WO2026022331A2 - Composite particle - Google Patents

Composite particle

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Publication number
WO2026022331A2
WO2026022331A2 PCT/EP2025/071407 EP2025071407W WO2026022331A2 WO 2026022331 A2 WO2026022331 A2 WO 2026022331A2 EP 2025071407 W EP2025071407 W EP 2025071407W WO 2026022331 A2 WO2026022331 A2 WO 2026022331A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
cross
monomers
monomer
monomer mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/071407
Other languages
French (fr)
Other versions
WO2026022331A3 (en
Inventor
Klin Aloysius RODRIGUES
Jobie Lebron JONES
Matthew Michael VANDERHOOF
Zeena Cherian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nouryon Chemicals International BV
Original Assignee
Nouryon Chemicals International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nouryon Chemicals International BV filed Critical Nouryon Chemicals International BV
Publication of WO2026022331A2 publication Critical patent/WO2026022331A2/en
Publication of WO2026022331A3 publication Critical patent/WO2026022331A3/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • PFAS Per- and polyfluoroalkyl substances
  • DPUR dirt pickup resistance
  • block resistance prevents painted surfaces from sticking to one another, especially under pressure or elevated temperatures.
  • This disclosure provides a composite particle that includes the reaction product of: A. a silica particle; and B.
  • a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: 1 PCT PATENT APPLICATION 364.1746PC3 (1) a comb polymer having the formula (I): a + b + c + d + e 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X 1 and X 2 independently is O or NH; (iii) R 1 is a C 1 -C 32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3
  • FIG. 1 is a drawing of a silica particle without any polymer bonded thereto;
  • FIG.2 is a drawing of an embodiment of the composite particle that shows both attachment of the comb polymer and the acrylate polymer, even though only one or neither polymer is required to be present;
  • FIG. 1 is a drawing of a silica particle without any polymer bonded thereto;
  • FIG.2 is a drawing of an embodiment of the composite particle that shows both attachment of the comb polymer and the acrylate polymer, even though only one or neither polymer is required to be present;
  • FIG. 1 is a drawing of a silica particle without any polymer bonded thereto;
  • FIG.2 is a drawing of an embodiment of the composite particle that shows both attachment of the comb polymer and the acrylate polymer, even though only one or neither polymer is required to be present;
  • FIG. 1 is a drawing of a silica particle without any polymer bonded thereto;
  • FIG.2 is a drawing of an embodiment
  • FIG. 3 is a cross-sectional view of one embodiment of the core shell polymer wherein each of an at least one core polymer, a first shell polymer, and a second shell polymer has a cross- link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is greater than the cross-link density of the first shell polymer and greater than the cross-link density of the at least one core polymer; [0010] FIG.
  • FIG. 4 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the first shell polymer and greater than the cross- link density of the at least one core polymer; [0011] FIG.
  • FIG. 5 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is greater than the cross-link density of the at least one core polymer and greater than the cross-link density of the first shell polymer; [0012] FIG.
  • FIG. 6 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second 5 PCT PATENT APPLICATION 364.1746PC3 shell polymer is less than the cross-link density of the at least one core polymer and less than the cross-link density of the first shell polymer; [0013] FIG.
  • FIG. 7 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the at least one core polymer and greater than the cross-link density of the first shell polymer; [0014] FIG.
  • FIG. 8 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the at least one core polymer and less than the cross-link density of the first shell polymer; and [0015] FIG. 9 is a drawing of a composite particle of the Examples 2A-2B. DETAILED DESCRIPTION [0016] The following detailed description is merely exemplary in nature and is not intended to limit the current composition.
  • Embodiments of the present disclosure are generally directed to polymer composites with silica, compositions including the same, and methods for forming the same.
  • conventional techniques related to making polymers and such compositions may not be described in detail herein.
  • the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein.
  • steps in the manufacture of polymers and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.
  • R1, R2, etc. do not indicate that more than 1 group (e.g. R group) is present. They are used merely to differentiate between groups. However, the subscripts for chemical elements such as carbon (e.g. C1-C22) are indicative of the total number of atoms of that chemical element.
  • percent actives is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives.
  • any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person.
  • the terminology “free of” describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of” describes embodiments that have zero weight percent of the compound or element at issue.
  • the terminology “consists essentially of” may describe various non-limiting embodiments that are free of one or more optional compounds described herein and/or free of one or more polymers, surfactants, additives, solvents, etc.
  • a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: (1) a comb polymer having the formula (I): a + b + c + d + e 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR 6 - CHR 7 - groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R 2 is -S-R 11 -Si(OR’) 3 ; (v) R3 is H a C1-
  • composite particle typically describes a particle that includes, or is made up of, smaller particles or parts or pieces.
  • the composite particle includes the silica particle (e.g. a first part of the composite particle), e.g. as shown in FIG.1, and a polymer (e.g. a second part of the composite particle) attached to the surface of the silica particle, e.g. as shown in FIG. 2.
  • the composite particle includes the first and second “parts” attached or bonded together.
  • the composite particle may alternatively be described as a single particle that is formed from two or more substituents, e.g. the silica particle and the polymer.
  • the composite particle is not particularly limited in size or shape.
  • the size of the composite particle may be approximately the size of the silica particle itself (e.g. plus a percentage that is greater than about zero and up to about 1%) because the polymer attached thereto does not add appreciable physical size to the overwhelmingly larger physical size of silica particle itself. Accordingly, any particle size or shape described herein may describe the silica particles themselves or the composite particle.
  • Silica Particle [0028] Crystalline silica is a form of silicon dioxide (SiO2) that has a well-ordered, repeating atomic structure, distinguishing it from amorphous silica, which lacks such organization.
  • crystalline and/or amorphous silica may be used.
  • Crystalline silica exists in several polymorphs, with the most common being quartz, which is the most abundant and stable form under normal environmental conditions. Quartz is naturally present in sand, soil, and rock, and is widely used in construction and industrial materials.
  • Cristobalite is another form of crystalline silica that develops at high temperatures, often during industrial processes like ceramic firing or the calcination of diatomaceous earth. It is considered more chemically reactive and potentially more hazardous than quartz.
  • Tridymite also formed at elevated temperatures, is less common and found mainly in high-temperature industrial environments or volcanic rocks.
  • the silica particle has a surface, i.e., an outer surface.
