'able 2: Monomer composition using Lauryl Methacrylate as hydrophobic monomer 20 wt.% LMA Monomer Composition Monomer BOTM*BUTYL ACRYLATE 3028 %METHYL METHACRYLATE 4944 %LAURYL METHACRYLATE 2008 %METHACRYLIC ACID (250 PPM MEHQ) 02 %*BOTM = based on total monomer

[0079] T able 3: Monomer composition using stearyl acrylate as the hydrophobic monomerPage 20 of 4662821089 123134P120% SA Monomer Composition 8 Monomer BOTM*Methyl beta-cyclodextrin214.14 2.23 %BUTYL ACRYLATE 15 PPM MEHQ 30.32 %METHYL METHACRYLATE 49.50 %Stearyl Acrylate 19.98 %METHACRYLIC ACID (250 PPM MEHQ) 0.20 %*BOTM = based on total monomer

[0080] EXAMPLE 2:

[0081] Emulsion Polymerization using initiator before cyclodextrin:

[0082] The emulsion polymerization was carried out in the same reaction vessel arrangement as in Example 1. The vessel was charged with deionized water and heated to about 81°C. A monomer mixture containing the monomers shown in Table 2 or Table 3 was mixed, together with 9 g ionic and 6.4 g of nonionic surfactant as shown in Table 3 in amounts to total 1000 g of monomer mixture. Approximately 3% of the monomer mixture with an additional 4 g of ionic surfactant was added to the vessel while maintaining reaction temperature Next, 2.25 g ammonium persulfate initiator dissolved in water was added to the reactor and the reaction mixture was held with mixing for about 10 to about 20 minutes, after which 14.14 g of Cavasol-W7-M, a methyl-beta-cyclodextrin, from Wacker Chemie AG, Munich Germany, was diluted with an approximately equal mass of water and added to the vessel. The vessel was held with low shear mixing for about 10 minutes. Thereafter, over about 3 hours, the remaining monomer mixture and 0 3 g ammonium persulfate in 70 g water were together added to the reaction vessel and the vessel held at about 81°C. A The vessel was cooled to about 65°C, and a cleanup containing tert-butyl hydrogen peroxide 0.65 g in 10 g water and the a reducer, Bruggolite FF6, 0.65 g in 12 g w'ater were added over 30 minutes and the vessel was held at 65°C for 30 min. After cooling to 35°C, the precipitate was filtered in a 0.75 micron nylon mesh.

[0083] EXAMPLE 3

[0084] Latex dispersions prepared by either the methods of Example 1 or Example 2 were evaluated for particle size by dynamic light scattering using a Nanotrac Wave from Microtrac Inc. according to the test method described herein. Results are provided in Table 4 below.

[0085] Grit level was determined according to the test method described herein, with results reported in Table 3. Any polymer deposits present on the reactor surface were evaluated visually for amount (clean, slight, significant) and quality (e.g., tacky, grit, color, hard).2Cavasol-W7-M, as described above.Page 21 of 4662821089 123134P1

[0086] Table 4: Latex Dispersion ResultsLatex Filter Reactor Sample Monomer Ionic Non-ionicComposition Surfactant Surfactant Particle Order ofCD addition Grit Surface Size, nm (PPm) Deposits A Compare LMA (Table 1) Poly step B-23 Rhodasurf BC-630 369 Before min Clean B Compare LMA (Table 1) Polystep B-23 Rhodasurf BC-630 144.5 After min Gritty' C Compare LMA (Table 1) Polystep B-23 Rhodasurf BC-630 118 After min Tacky, built D Compare SA (Table 2) Poly step B-23 Rhodasurf BC-630 131 After 5 Slight E Inventive LMA (Table 1) Soprophor 4D384 Soprophor BSU 97 Before min Slight F Inventive SA (Table 2) Soprophor 4D384 Soprophor BSU 103 After min SlightG Inventive LMA (Table 1) Soprophor 4D384 Soprophor BSU 118 After min Slight

[0087] In Table 4 above, the ionic surfactant Polystep B-23, from Stepan Company, Northfield, Illinois, is an ethoxylated lauryl ether sulfate containing 12 moles of ethylene oxide.Poly step B-23 had an approximate cross-sectional area of the hydrophobic end of about 1.4 square angstroms. Rhodasurf BC-630 is an ethoxylated tridecyl alcohol from Synesqo, Belgium. Soprophor 4D384, from Synesqo, Belgium, is an ionic, tristyryl phenol poly(oxyethylene) sulfate. Soprophor BSU is a non-ionic tri styrylphenol surfactant from Synesqo, Belgium.

[0088] All latex dispersions of Table 3 were produced at a solids content of 42 wt.%, +- 2 wt.%. Differential scanning calorimetry showed a Tg of SA samples to be 13°C and of LMA samples to be 13°C.