  • the smoothness or roughness of the surface is not particularly limited and can be any known in the art.
  • the porosity of the surface is not particularly limited and also may be any known in the art.
  • the surface charge (e.g. zeta potential) of the surface is also not particularly limited and also may be any known in the art.
  • the silica utilized herein may be in any form known in the art.
  • the preferred type of silica is colloidal silica.
  • Colloidal silicas are suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase.
  • the silica is utilized as a sol including colloidal silica, e.g. also known as a silica sol.
  • the terminology “sol” typically describes a stable dispersion of colloidal silica (SiO2) particles in a liquid, such as water.
  • the silica sol may also be described as a colloidal silica dispersion.
  • the sol includes colloidal silica, e.g.
  • silica particles In various embodiments, the terms “silica sol” and “colloidal silica” have the same meaning. In other embodiments, the term “colloidal silica” refers to a dispersion comprising about 1 to about 50 wt% silica particles dispersed in an aqueous medium.
  • the aqueous medium may comprise organic solvent, but where it does so it typically comprises less than 10 wt% organic solvent. If an organic solvent is present, the aqueous medium more typically includes no more than about 5 wt% organic solvent.
  • Typical organic solvents when present, are water- miscible, for example being chosen from one or more of C1-4 alkyl alcohols, C1-4 aldehydes, C1-4 ketones, C1-4 carboxylic acids their C1-4 alkyl esters, and combinations thereof.
  • the sol may include one or more individual types of colloidal silica. In such embodiments, at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both.
  • the composition as a whole may include one or more independent sols.
  • at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both.
  • the sol itself is not particularly limited and can have a SiO2 content of from about 5 to 12 PCT PATENT APPLICATION 364.1746PC3 about 60 wt% depending on particle size. In various embodiments, this content is from about 10 to about 55, about 15 to about 50, about 20 to about 45, about 25 to about 40, or about 30 to about 35, weight % based on a total weight of the sol.
  • the sol may or may not be diluted for use herein.
  • Aqueous silica sols can be basic, having a pH of from about 2.0 to about 11 or 12, for example from about, 4.0 to about 11.0 or 6.0 to about 10.0.
  • Other optional components of such sols include the presence of alkali metals, typically one or more of lithium, sodium and potassium. Typically sodium is the sole or predominant alkali metal.
  • the alkali metals can be derived from soluble silicate solutions (e.g. water glass) that can be used to make the colloidal silica using conventional processes.
  • aqueous alkali metal silicates or water glass examples include lithium, sodium and potassium silicates, typically sodium silicate.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the silica particles are typically amorphous nanoparticles, and most typically have a particle diameter of from about 2 to about 170 nm.
  • the colloidal silica particles typically have an average particle diameter of from about 2 to about 100 nm or from about 3 to about 75 nm.
  • the particle diameter is from about 4 to about 50 nm, from about 5 to about 30 nm or from about 7 to about 25 nm. In other embodiments, the particle diameter is from about 5 to about 25, about 10 to about 20, about 10 to about 15, etc. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0037]
  • the particle diameter can be calculated from the titrated specific surface area using a method described in "The Chemistry of Silica", by Iler, K. Ralph, page 465, John Wiley & Sons (1979).
  • ES-DMA electro-spray 13 PCT PATENT APPLICATION 364.1746PC3 differential mobility analysis
  • CLS centrifugal liquid analysis
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • the colloidal silica has an S value of from about 20 to about 95 %, for example from about 30% to about 90% or from about 50 to about 85%
  • the S-value is measured and calculated as described by Iler & Dalton (Iler & Dalton; J. Phys. Chem. 60(1956), 955-957).
  • the S-value indicates a degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation.
  • all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein.
  • the colloidal silica is made from particle growth from a soluble silicate or a polysilicic acid solution, and is not prepared by creating a dispersion from a solid form of silica nanoparticle.
  • the colloidal silica is not derived from solid forms of silica such as amorphous forms of fumed silica, silica fume and precipitated silica.
  • the colloidal silica is not derived from crystalline forms of silica, such as micro-quartz or nano-quartz, which suffer the additional disadvantage of potential health risks.
  • Soluble silicate-derived colloidal silicas tend to have less aggregation of the silica particles compared to dispersions made from solid forms of silica. This is because, in general, solid forms of silica nanoparticles tend to be in the form of agglomerates of the primary nanoparticles, and it is not usually possible to disperse such silicas to create a colloidal silica comprising predominantly the discrete primary particles because larger agglomerates tend to remain. The silica particles in such colloidal silicas therefore tend to settle (precipitate) relatively rapidly. In contrast, colloidal silicas made from particle growth from a soluble silicate or a polysilicic acid solution do not include such large silica agglomerates.
  • the colloidal silica is made by converting soluble alkali metal silicate to polysilicic acid (with a pH typically of from about 1 to about 3) by ion exchange or treatment with acid, and raising the pH to about 7 or more, typically about 8 to about 1112, for example about 9 to about 11, using a basic alkali metal salt such as alkali metal hydroxide or alkali metal silicate.
  • the content of alkali metals in the starting silica sol can be of from about 0.1 to about 5.0 wt%, expressed as alkali metal oxide.
  • this content is from about 14 PCT PATENT APPLICATION 364.1746PC3 0.2 to about 3.0 wt%.
  • the silica concentration in the colloidal silica is of from about 1 to about 40 wt%, for example from about 2 to about 35 wt% or from about 3 to about 30 wt%.
  • silica concentrations are typically expressed as SiO2.
  • a typical minimum concentration is about 5 wt%, and most typical ranges are therefore about 5 to about 50 wt%, and more typically about 5 to about 40 wt%, for example about 5 to about 35 wt% or about 5 to about 30 wt%.
  • the colloidal silica particles typically have a surface area of from about 30 to about 1000 m2g-1, for example of from about 40 to about 700 m2g-1, such as of from about 60 to about 550 m2g-1 and more typically from 90 to about 400 m2g-1 and most typically from about 120 to about 250 m2g-1.
  • the specific surface area of colloidal silica particles in a silica sol can be calculated from NaOH titration following the method of Sears (Sears; Anal. Chem., 1956, 28(12), 1981-1983).
  • the density of the silica sol is at least in part dependent on the silica content, and is typically of from about 1.01 to about 1.45 g cm-3, and typically of from about 1.01 to about 1.30 g cm-3.
  • a silica sol of density 1.2 g cm-3 has typically a silica content of 30 wt-% SiO2 while a silica sol of density 1.4 g cm-3 has typically a silica content of 50-wt% SiO2.
  • Density can be determined using ASTM D4052-18a.
  • the colloidal silica particles can be dispersed in the presence of stabilizing cations, which can be chosen from alkali metals (e.g. K+, Na+, Li+), ammonium 15 PCT PATENT APPLICATION 364.1746PC3 (NH4+), organic cations, quaternary amino, tertiary amino, secondary amino, and primary amino, or mixtures thereof. Typically, they are selected from alkali metals and ammonium.
  • alkali metals e.g. K+, Na+, Li+
  • NH4+ ammonium 15 PCT PATENT APPLICATION 364.1746PC3
  • organic cations quaternary amino, tertiary amino, secondary amino, and primary amino, or mixtures thereof.
  • sols that can be used as starting aqueous silica sols include silica sols marketed under the name LevasilTM or BindzilTM from Nouryon.
  • the polymer is attached to the surface of the silica particle via an O-Si bond.
  • the O- Si bond may be formed by any reaction known in the art. Typically, the reaction is a condensation reaction such that an Si-O-Si bond is formed, e.g. as shown in the Figures.
  • the polymer can be chosen from the comb polymer, the acrylate polymer, the core shell polymer, and combinations thereof.
  • the reaction may occur at any point to form the composite particles.
  • reactive groups of any of the polymers herein may react with the silica thereby forming the composite particles during any step of a method to form a paint, a coating composition, cosmetics, sunscreens, etc. or any composition described herein.
  • the composite particles may be formed during the formation of the paint, coating composition, cosmetics, sunscreens, etc. or may be formed entirely independently and later added to the paint, coating composition, cosmetics, sunscreens, etc. or any composition described herein.
  • a + b + c + d + e 100 mol%.
  • the particular amount of any one of a, b, c, d, and e is not particularly limited.
  • any one of a, b, c, d, and/or e can each independently be about 1 to about 99 mol percent based on a total number of moles of a, b, c, d, and e in the comb polymer.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • a is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer.
  • a is from about 1 to about 25, about 2 to about 24, about 3 to about 23, about 4 to about 24, about 5 to about 25, about 6 to about 24, about 7 to about 23, about 8 to about 22, about 9 to about 21, about 10 to about 20, about 11 to about 19, about 12 to about 18, about 13 to about 17, about 14 to about 16, or about 15 to about 16, mol%.
  • a is from 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, or about 10 to about 11, mol %.
  • a is about 6 to about 14, about 7 to about 13, about 8 to about 12, or about 9 to about 11, mol %.
  • b is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, b is from about 0 to about 95 mol%.
  • b is from about 60 to about 90, about 65 to about 85, about 70 to about 80, or about 75 to about 80, mol %. In another embodiment, b is from about 70 to about 85, about 70 to about 75, or about 80 to about 85, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between 18 PCT PATENT APPLICATION 364.1746PC3 those set forth above, are hereby expressly contemplated for use herein.
  • c is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer.
  • c is from about zero to about 90 mol%.
  • c is from about 2 to about 20, about 3 to about 19, about 4 to about 18, about 5 to about 17, about 6 to about 16, about 7 to about 15, about 8 to about 14, about 9 to about 13, about 10 to about 12, or about 11 to about 12, mol %.
  • c is about 5 to about 15, about 6 to about 14, about 7 to about 13, about 8 to about 12, about 9 to about 11, or about 10 to about 11, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • d is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer.
  • d is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • e is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer.
  • e is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %.
  • all values and ranges thereof, both whole and fractional, 19 PCT PATENT APPLICATION 364.1746PC3 including and between those set forth above, are hereby expressly contemplated for use herein.
  • each of d and e is optional so long as at least one of d and e is greater than zero.
  • the comb polymer can have d without e or can have e without d, or can have d and e, but cannot be lacking both d and e.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, of each of a, b, c, d, and e, independently, are hereby expressly contemplated for use with each other herein.
  • n is about 1 to about 300. In various embodiments, n is about 1. In other embodiments, n is greater than 1. When n is > 1, then the individual -O-CHR6-CHR7- groups are the same or different.
  • n is from 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6. In further embodiments, n is about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55. In other embodiments, n is about 10 to about 90, about 20 to about 80, about 30 to about 70, about 40 to about 60, or about 50. In further embodiments, n is about 25 to about 100, about 25 to about 50, about 50 to about 75, about 50 to about 100, about 25 to about 75, or about 75 to about 100.
  • n is from about 100 to about 300, about 110 to about 290, about 120 to about 280, about 130 to about 270, about 140 to about 260, about 150 20 PCT PATENT APPLICATION 364.1746PC3 to about 250, about 160 to about 240, about 170 to about 230, about 180 to about 220, about 190 to about 210, or about 200 to about 210.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • R6 and R7 which is referenced in the -O-CHR6-CHR7-group described above, is H or a C1-10 hydrocarbyl.
  • the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.
  • Each of X, X 1 , and X 2 may independently be O or NH.
  • R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group.
  • R1 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms.
  • this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc.
  • all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.
  • R2 is -S-R11-Si(OR’)3.
  • R2 is not that group then it may be any number of groups that are common to solution polymers including, but not limited to, H, CH 3 , or an end group derived from an initiator, an alcohol or glycol or non Si containing mercaptans.
  • this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g.1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.
  • R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group.
  • R11 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms.
  • this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc.
  • all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.
  • R3 is a C1-C32 linear or branched hydrocarbyl group or aryl group.
  • R 3 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms.
  • 21 PCT PATENT APPLICATION 364.1746PC3 this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.
  • each of R 4 and R 5 is independently H or CH 3 .
  • R6 is H or a C1-10 hydrocarbyl.
  • the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0068] R 7 is H or a C 1 - 10 hydrocarbyl.
  • the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0069] In further embodiments, each of R8 and R9 is independently H or CH3. [0070] Relative to R10, this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.
  • a is 0.5-75 mol%; 22 PCT PATENT APPLICATION 364.1746PC3 b is 0-99 mol%; c is 0-99 mol%; d is 0 -10 mol%; and e is 0-10 mol%.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • the polymer itself and for example, the composite particle as a whole, may be free of, or include less than, 5, 4, 3, 2, 1, 0.5, or 0.1, mol% of one or more other 23 PCT PATENT APPLICATION 364.1746PC3 polymers not described herein.