[0089] As shown in Table 4 above, comparative Samples A-D using either monomer composition of Table 2 or Table 3 combined with the tridecyl alkyl poly(oxyethylene) ionic surfactant having an approximate cross-sectional area of the hydrophobic end of about 1.4 square angstroms resulted in formed latex dispersions having either high particle sizes, observable grit, or deposits on the reactor surfaces. On the other hand, the inventive latex dispersions E, F, and G made with the same monomer compositions of Table 2 or Table 3, but using the tristyryl phenol poly(oxyethylene) surfactant, resulted in latex dispersions having a low particle size, minimal grit, good dispersion quality, and less reactor surface deposits. All the latex dispersions of these Examples were made without using any high shear mixing such as mini-emulsification or sonication.

[0090] EXAMPLE 4:

[0091] The cross sectional area of the hydrophobic end of various surfactants was estimated by a computer-assisted analysis of the molecular size of the hydrophobic end of a surfactant as viewed from the axis on which it is the narrowest. The geometric cross-sectional area of the hydrophobic end was calculated using Chem3D software from Revvity Signals, v. 21.0.0.28. InPage 22 of 4662821089 123134P1the software, distances are measured using a measuring tool after running an MM2 force field optimization to minimize the energy of the molecular conformation of the target molecule. The distance reported is the diameter of a circle defining the cross-sectional area being analyzed, using the software to account for bond angles and bond lengths between each molecular atom.

[0092] The cross-sectional area of the hydrophobic end of five molecules were analyzed by the foregoing method. Some molecules are described using the structure of Formula I.

[0093] Table 5: Computer- Assisted Analysis of Surfactant Hydrophobic End Size Cross-sectional Cross-sectionalradius area (square Name / description of hydrophobic end (angstroms) angstroms)Tristyryl phenol 5.1 82.2Distyryl phenol 4.9 74.5Monostyryl phenol 3.6 40.9Formula 1, R2=H, R3 =H, R4=aryl 11.3 99.7 Formula 1, R2=H, R3=H, R4=C6 alkyl 19.7 305Linear tridecane 1.55 7.6

[0094] The results show that various embodiments of hydrophobic surfactants of the present disclosure would be sterically hindered from complexing with a cyclodextrin, which have been reported to have a cross-sectional radius of less than 4.25 angstroms. Thus, the Example shows that such surfactants having a sufficiently large hydrophobic end could be used in place of the tristyryl phenol surfactants of Examples 1 and 2 and are believed to be able to produce latex polymers having a particle size of less than 200 nm.

[0095] Unless otherwise specified, all measurements herein are made at 23 ± 1°C and 50% relative humidity. The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, such as dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. All ranges noted are intended to mean any endpoint within that range. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0096] Illustrative embodiments have been described, hereinabove. It will be apparent to those skilled in the art that the above compositions and methods may incorporate changes and modifications without departing from the general scope of this disclosure. It is intended to include all such modifications and alterations within the scope of the present disclosure.Furthermore, to the extent that the term "includes" is used in either the detailed description orPage 23 of 4662821089 123134P1the claims, such term is intended to be inclusive in a manner similar to the term "comprising" as "comprising" is interpreted when employed as a transitional word in a claim.

[0097] It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “an antioxidant” includes two or more different antioxidants. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items

[0098] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0099] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.[000100] It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, for example, a range from 1 to 4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4 as well as any range of such values.[000101] It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with eachPage 24 of 4662821089 123134P1specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein. Thus, a range from 1 to 4 also means a range from 1 to 3, 1 to 2, 2 to 4, 2 to 3, and so forth.[000102] Furthermore, specific amounts or numerical values of a component, compound, substituent or parameter disclosed in the description or an example is to be interpreted as a disclosure of either a lower or an upper limit of a range and thus can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent or parameter disclosed elsewhere in the application to form a range for that component, compound, substituent or parameter.[000103] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.LIST OF EXEMPLARY EMBODIMENTS[000104] The following is an exemplary list of preferred embodiments to the present disclosure. While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.[000105] Embodiment 1: A method of producing a hydrophobic acrylic polymer by latex dispersion polymerization, the method comprising mixing a reactant mixture including: a (meth)acrylate monomer including a linear or branched saturated aliphatic group having at least 8 carbons; a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin or a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof; a surfactant having a structure hindered from complexing with the macromolecular organic compound; and an initiator.[000106] Embodiment 2: The method of Embodiment 1, wherein the surfactant has a hydrophobic group including more than one benzene ring.Page 25 of 4662821089 123134P1[000107] Embodiment 3: The method of any one of the preceding Embodiments, wherein the surfactant is sterically hindered from complexing with the macromolecular organic compound.[000108] Embodiment 4: The method of any one of the preceding Embodiments, wherein the surfactant lacks a linear hydrocarbon hydrophobic group.[000109] Embodiment 5: The method of any one of the preceding Embodiments, wherein the reactant mixture is free of alkyd monomers.[000110] Embodiment 6: The method of any one of the preceding Embodiments, wherein the hydrophobic acrylic polymer has a peak particle size of less than about 200 nm, and wherein the peak particle size is determined by dynamic light-scattering.[000111] Embodiment 7: The method of any one of the preceding Embodiments, wherein the surfactant is an ethoxylated tristyryl phenol.[000112] Embodiment 8: The method of any one of the preceding Embodiments, wherein the saturated aliphatic group of the (meth)acrylate monomer has a linear chain of least 8 carbons, of least 10 carbons, of least 12 carbons, of least 16 carbons, or of least 20 carbons.[000113] Embodiment 9: The method of Embodiment 8, wherein the saturated aliphatic group of the (meth)acrylate monomer has no more than 30 carbons, no more than 28 carbons, no more than 24 carbons, no more than 22 carbons, or no more than 20 carbons.[000114] Embodiment 10: The method of any one of the preceding Embodiments, wherein the reactant mixture is essentially free of, substantially free of, or free of ethoxylated surfactants lacking a benzene ring.[000115] Embodiment 11: The method of any one of the preceding Embodiments, wherein the linear or branched saturated aliphatic group of the (meth)acrylate monomer has at least 10 carbons, at least 12 carbons, or at least 14 carbons.[000116] Embodiment 12: The method of Embodiment 11, wherein the (meth)acrylate monomer is stearyl acrylate.[000117] Embodiment 13: The method of Embodiment 11, wherein the (meth)acrylate monomer is stearyl methacrylate.[000118] Embodiment 14: The method of Embodiment 11, wherein the (meth)acrylate monomer is lauryl methacrylate.Page 26 of 4662821089 123134P1[000119] Embodiment 15: The method of Embodiment 11, wherein the (meth)acrylate monomer is isooctyl acrylate.[000120] Embodiment 16: The method of Embodiment 11, wherein the (meth)acrylate monomer is isobomyl acrylate.[000121] Embodiment 17: The method of any one of the preceding Embodiments, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.01 wt.%.[000122] Embodiment 18: The method of any one of the preceding Embodiments, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.005 wt.%.[000123] Embodiment 19: The method of any one of Embodiment 1 to 18, wherein the linear or branched saturated aliphatic group has at least 8 carbons, at least 10 carbons, or at least 12 carbons.[000124] Embodiment 20: The method of Embodiment 19, wherein the linear or branched saturated aliphatic group has at most 24 carbons, at most 20 carbons, at most 18 carbons, or at most 16 carbons.[000125] Embodiment 21: The method of any one of the preceding Embodiments, wherein the macromolecular organic compound is a cyclodextrin selected from the group consisting of an alpha-cyclodextrin, a beta-cyclodextrin, and a gamma-cyclodextrin, and preferably a betacyclodextrin.[000126] Embodiment 22: The method of any one of the preceding Embodiments, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at least 5: 1 or at least 1:1.[000127] Embodiment 23: The method of any one of the preceding Embodiments, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at most 1:5000, 1:1000, or 1:500.[000128] Embodiment 24: The method of any one of the preceding Embodiments, wherein the reactant mixture further includes one or more short-chain (meth)acrylate monomers having a linear or branched aliphatic group with less than 8 carbons.