  • such polymers may be graft (co)polymers, (co)polymers, graft comb polymers, comb polymers that are not the comb polymer of this disclosure, or acrylate polymers that are not the acrylate polymer of this disclosure, etc.
  • the composite particle may also include just a single type of comb polymer or a single type of acrylate polymer or both a single type of a comb polymer and a single type of an acrylate polymer, and thus be free of second types of comb polymers and/or acrylate polymers.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • Acrylate Polymer [0078] Referring now to the acrylate polymer, the acrylate polymer includes the at least one Si-OR’ group.
  • the acrylate polymer is not limited in itself and may be any known in the art.
  • Non-limiting examples of suitable acrylate monomers include C1-C32 alkyl esters of acrylic and methacrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 10-hydroxydecyl (
  • Suitable co monomers include styrene, ⁇ -methyl styrene, vinyl toluene, t-butyl styrene, iso-propyl styrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprylate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, butadiene, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene 24 PCT PATENT APPLICATION 364.1746PC3 acrylic acid, maleic acid, methacrylic acid, itaconic acidallyl meth
  • any one or more of the above monomers may be free or, or include, the at least one Si- OR’ group
  • any one or more of the above monomers, each which may itself include, or be free of, the at least one Si-OR’ group may be used to form the acrylate polymer of this disclosure so long as the acrylate polymer includes the at least one Si-OR’ group.
  • the acrylate polymer can be formed using any method known in the including, but not limited to, free radical polymerization; emulsion polymerization; solution polymerization; suspension polymerization; bulk polymerization; radiation-induced polymerization; anionic polymerization; and/or controlled/living radical polymerization.
  • the acrylate polymer can be provided from any commercial source.
  • the terminology “consist essentially of” describes embodiments wherein the polymer is free of, or includes less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight or mole percent, of one or more polymers, elements, compounds, solvents, etc. that are not the polymer of this disclosure, i.e., that are extraneous polymers.
  • the acrylate polymer is the reaction product of an acrylate monomer that does not include the at least one Si-OR’ group and one or more silicon containing monomers, e.g. a silane and/or a silanol, that provide the at least one Si-OR’ group.
  • the acrylate polymer is the reaction product of a single acrylate monomer and one or both of a silane and a silanol.
  • the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, and one or both a silane and a silanol.
  • the silane is vinyl trimethoxy silane and the silanol is vinyl trimethoxy silanol.
  • the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, and vinyl trimethoxy silanol.
  • the acrylate polymer is the reaction product of a first acrylate monomer, a second acrylate monomer, and one or both of a silane and a silanol.
  • the acrylate polymer may be formed using one or more monomers, e.g. a (meth)acrylic ester monomer including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ureido-functional (meth)acrylates and acetoacetates, acetamides or cyanoacetates of (meth)acrylic acid; styrene or substituted styrenes; vinyl toluene; butadiene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrollidone; (meth)acrylonitrile; and N-alkylol (meth)
  • Optional multiethylenically unsaturated monomers include, for example, allyl (meth)acrylate, diallyl phthalate, butadiene, 1,4-butylene glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and divinyl benzene.
  • the acrylate polymer may be formed, without a phosphate monomer, as described in one or more of US20080146724A1 and US8710133B2, each of which 26 PCT PATENT APPLICATION 364.1746PC3 is expressly incorporated herein by reference in its entirety in various non-limiting embodiments.
  • Method of Making the Comb Polymer [0089] This disclosure also provides a method of forming the comb polymer that includes the step of (a) mixing monomers A, B, C, D, and/or chain transfer agent E, with water, and preferably an acid which may be any known in the art, to hydrolyze a silane to a silanol and form a mixture.
  • the method also includes the step of (b) introducing this mixture along with an initiator to a reactor under starve-fed conditions.
  • the individual monomers may be any described herein or known in the art to be used form the comb polymer.
  • Monomers A, B, and C have the following formulas: (Monomer C); and wherein each substituent is as described above.
  • monomer D has the formula: 27 PCT PATENT APPLICATION 364.1746PC3 (Monomer D).
  • Chain Transfer Agent E has the formula: (Chain Transfer Agent E).
  • the chain transfer agent is a silanol, e.g. -S-R 11 -Si(OH) 3 ; - S-R 11 -Si(OCH 3 ) 3 ; -S-R 11 -Si(OCH 2 CH 3 ) 3 , or combinations thereof.
  • the chain transfer agent may be gamma-mercaptopropyl trimethoxy silane or mercaptopropyl trimethoxy silanol or combinations thereof.
  • the molar ratio of Monomers A:B:C:(D and/or E) may each independently be from (about 1:about 99).
  • the molar ratio of Monomers A:B:C:(D and/or E) is (about 1 to about 25) : (about 50 to about 95) : (about 1 to about 25) : (about 1 to about 25).
  • any one or more of Monomers A, B, C, and D and/or E may be utilized as 28 PCT PATENT APPLICATION 364.1746PC3 described anywhere in this disclosure in terms of identity and amount.
  • the method then also includes the step of reacting Monomers A, B, C, and (D and/or E) to form the comb polymer.
  • Monomers A, B, C, and (D and/or E) are hereby expressly contemplated for use herein.
  • the comb polymer is typically prepared from a polymerization mixture in an aqueous medium in the presence of any initiator or initiating system capable of liberating free radicals under the reaction conditions employed.
  • the free radical initiators can be present in an amount of from about 0.01% to about 10 mol% based on total moles of monomer.
  • an initiating system is soluble in water to at least 0.1 weight percent, typically to at least 1 weight percent and most typically to at least 10 weight percent at 25°C.
  • Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as erythorbic acid, and metal ion based initiating systems.
  • Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide.
  • the inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate, are typical.
  • the initiators comprise metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides.
  • Organic peracids such as peracetic acid can be used.
  • Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • reducing agents such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • a typical system is persulfate alone such as sodium or ammonium persulfate or a redox system with iron and persulfate with hydrogen peroxide.
  • Azo initiators especially water-soluble azo initiators, may also be used.
  • Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'- Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis ⁇ 2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane ⁇ dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1- pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Azobi
  • the molecular weight of the comb polymer may be controlled by various compounds used in the art including, for example, chain transfer agents such as mercaptans, ferric and cupric salts, bisulfites, and lower secondary alcohols, typically isopropanol.
  • chain transfer agents such as mercaptans, ferric and cupric salts, bisulfites, and lower secondary alcohols, typically isopropanol.
  • the comb polymer starts to be more and more water insoluble as the content of monomer b increases over 75 mol%. Higher molecular weight comb polymers tend to acerbate the water insolubility.
  • a chain transfer agent can be used to minimize the effect on water insolubility by lowering the molecular weight of the comb polymer, e.g. when b is > 75 mol% or 79 mol%.
  • typical chain transfer agents are thiols such as 3-mercaptopropionic acid or 2-mercaptoethanol or lower secondary alcohols, typically isopropanol.
  • the chain transfer agent is chosen from mercaptans (e.g., n-dodecyl mercaptan); thiols (e.g., 2-mercaptoethanol); carbon tetrachloride (CCl4); alcohols (e.g., ethanol, isopropanol); sulfides (e.g., dimethyl disulfide); trithiocarbonates (e.g., ethyl xanthate); organic halides (e.g., bromoform); organic acids (e.g., acetic acid); nitro compounds (e.g., nitroethane); silicon-based compounds; and combinations thereof.
  • mercaptans e.g., n-dodecyl mercaptan
  • thiols e.g., 2-mercaptoethanol
  • carbon tetrachloride (CCl4) CCl4
  • alcohols e.g., ethanol, isopropano
  • starve-fed typically means introducing monomers gradually to a reactor at a rate sufficiently slow enough that the majority of each monomer introduced is consumed by the reaction before additional monomer is added.
  • At least 50% of the monomers are consumed by the reaction before more monomers are added, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%, or at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, or at least 86%, or at least 87%, or at least 88%, or at least 89%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% of the monomers are consumed by the reaction before more monomers are added to the reactor.
  • the core shell polymer may be any as is described in PCT/EP2024/058374, which is expressly incorporated herein by reference in its entirety in various non-limiting embodiments.
  • core-shell morphology As used herein and throughout the specification, the terms “core-shell morphology”, “core-shell structure”, “core polymer”, “staged core polymer” and “two-staged polymer” or “multi-staged polymer” may be used interchangeably and mean a polymer or polymer particle prepared by a sequential or staged polymerization process wherein each sequence or stage of monomer repeating units is added to the polymerization reactor, in a batch or continuous process, and begins to undergo polymerization which may be before, or concurrently with, the addition and polymerization of the subsequent sequence or stage of repeating units is commenced.
  • the polymerization of one stage will be substantially complete before the monomers of the next stage are added to the polymerization reactor. In other embodiments, the polymerization of one stage may be only partially complete before the monomers of the next stage are added to the polymerization reactor.
  • the core shell polymer itself includes at least one core polymer and at least one shell polymer that is disposed about the at least one core polymer. The at least one core polymer is the polymerization reaction product of a first monomer mixture.
  • the first monomer mixture 31 PCT PATENT APPLICATION 364.1746PC3 includes a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; and f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 8 or greater carbon atoms.
  • a1) is present in the first monomer mixture.
  • f1) is not present in the first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in the first monomer mixture.
  • f1) is present in the first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the first monomer mixture.
  • at least one of b1) and f1) is present in the first monomer mixture.
  • the at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture.
  • the second monomer mixture includes a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 8 or greater carbon atoms.
  • e2) is present in the second monomer mixture.
  • a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in the second monomer mixture.
  • a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the second monomer mixture.
  • At least one of b2) and f2) is present in the second monomer mixture while at least one of the first monomer mixture and the second monomer mixture includes a1) or a2) in an amount greater than zero mol %, respectively.
  • at least one of g1) and g2) is utilized.
  • the core shell polymer can be in a form in which a core portion (e.g. core polymer) is completely coated or encapsulated, or non-completely coated or encapsulated, within or by a shell portion (e.g. shell polymer).
  • a core portion e.g. core polymer
  • a shell portion e.g. shell polymer
  • core polymer and “shell polymer” and like terminology are employed herein to describe the polymeric material in a general way without attempting to identify any particular polymers as strictly “shell” or strictly “core” polymers.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • core-shell polymers have a structure in which a polymer(s) forming the core portion, sequence or stage (e.g. core polymer) and the polymer(s) forming the shell portion, sequence or stage (e.g. shell polymer) are physically and/or chemically bonded and/or attracted to each other.
  • the structure and/or chemical composition (e.g. monomer mixture and/or amount) of the core-shell polymer can change from the inside to the outside (i.e., from the at least one core polymer to the at least one shell polymer) and, as a result, may form gradient zones that can have different physical and chemical properties from each other.
  • These gradient zones can be somewhat gradual, yielding a morphology having a gradient of polymeric structure or composition along any radius thereof.
  • the gradient zones can be relatively well defined when moving outward along a radius from the center of the core-shell polymer, yielding a morphology having a relatively distinct core portion including one polymeric composition, and a relatively distinct shell portion including a different polymeric composition.
  • the terminology “gradient” typically describes a pattern with a progressive change (e.g. increase or decrease) in a characteristic at issue.
  • the core-shell polymer can change when considered from the inside to the outside, or when considered from the outside to the inside, relative to a progressive change in physical and/or chemical properties, e.g. an amount of cross-linking.
  • 33 PCT PATENT APPLICATION 364.1746PC3 [00105]
  • the core-shell morphology can include multiple layers or zones of differing polymeric composition. A rate of change in polymeric morphology is not particularly critical as long as the polymer exhibits the desired physical properties described herein.
  • the terms “core” and “shell” refer to the polymeric content of the inside and the outside of the core-shell polymer, respectively, and the use of such terms should not be construed as meaning that the core-shell polymer will necessarily exhibit a distinct interface between the polymers of the inside and the outside.
  • the core-shell polymers can include one or more core polymers and one or more shell polymers, which can be the same as or different from the at least one core polymer and from each other with respect to both the type and proportions of monomers used to form a polymer backbone.
  • one or both of the at least one core polymer and the at least one shell polymer includes an increasing gradient of cross-link density measured in an outward direction extending from a center of the at least one core polymer towards the at least one shell polymer wherein the cross-link density of the at least one core polymer is less than the cross-link density of the at least one shell polymer.