[000129] Embodiment 25: The method of Embodiment 24, wherein the short-chain (meth)acrylate monomers include butyl (meth)acrylate, methyl (meth)acrylate, vinyl acetate, or methyl (meth)acrylic acid.Page 27 of 4662821089 123134P1[000130] Embodiment 26: The method of any one of the preceding Embodiments, wherein the surfactant is a compound of formula (I):whereinRi is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;R3 is selected from the group consisting of H, linear or branched Ci to Ce alkyl, and C4 to C7 cycloalkyl, aryl, and heteroaryl;R4 is optionally present and selected from the group consisting of linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4 are independently selected for each Ri;Rs is H, SO4’A+, or PO4'A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.[000131] Embodiment 27: The method of Embodiment 26, wherein R2is Ci to Ce alkyl.[000132] Embodiment 28: The method of any one of Embodiments 26-27, wherein R3 is Ci to Ce alkyl.[000133] Embodiment 29: The method of any one of Embodiments 26-27, wherein R3 is El.[000134] Embodiment 30: The method of any one of Embodiments 26-27, wherein R4 is aryl.[000135] Embodiment 31: The method of any one of Embodiments 26-30, wherein the compound of formula (I) is a compound of formula (II) and / or a compound of formula (III):Page 28 of 4662821089 123134P1[000136] Embodiment 32: The method of any one of Embodiment 26-28 or 31, wherein \ Heach Ri is[000137] Embodiment 33: The method of any one of Embodiments 1-32, wherein the total surfactant in the reaction mixture is at least 0.1, 0.2, or 0.5 wt.% based on total monomer (BOTM).[000138] Embodiment 34: The method of any one of Embodiments 1-33, wherein the total surfactant in the reaction mixture is at most 8, at most 4, or at least 1 wt.% based on total monomer (BOTM).[000139] Embodiment 35: The method any one of Embodiments 1-34 wherein the surfactant is nonionic.[000140] Embodiment 36: The method of any one of Embodiments 1-35 wherein the surfactant is ionic and partially or wholly neutralized.[000141] Embodiment 37: The method of any one of the preceding Embodiments, wherein the initiator is added before the surfactant.[000142] Embodiment 38: The method of any one of the preceding Embodiments, wherein the initiator is added after the surfactant.[000143] Embodiment 39: The method of any one of the preceding Embodiments, wherein the method is devoid of high-shear mixing including sonication, mini-emulsification, microfluidization, homogenization, and colloid milling.[000144] Embodiment 40: The method of any one of Embodiments 1 to 39, wherein the surfactant hindered from complexing with the macromolecular organic compound has a cross-Page 29 of 4662821089 123134P1sectional area of the hydrophobic end of at least about 50 square angstroms, at least about 60 square angstroms, or at least about 63 square angstroms.[0001451 Embodiment 41: An aqueous latex dispersion prepared by the method of any one of the preceding Embodiments.[000146] Embodiment 42: An aqueous latex dispersion comprising: a hydrophobic polymer wherein at least 10 weight percent, at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 50 weight percent, or at least 75 weight percent of monomer units in the hydrophobic polymer are derived from a (meth)acrylate monomer having a linear or branched, saturated hydrocarbon chain of at least 8 carbons; and a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin and a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof; and a surfactant hindered from complexing with the macromolecular organic compound; wherein the latex polymer dispersion has a peak particle size of not greater than about 200 nm.[000147] Embodiment 43: The aqueous latex dispersion of Embodiment 42, wherein less than about 80 weight percent, less than about 60 weight percent, or less than about 30 weight percent of monomer units in the hydrophobic polymer are derived from the (meth)acrylate monomer having a linear or branched, saturated hydrocarbon chain of at least 8 carbons.[000148] Embodiment 44: The aqueous latex dispersion of any one of Embodiments 42 or 43, wherein the latex polymer emulsion has a peak particle size of not greater than about 175 nm, not greater than about 150 nm, not greater than about 125 nm, or not greater than about 100 nm.[000149] Embodiment 45: The aqueous latex dispersion of any one of Embodiments 42 to 44, wherein the surfactant has a hydrophobic group including more than one benzene ring.[000150] Embodiment 46: The aqueous latex dispersion of any one of Embodiments 42 to 45, wherein the macromolecular organic compound is a cyclodextrin.[000151] Embodiment 47: The aqueous latex dispersion of any one of Embodiments 42 to 46, wherein the surfactant lacks a linear hydrocarbon hydrophobic group.[000152] Embodiment 48: The aqueous latex dispersion of any one of Embodiments 42 to 47, wherein the reactant mixture is free of alkyd monomers.[000153] Embodiment 49: The aqueous latex dispersion of any one of Embodiments 42 to 48, wherein the surfactant is an ethoxylated tristyryl phenol.Page 30 of 4662821089 123134P1[000154] Embodiment 50: The aqueous latex dispersion of any one of Embodiments 42 to 49, wherein the reactant mixture is essentially free of, substantially free of, or free of ethoxylated surfactants lacking a benzene ring.[000155] Embodiment 51: The aqueous latex dispersion of any one of Embodiments 42 to 50, wherein the linear or branched saturated hydrocarbon group of the (meth)acrylate monomer has at least 10, at least 12, or at least 14 carbons.[000156] Embodiment 52: The aqueous latex dispersion of any one of Embodiments 42 to 51, wherein the (meth)acrylate monomer is stearyl acrylate.[000157] Embodiment 53: The aqueous latex dispersion of any one of Embodiments 42 to 52, wherein the (meth)acrylate monomer is stearyl methacrylate.[000158] Embodiment 54: The aqueous latex dispersion of any one of Embodiments 42 to 53, wherein the (meth)acrylate monomer is lauryl methacrylate.