  • one or both of the at least one core polymer and the at least one shell polymer includes an increasing gradient of cross-link density measured in an inward direction extending from an outermost layer of the at least one shell polymer towards a center of the at least one core polymer towards wherein the cross-link density of the at least one core polymer is greater than the cross-link density of the at least one shell polymer.
  • the core-shell polymer may be present in the composition in any amount. Typically, the core-shell polymer is present in an amount of from about 0.01 to about 10 weight percent, about 0.05 to about 2 weight percent, or about 0.1 to about 2 weight percent, based on a total weight of the composition.
  • this amount is from about 0.1 to about 1.9, about 0.2 to about 1.8, about 0.3 to about 1.7, about 0.4 to about 1.6, about 0.5 to about 1.5, about 0.6 to about 1.4, about 0.7 to about 1.3, about 0.8 to about 1.2, about 0.9 to about 1.1, or about 1, weight percent, based on a total weigh of the composition.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the at least one core polymer is independent from the at least one shell polymer.
  • the terminology “at least one” means that a single core polymer may be utilized. Alternatively, more than one core polymer may be utilized.
  • one or more seed polymers may be utilized and then encapsulated, either partially or entirely, by one or more other polymers, wherein the entire complex of seed polymers and encapsulating polymers may be described as a “core” polymer. Any one or more of these seeds polymers and/or encapsulating polymers may be any polymer described herein.
  • the at least one core polymer may be a single core polymer.
  • the at least one core polymer can be, include, consist essentially of, or consist of, the polymerization reaction product of monomers present in the first monomer mixture, as first introduced above.
  • the monomers used to form the at least one core polymer may be chosen from a), b), c), d), e), f), g) and combinations thereof. In one embodiment, only a) and b) are utilized to form the at least one core polymer.
  • any one or more of c, d, e, f, and g may be utilized or omitted from use so long as at least one of g1) and g2) is utilized, as described in greater detail below.
  • the monomers typically described for use in the first monomer mixture are labeled a1), b1), c1), d1), e1), f1) and g1).
  • the nomenclature “1” describes the potential inclusion in the first monomer mixture.
  • the monomers typically described for use in the second monomer mixture are labeled a2), b2), c2), d2), e2), f2), and g2).
  • any of a1) and a2) may be any monomer described herein as “a”, any of b1) and b2) may be any monomer described herein as “b”, any of c1) and c2) may be any monomer described herein as “c”, any of d1) and d2) may be any monomer described herein as “d”, any of e1) and e2) may be any monomer described herein as “e”, any of f1) and f2) may be any monomer described herein as “f”, and any of g1) and g2) may be any monomer described herein as “g”.
  • this amount may be about 5 to about 55, about 10 to about 50, about 15 to about 45, about 20 to about 40, about 25 to about 35, or about 30 to about 35, mol %.
  • the monomer mixture includes about 12 to about 60 mol % of a1) based on a total number of moles of the monomers. In other embodiments, this amount is from greater than about 0 to about 10, about 1 to about 9, about 2 to about 8, about 3 to about 7, about 4 to about 6, or about 4 to about 5, mol % of a1) based on a total number of moles of the monomers.
  • this amount is from about 15 to about 60, about 20 to about 55, about 25 to about 50, about 30 to about 45, or about 35 to about 40, mol % based on a total number of moles of monomer.
  • all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. This is because if f1 is not present a stable emulsion is not formed if a1 is substantially greater than 60 mole%.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the first monomer mixture. For example, this amount may be about 5 to about 75, about 10 to about 70, about 15 to about 65, about 20 to about 60, about 25 to about 55, about 30 to about 50, about 35 to about 45, or about 35 to about 40, mol %. In other embodiments, this amount is from greater than about 0 to about 10, about 1 to about 9, about 2 to about 8, about 3 to about 7, about 4 to about 6, or about 4 to about 5, mol % of a1) based on a total number of moles of the monomers in the first monomer mixture.
  • f1 delivers a high level of hydrophobicity which allows for the formation of stable emulsion.
  • all whole and fractional 36 PCT PATENT APPLICATION 364.1746PC3 values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • at least one of b1) and f1) is present in the first monomer mixture. This is because a hydrophobic monomer is needed to form a emulsion.
  • at least one of g1) and g2) is utilized.
  • the a) anionic ethylenically unsaturated monomer may describe a1) and/or a2).
  • anionic ethylenically unsaturated monomer means an ethylenically unsaturated monomer which is capable of developing a negative charge when the polymer that it is used to form is in an aqueous solution, and which anionic monomer is not an associative monomer, as described below. One or more may be used as described above.
  • the anionic ethylenically unsaturated monomer is an acid.
  • the anionic ethylenically unsaturated monomers can include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, ⁇ -chloro-acrylic acid, ⁇ -cyano acrylic acid, ⁇ -methyl-acrylic acid (crotonic acid), ⁇ -phenyl acrylic acid, ⁇ -acryloxy propionic acid, sorbic acid, ⁇ -chloro sorbic acid, angelic acid, 2-carboxyethyl (meth)acrylate, cinnamic acid, p-chloro cinnamic acid, ⁇ -styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, muconic acid, 2- acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic
  • the anionic ethylenically unsaturated monomer may be methacrylic acid, maleic acid, acrylic acid, itaconic acid, 2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof. In one embodiment, most typically the anionic ethylenically unsaturated monomer is methacrylic acid or acrylic acid, or combinations thereof.
  • the term “(meth)acrylic” acid is meant to include both acrylic acid and methacrylic acid.
  • alkyl (meth)acrylate as used herein is meant to include alkyl acrylate and alkyl methacrylate.
  • the b) short chain hydrophobic ethylenically unsaturated monomer may describe b1) and/or b2).
  • the term “short chain hydrophobic ethylenically unsaturated monomer” means a monomer that has a side chain including a hydrophobe that has 7 or fewer carbon atoms. e.g., 7, 6, 5, 4, 3, 2, or 1 carbon atom.
  • This monomer is hydrophobic and tends to enable the formation of an emulsion system when reacted with am anionic ethylenically unsaturated monomer.
  • One or more may be used as described above.
  • the hydrophobic ethylenically unsaturated monomer can be sparingly soluble in water and have a water solubility of less than about 6, 5, 4, 3, 2, 1.6, 1, etc. grams per about 100 mls of water at about 25°C.