[000159] Embodiment 55: The aqueous latex dispersion of any one of Embodiments 42 to 54, wherein the (meth)acrylate monomer is isooctyl acrylate.[000160] Embodiment 56: The aqueous latex dispersion of any one of Embodiments 42 to 55, wherein the (meth)acrylate monomer is isobornyl acrylate.[000161] Embodiment 57: The aqueous latex dispersion of any one of Embodiments 42 to 56, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.01 wt.%.[000162] Embodiment 58: The aqueous latex dispersion of any one of Embodiments 42 to 57, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.005 wt.%.[000163] Embodiment 59: The aqueous latex dispersion of any one of Embodiments 42 to 59, wherein the aliphatic group is a linear saturated aliphatic group having at least 8 carbons or a linear or branched saturated aliphatic group having at least 8 carbons, at least 10 carbons, at least 14 carbons, or at least 16 carbons.[000164] Embodiment 60: The aqueous latex dispersion of any one of Embodiments 42 to 59, wherein the linear or branched saturated aliphatic groups has no more than 30 carbons, no more than 28 carbons, no more than 26 carbons, no more than 24 carbons, no more than 22 carbons, or no more than 20 carbons.[000165] Embodiment 61: The aqueous latex dispersion of any one of Embodiments 42 to 60, wherein the macromolecular organic compound is a cyclodextrin selected from the groupPage 31 of 4662821089 123134P1consisting of an alpha-cyclodextrin, a beta-cyclodextrin, and a gamma-cyclodextrin, preferably a beta-cyclodextrin.[000166] Embodiment 62: The aqueous latex dispersion of any one of Embodiments 42 to 61, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at least 5:1 or at least 1:1.[000167] Embodiment 63: The aqueous latex dispersion of any one of Embodiments 42 to 62, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at most 1:5000, 1:1000, or 1:500.[000168] Embodiment 64: The aqueous latex dispersion of any one of Embodiments 42 to 63, wherein the hydrophobic polymer further includes one or more short-chain (meth)acrylate monomers lacking a linear or branched aliphatic group having less than 8 carbons.[000169] Embodiment 65: The aqueous latex dispersion of Embodiment 64, wherein the short-chain (meth)acrylate monomers include butyl (meth)acrylate, methyl (meth)acrylate, vinyl acetate, or methyl (meth)acrylic acid.[000170] Embodiment 66: The aqueous latex dispersion of any one of Embodiments 42-65, wherein the surfactant is a compound of formula (I):whereinRi is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;R3is selected from the group consisting of H, linear or branched Ci to Ce alkyl, and C4 to C7 cycloalkyl, aryl, and heteroaryl;R4 is optionally present and selected from the group consisting of linear or branched Ci to Ce alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4 are independently selected for each Ri;Page 32 of 4662821089 123134P1Rs is H, S04’A+, or PO4'A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.[000171] Embodiment 67: The aqueous latex dispersion of Embodiment 66, wherein R2 is Ci to Ce alkyl.[000172] Embodiment 68: The aqueous latex dispersion of any one of Embodiments 67 to 68, wherein R3 is Ci to Ce alkyl.[000173] Embodiment 69: The aqueous latex dispersion of any one of Embodiments 66 to 68, wherein R3 is H.[000174] Embodiment 70: The aqueous latex dispersion of any one of Embodiments 66 to 69, wherein R4 is aryl.[000175] Embodiment 71: The aqueous latex dispersion of Embodiment 66, wherein the compound of formula (I) is a compound of formula (II) and / or a compound of formula (III):(HI)[000176] Embodiment 72: The aqueous latex dispersion of Embodiment 72, wherein eachRi is[000177] Embodiment 73: The aqueous latex dispersion of any of Embodiments 42-72, wherein the total surfactant in the latex dispersion is at least 0.1, 0.2, or 0.5 wt.% based on total monomer (BOTM).Page 33 of 4662821089 123134P1[000178] Embodiment 74: The aqueous latex dispersion of any of Embodiments 42-73, wherein the total surfactant in the latex dispersion is at most 8, at most 4, or at least 1 wt.% based on total monomer (BOTM).[000179] Embodiment 75: The aqueous latex dispersion of any one of Embodiments 42 to 72, wherein the surfactant hindered from complexing with the macromolecular organic compound has a cross-sectional area of the hydrophobic end of at least about 40 square angstroms, at least about 60 square angstroms, or at least about 65 square angstroms.[000180] Embodiment 76: The aqueous latex dispersion of any one of Embodiments 42 to 75, wherein the hydrophobic polymer has a glass transition temperature (Tg) of between less than -30°C, or between -30°C and 0°C, or between 0°C and 30°C, or between 15°C and 30°C.[000181] Embodiment 77: The aqueous latex dispersion of any one of Embodiments 42 to 76, wherein the hydrophobic polymer has an Mn of at least 500,000, or at least 200,000, or at least 100,000.[000182] Embodiment 78: The aqueous latex dispersion of any one of Embodiments 42 to 77, wherein the latex dispersion has at least 20, at least 40, at least 50, or at least 60 percent NVM.[000183] Embodiment 79: The aqueous latex dispersion of any one of Embodiments 42 to 78, wherein the latex dispersion is composed of polymer particles having a single-phase.[000184] Embodiment 80: The aqueous latex dispersion of any one of Embodiments 42 to 79, wherein the latex dispersion is composed of polymer particles having more than one phase.[000185] Embodiment 81: The aqueous latex dispersion of Embodiment 80, wherein the particle particles have a core-shell structure.[000186] Embodiment 82: A paint or stain composition comprising: a film-forming amount of an aqueous latex dispersion of any one of Embodiment 42 to 81, and at least one additive.[000187] Embodiment 83: A paint or coating composition of Embodiment 82, wherein the composition includes at least one opacifying pigment.Page 34 of 4662821089 1