  • These hydrophobic ethylenically unsaturated monomers may include linear or branched alk(en)yl, cycloalkyl, aryl, or alk(en)aryl moieties.
  • Suitable hydrophobic ethylenically unsaturated monomers include C1-C7 alkyl esters of acrylic acid, maleic acid, itaconic acid and methacrylic acid; C1-C7 alkyl amides of acrylic acid, maleic acid, itaconic acid and methacrylic acid; benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and styrene, alpha-methyl styrene, vinyl toluene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl valerate, vinyl hexanoate, vinyl caprolactam, (meth)acrylonitrile, isobutylene, diisobutylene, isoprene, vinyl chloride, vinyli
  • the b1) hydrophobic ethylenically unsaturated monomers are utilized in an amount such that an amount of a1) and b1) sums to about 100 mol%.
  • the amount of b1) is from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the first monomer mixture described above typically not including an amount of any crosslinking monomer or agent used.
  • the c) associative monomer may describe c1) and/or c2).
  • the term “associative monomer” describes an ethylenically unsaturated monomer including 38 PCT PATENT APPLICATION 364.1746PC3 a hydrophobe and a spacer moiety which allows the hydrophobe to be sufficiently far away from the backbone of the core or shell polymer to form hydrophobic associations in aqueous solutions, and wherein the hydrophobe includes at least six carbon atoms.
  • the spacer moieties are usually ethoxylate groups but any other group that extends the hydrophobe away from the backbone of the core and/or shell polymer may be used. One or more may be used as described above.
  • the hydrophobes with a spacer moiety may include, but are not limited to, alcohol ethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated silicones and the like.
  • the typical hydrophobes with spacer moieties include alcohol ethoxylates and/or alkylphenoxy ethoxylates.
  • alcohol ethoxylates have carbon chain lengths of from about 6 to about 40 and from about 6 to about 100 moles of ethoxylation. In yet another embodiment, alcohol ethoxylates have carbon chain lengths of from about 12 to about 22 and from about 15 to about 30 moles of ethoxylation. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00125]
  • the hydrophobes may be linear or branched alk(en)yl, cycloalkyl, aryl, alk(en)aryl or an alkoxylated derivative.
  • the most typical hydrophobes are linear or branched alcohols and amines that include about 12 to about 32 carbons.
  • the associative monomer may include an ethylenically unsaturated monomer covalently linked to the hydrophobe.
  • the ethylenically unsaturated monomer part of the associative monomer typically is a (meth)acrylate, itaconate and/or maleate which includes ester linking groups.
  • the associative monomer may also include amide, urea, urethane, ether, alkyl, aryl and other suitable linking groups.
  • the hydrophobe may be an alkylamine or dialkylamine ethoxylate.
  • the (meth)acrylate group is most typical.
  • typical associative monomers are C 12-32 (EO) 10-30 meth(acrylates) or C 12-32 (EO) 10-30 itaconates or C 12-32 (EO) 10-30 maleates.
  • the associative monomer has the structure of formula (I) 39 PCT PATENT APPLICATION 364.1746PC3 wherein: R1 is chosen from -H, -CH3, -COOH, or -CH2COOH; A is chosen from -CH2C(O)O-, -C(O)O-, -O-, –CH2O-, -CH2C(O)N-, -C(O)N-, -CH2-, -O-C(O)-, -NHC(O)O-, -NHC(O)NH-, -C 6 H 4 (R 5 )-NH-C(O)-O-, -C 6 H 4 (R 5 )-NH-C(O)-NH-, -C(O)O-CH 2 - CH(CH2OH)-O-, -C(O)O-CH2-CH(CH2OH)-NH-, -C(O)O-CH
  • Suitable associative monomers include methacrylate and itaconate esters of a hydrophilic ethoxylate chain and a hydrophobic alkyl chain.
  • the associative monomer is an alkyl ethoxylate methacrylate ester having the structure of formula I(A): [00129] In one embo -based associative monomer such as cetyl ethoxylate itaconate, behenyl ethoxylate itaconate, or stearyl ethoxylate itaconate having the structure of formula I (B, C, D respectively) 40 PCT PATENT APPLICATION 364.1746PC3 [00130] In various embodiments, the associative monomers are utilized in an amount of from about 0.01 mol% to about 3 mol%, or from about 0.05 mol% to about 2 mol%, or from about 0.1 mol% to about 1 mol%, based on a total number of moles in the monomer mixture, In various non- limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein.
  • the residue of the one or more optional associative monomers is not present in the at least one core polymer and/or the at least one shell polymer. In other words, in such embodiments, no associative monomers are used.
  • one or more c1) and c2) associative monomers may not be present in the first and/or second monomer mixtures.
  • d) Cross-Linking Monomers Cross-Linking Agents
  • the d) cross-linking monomers may describe d1) and/or d2). Referring now to the cross-linking monomers, one or more may be used as described above. Alternatively, these monomers may be omitted from use.
  • the at least one core polymer is not cross-linked. However, some cross-linking can be used so long as the amount of cross-linking does not overly inhibit the ability of the core-shell polymer to swell as described herein. 41 PCT PATENT APPLICATION 364.1746PC3 [00133]
  • the at least one shell polymer is formed using the cross-linking monomer/agent while the at least one core polymer is not.
  • both the at least one shell polymer and the at least one core polymer may be formed using the cross-linking monomer/agent. However, if an amount of cross-linker is the same in both polymers, typically the core-shell polymer of this disclosure is not formed and instead a traditional polymer is formed.
  • the at least one core polymer includes a residue of the one or more crosslinking monomers in an amount that is less than an amount of the residue of the one or more crosslinking monomers in the shell by about 5 mol % of that amount or less.
  • the at least one core polymer can be formed using a molar amount of the cross-linking monomer/agent that is about 5 mol % less than the amount of the cross-linking monomer/agent used to form the at least one shell polymer. In other embodiments, this amount is from about 5 to about 10 mol % less. In other embodiments, this amount is about 5, 4, 3, 2, 1, or even 0.5, mol % less.
  • the cross-linking monomer/agent can be chosen from one or more of a crosslinking monomer having two or more carbon-carbon double bonds, a polyfunctional crosslinking compound that reacts with pendant functional groups on the relevant polymer, and combinations thereof.