Claims

23134P1CLAIMSWhat is Claimed is:

1. A method of producing a hydrophobic acrylic polymer by latex dispersion polymerization, the method comprising mixing a reactant mixture including:a (meth)acrylate monomer including a linear or branched saturated aliphatic group having at least 8 carbons;a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin or a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof;a surfactant having a structure hindered from complexing with the macromolecular organic compound; andan initiator.

2. The method of claim 1, wherein the surfactant has a hydrophobic group including more than one benzene ring.

3. The method of any one of the preceding claims, wherein the surfactant is sterically hindered from complexing with the macromolecular organic compound.

4. The method of any one of the preceding claims, wherein the surfactant lacks a linear hydrocarbon hydrophobic group.

5. The method of any one of the preceding claims, wherein the reactant mixture is free of alkyd monomers.

6. The method of any one of the preceding claims, wherein the hydrophobic acrylic polymer has a peak particle size of less than about 200 nm, and wherein the peak particle size is determined by dynamic light-scattering.Page 35 of 4662821089 123134P17. The method of any one of the preceding claims, wherein the surfactant is an ethoxylated tri styryl phenol.

8. The method of any one of the preceding claims, wherein the saturated aliphatic group of the (meth)acrylate monomer has a linear chain of least 8 carbons, of least 10 carbons, of least 12 carbons, of least 16 carbons, or of least 20 carbons.

9. The method of claim 8, wherein the saturated aliphatic group of the (meth)acrylate monomer has no more than 30 carbons, no more than 28 carbons, no more than 24 carbons, no more than 22 carbons, or no more than 20 carbons.

10. The method of any one of the preceding claims, wherein the reactant mixture is essentially free of, substantially free of, or free of ethoxylated surfactants lacking a benzene ring.

11. The method of any one of the preceding claims, wherein the linear or branched saturated aliphatic group of the (meth)acrylate monomer has at least 10 carbons, at least 12 carbons, or at least 14 carbons.

12. The method of claim 11, wherein the (meth)acrylate monomer is stearyl acrylate.

13. The method of claim 11, wherein the (meth)acrylate monomer is stearyl methacrylate.

14. The method of claim 11, wherein the (meth)acrylate monomer is lauryl methacrylate.

15. The method of claim 11, wherein the (meth)acrylate monomer is isooctyl acrylate.

16. The method of claim 11, wherein the (meth)acrylate monomer is isobornyl acrylate.Page 36 of 4662821089 123134P117. The method of any one of the preceding claims, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.01 wt.%.

18. The method of any one of the preceding claims, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.005 wt.%.

19. The method of any one of claims 1 to 18, wherein the linear or branched saturated aliphatic group has at least 8 carbons, at least 10 carbons, or at least 12 carbons.

20. The method of claim 19, wherein the linear or branched saturated aliphatic group has at most 24 carbons, at most 20 carbons, at most 18 carbons, or at most 16 carbons.

21. The method of any one of the preceding claims, wherein the macromolecular organic compound is a cyclodextrin selected from the group consisting of an alpha-cyclodextrin, a beta-cyclodextrin, and a gamma-cyclodextrin, and preferably a beta-cyclodextrin.

22. The method of any one of the preceding claims, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at least 5:1 or at least 1:1.

23. The method of any one of the preceding claims, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at most 1: 5000, 1: 1000, or 1:500.

24. The method of any one of the preceding claims, wherein the reactant mixture further includes one or more short-chain (meth)acrylate monomers having a linear or branched aliphatic group with less than 8 carbons.

25. The method of claim 24, wherein the short-chain (meth)acrylate monomers include butyl (meth)acrylate, methyl (meth)acrylate, vinyl acetate, or methyl (meth)acrylic acid.

26. The method of any one of the preceding claims, wherein the surfactant is a compound of formula (I):Page 37 of 4662821089 123134P1R5(I)whereinRi is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched Ci to C6 alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;R3is selected from the group consisting of H, linear or branched Ci to Ce alkyl, and C4 to C7 cycloalkyl, aryl, and heteroaryl;R4 is optionally present and selected from the group consisting of linear or branched Ci to G> alkyl, C4 to C7 cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4 are independently selected for each Ri;Rs is H, SO4’A+, or PO4'A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.

27. The method of claim 26, wherein R2is Ci to Ce alkyl.

28. The method of any one of claims 26-27, wherein R3is Ci to Ce alkyl.

29. The method of any one of claims 26-27, wherein R3is H.

30. The method of any one of claims 26-27, wherein R4 is aryl.

31. The method of any one of claims 26-30, wherein the compound of formula (I) is a compound of formula (11) and / or a compound of formula (111):Page 38 of 4662821089 123134P132. The method of any one of claims 26-28 or 31, wherein each Ri is33. The method of any one of claims 1-32, wherein the total surfactant in the reaction mixture is at least 0.1, 0.2, or 0.5 wt.% based on total monomer (BOTM).

34. The method of any one of claims 1-33, wherein the total surfactant in the reaction mixture is at most 8, at most 4, or at least 1 wt.% based on total monomer (BOTM).

35. The method any one of claims 1-34 wherein the surfactant is nonionic.

36. The method of any one of claims 1-35 wherein the surfactant is ionic and partially or wholly neutralized.

37. The method of any one of the preceding claims, wherein the initiator is added before the surfactant.

38. The method of any one of the preceding claims, wherein the initiator is added after the surfactant.

39. The method of any one of the preceding claims, wherein the method is devoid of high-shear mixing including sonication, mini-emulsification, micro-fluidization, homogenization, and colloid milling.Page 39 of 4662821089 123134P140. The method of any one of claims 1 to 39, wherein the surfactant hindered from complexing with the macromolecular organic compound has a cross-sectional area of the hydrophobic end of at least about 50 square angstroms, at least about 60 square angstroms, or at least about 63 square angstroms.

41. An aqueous latex dispersion prepared by the method of any one of the preceding claims.

42. An aqueous latex dispersion comprising:a hydrophobic polymer wherein at least 10 weight percent, at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 50 weight percent, or at least 75 weight percent of monomer units in the hydrophobic polymer are derived from a (meth)acrylate monomer having a linear or branched, saturated hydrocarbon chain of at least 8 carbons; and a macromolecular organic compound having a hydrophobic cavity and selected from the group consisting of cyclodextrin and a cyclodextrin derivative; cyclic oligosaccharides including cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene or cavitand; or combinations thereof; anda surfactant hindered from complexing with the macromolecular organic compound; wherein the latex polymer dispersion has a peak particle size of not greater than about 200 nm.

43. The aqueous latex dispersion of claim 42, wherein less than about 80 weight percent, less than about 60 weight percent, or less than about 30 weight percent of monomer units in the hydrophobic polymer are derived from the (meth)acrylate monomer having a linear or branched, saturated hydrocarbon chain of at least 8 carbons.

44. The aqueous latex dispersion of any one of claims 42 or 43, wherein the latex polymer emulsion has a peak particle size of not greater than about 175 nm, not greater than about 150 nm, not greater than about 125 nm, or not greater than about 100 nm.Page 40 of 4662821089 123134P145. The aqueous latex dispersion of any one of claims 42 to 44, wherein the surfactant has a hydrophobic group including more than one benzene ring.

46. The aqueous latex dispersion of any one of claims 42 to 45, wherein the macromolecular organic compound is a cyclodextrin.

47. The aqueous latex dispersion of any one of claims 42 to 46, wherein the surfactant lacks a linear hydrocarbon hydrophobic group.

48. The aqueous latex dispersion of any one of claims 42 to 47, wherein the reactant mixture is free of alkyd monomers.

49. The aqueous latex dispersion of any one of claims 42 to 48, wherein the surfactant is an ethoxylated tri styryl phenol.

50. The aqueous latex dispersion of any one of claims 42 to 49, wherein the reactant mixture is essentially free of, substantially free of, or free of ethoxylated surfactants lacking a benzene ring.

51. The aqueous latex dispersion of any one of claims 42 to 50, wherein the linear or branched saturated hydrocarbon group of the (meth)acrylate monomer has at least 10, at least 12, or at least 14 carbons.

52. The aqueous latex dispersion of any one of claims 42 to 51, wherein the (meth)acrylate monomer is stearyl acrylate.

53. The aqueous latex dispersion of any one of claims 42 to 52, wherein the (meth)acrylate monomer is stearyl methacrylate.

54. The aqueous latex dispersion of any one of claims 42 to 53, wherein the (meth)acrylate monomer is lauryl methacrylate.Page 41 of 4662821089 123134P155. The aqueous latex dispersion of any one of claims 42 to 54, wherein the (meth)acrylate monomer is isooctyl acrylate.

56. The aqueous latex dispersion of any one of claims 42 to 55, wherein the (meth)acrylate monomer is isobomyl acrylate.

57. The aqueous latex dispersion of any one of claims 42 to 56, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.01 wt.%.

58. The aqueous latex dispersion of any one of claims 42 to 57, wherein the solubility limit of the (meth)acrylate monomer in water is less than 0.005 wt.%.

59. The aqueous latex dispersion of any one of claims 42 to 58, wherein the aliphatic group is a linear saturated aliphatic group having at least 8 carbons or a linear or branched saturated aliphatic group having at least 8 carbons, at least 10 carbons, at least 14 carbons, or at least 16 carbons.

60. The aqueous latex dispersion of any one of claims 42 to 59, wherein the linear or branched saturated aliphatic groups has no more than 30 carbons, no more than 28 carbons, no more than 26 carbons, no more than 24 carbons, no more than 22 carbons, or no more than 20 carbons.

61. The aqueous latex dispersion of any one of claims 42 to 60, wherein the macromolecular organic compound is a cyclodextrin selected from the group consisting of an alpha-cyclodextrin, a beta-cyclodextrin, and a gamma-cyclodextrin, preferably a betacyclodextrin.

62. The aqueous latex dispersion of any one of claims 42 to 61, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at least 5:1 or at least 1:1.Page 42 of 4662821089 123134P163. The aqueous latex dispersion of any one of claims 42 to 62, wherein a molar ratio of the macromolecular compound to the (meth)acrylate monomer is at most 1: 5000, 1: 1000, or 1:500.

64. The aqueous latex dispersion of any one of claims 42 to 63, wherein the hydrophobic polymer further includes one or more short-chain (meth)acrylate monomers lacking a linear or branched aliphatic group having less than 8 carbons.

65. The aqueous latex dispersion of claim 64, wherein the short-chain (meth)acrylate monomers include butyl (meth)acrylate, methyl (meth)acrylate, vinyl acetate, or methyl (meth)acrylic acid.

66. The aqueous latex dispersion of any one of claims 42-65, wherein the surfactant is a compound of formula (I):R5whereinR1is -C-(R2)(R3)(R4) or -C=(R2)(R3),R2is selected from the group consisting of a linear or branched C1to C6alkyl, C4to C7cycloalkyl, aryl, and heteroaryl;R3is selected from the group consisting of H, linear or branched C1to C6alkyl, and C4to C7cycloalkyl, aryl, and heteroaryl;R4is optionally present and selected from the group consisting of linear or branched C1to C6alkyl, C4to C7cycloalkyl, aryl, and heteroaryl;each R2, R3, and R4are independently selected for each R1;R5 is H, SO4’A+, or PO4A+, and if present, A+is selected from the group consisting of Li+, Na+, K+, NH4+, and a trialkylammonium cation;Page 43 of 4662821089 123134P1n is an integer from 6 to 25, or from 6 to 20, or from 12 to 20, or from 12 to 16; and m is an integer of 2 or 3.

67. The aqueous latex dispersion of claim 66, wherein R2is C1to C6alkyl.

68. The aqueous latex dispersion of any one of claims 66 or 67, wherein R3is C1to C6alkyl.

69. The aqueous latex dispersion of any one of claims 66 to 68, wherein R3 is H.

70. The aqueous latex dispersion of any one of claims 66 to 69, wherein R4 is aryl.

71. The aqueous latex dispersion of claim 66, wherein the compound of formula (I) is a compound of formula (II) and / or a compound of formula (III):

72. The aqueous latex dispersion of claim 71, wherein each Riis73. The aqueous latex dispersion of any of claims 42-72, wherein the total surfactant in the latex dispersion is at least 0.1, 0.2, or 0.5 wt.% based on total monomer (BOTM).

74. The aqueous latex dispersion of any of claims 42-73, wherein the total surfactant in the latex dispersion is at most 8, at most 4, or at least 1 wt.% based on total monomer (BOTM).Page 44 of 4662821089 123134P175. The aqueous latex dispersion of any one of claims 42 to 74, wherein the surfactant hindered from complexing with the macromolecular organic compound has a cross-sectional area of the hydrophobic end of at least about 40 square angstroms, at least about 60 square angstroms, or at least about 65 square angstroms.

76. The aqueous latex dispersion of any one of claims 42 to 75, wherein the hydrophobic polymer has a glass transition temperature (Tg) of between less than -30°C, or between -30°C and 0°C, or between 0°C and 30°C, or between 15°C and 30°C.

77. The aqueous latex dispersion of any one of claims 42 to 76, wherein the hydrophobic polymer has an Mn of at least 500,000, or at least 200,000, or at least 100,000.

78. The aqueous latex dispersion of any one of claims 42 to 77, wherein the latex dispersion has at least 20, at least 40, at least 50, or at least 60 percent NVM.

79. The aqueous latex dispersion of any one of claims 42 to 78, wherein the latex dispersion is composed of polymer particles having a single-phase.

80. The aqueous latex dispersion of any one of claims 42 to 79, wherein the latex dispersion is composed of polymer particles having more than one phase.

81. The aqueous latex dispersion of claims 80, wherein the particle particles have a core-shell structure.

82. A paint or stain composition comprising: a film-forming amount of an aqueous latex dispersion of any one of claims 42 to 81, and at least one additive.

83. A paint or coating composition of claim 82, wherein the composition includes at least one opacifying pigment.Page 45 of 4662821089 1

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