  • Exemplary cross-linking monomer/agents include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6- hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,2′-bis(4-(acryloxy-propyloxyphenyl)propane, 2,2′-bis(4-(acryloxydiethoxy-phenyl)propane, and zinc acrylate (i.e., 2(C 3 H 3 O 2 )Zn ++ ); tri(meth)acrylate compounds such as, trimethylolpropane tri(meth)acrylate, trimethylole
  • suitable compounds include divinyl glycol, divinyl benzene, and N,N'-methylenebisacrylamide, and combinations thereof.
  • suitable monomers can be synthesized via an esterification reaction of a polyol made from ethylene oxide or propylene oxide or combinations thereof with unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, or an addition reaction with unsaturated isocyanate such as 3-isopropenyl- ⁇ - ⁇ -dimethylbenzene isocyanate.
  • Exemplary polyfunctional cross-linking monomer/agents include polyhaloalkanols such as 1,3-dichloroisopropanol and 1,3-dibromoisopropanol; sulfonium zwitterions such as the tetrahydrothiophene adduct of novolac resins; haloepoxyalkanes such as epichlorohydrin, epibromohydrin, 2-methyl epichlorohydrin, and epiiodohydrin; polyglycidyl ethers such as 1,4- butanediol diglycidyl ether, glycerine-1,3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, bisphenol A-
  • nonionic ethylenically unsaturated monomers may describe e1) and/or e2).
  • nonionic ethylenically unsaturated monomer means an ethylenically unsaturated monomer which does not introduce a charge into the polymer that it is used to form, and which is neither a hydrophobic ethylenically unsaturated monomer nor an associative monomer nor a crosslinker, each as described herein. One or more may be used as described above or may be omitted.
  • nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, N-C 1 -C 3 alkyl(meth)acrylamides and N,N-C 1 -C 3 43 PCT PATENT APPLICATION 364.1746PC3 dialkyl(meth)acrylamides such as N-methylmethacrylamide, N-ethylacrylamide, N- propylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, and N,N – dimethylmethacrylamide; vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butanoate, ethoxylated alkyl, alkaryl or aryl monomers such as methoxypolyethylene glycol (meth)acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth)acrylate, C1 to C4 hydroxyalky
  • the optional C 1 to C 4 hydroxyalkyl esters of (meth)acrylic acid can include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (butane diol mono(meth)acrylate).
  • the monomer is chosen from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2- hydroxybutyl (meth)acrylate.
  • all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein.
  • the optional nonionic ethylenically unsaturated monomer is utilized in an amount of from about 0 to about 85, from about 1 to about 85, from about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the monomer mixture described above typically not including an amount of any crosslinking monomer/agent used.
  • all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein.
  • the f) long chain hydrophobic ethylenically unsaturated monomers may describe f1) and/or f2).
  • the one or more long chain hydrophobic ethylenically unsaturated monomers have a side chain including a hydrophobe that has 8 or greater carbon atoms. Although there is no particular upper limit for carbon atoms, in various embodiments, the upper limit is about 50, 45, 40, 35, 30, 25, 20, 15, or 10.
  • the number of carbon atoms is from about 8 to about 32, 10 to about 30, 12 to about 28, 14 to about 26, 16 to about 24, 18 to about 22, 44 PCT PATENT APPLICATION 364.1746PC3 or 20 to about 22.
  • at least one of f1) and f2) is independently chosen from C8-C32 alkyl esters of acrylic acid, maleic acid, itaconic acid and methacrylic acid; C8-C32 alkyl amides of acrylic acid, maleic acid, itaconic acid and methacrylic acid; 10-hydroxydecyl (meth)acrylate, t-butyl styrene, iso-propyl styrene, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, isobutylene, diisobutylene, isoprene, vinyl chloride
  • b1) and/or b2) and/or f1) and/or f2) may be chosen from the following, where appropriate, in view of the above definitions of such monomers: C1-C32 alkyl esters of acrylic and methacrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, n- propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hexyl (meth)acrylate,octyl (meth)acrylate, decyl (meth)acryl
  • ethyl acrylate, methyl acrylate, methyl methacrylate, vinyl acetate, butyl acrylate and combinations thereof are typical.
  • exemplary 45 PCT PATENT APPLICATION 364.1746PC3 alkyl (meth)acrylate monomers can be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, and mixtures thereof.
  • ethyl acrylate is typical.
  • the amount of the f1) long chain hydrophobic ethylenically unsaturated monomers is from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the first monomer mixture described above typically not including an amount of any crosslinking monomer or agent used.
  • g) One Or More Monomers Or Chain Transfer Agents With A Silane Or Silanol Group may describe g1) and/or g2). These are optionally used herein.
  • the one or more monomers or chain transfer agents with a silane or silanol group are not particularly limited and may be any known in the art.
  • the one or more monomers or chain transfer agents with a silane or silanol group is chosen from trimethylsilanol; dimethylsilanediol; methylsilanetriol; tetrahydroxysilane; 3-(trihydroxysilyl)propylamine; 3- (trihydroxysilyl)propionic acid; hydroxyl-terminated polydimethylsiloxane (PDMS-OH); trimethylsilane; dimethylsilane; methylsilane; phenylsilane; chlorotrimethylsilane; dichlorodimethylsilane; trichloromethylsilane; tetrachlorosilane; trimethoxysilane; triethoxysilane; methyldimethoxysilane; phenyltrimethoxysilane; 3- aminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane; vinyltrimethoxysilane; (3- g
  • the amount of the g1) and/or g2) one or more monomers or chain transfer agents with a silane or silanol group is about zero or about from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer 46 PCT PATENT APPLICATION 364.1746PC3 in the respective monomer mixture described above typically not including an amount of any crosslinking monomer or agent used.
  • At least one of g1) and g2) is utilized such that the amounts of both g1) and g2) utilized to form the respective polymers are not both zero. Said differently, an amount of g1) that is used is greater than zero, an amount of g2) is greater than zero, or amounts of both g1) and g2) that are used are both greater than zero. In other embodiments, the molar percent of residues of g1) and/or g2) is from about 0.01 to about 10 mol%, based on a total moles of reactants, e.g.
  • g1) may be used without g2).
  • g2) may be used without g1).
  • both g1) and g2) may be used.
  • both g1) and g2) may not be omitted herein.
  • g1) may be used in an amount more than that of g2).
  • g2) may be used in an amount more than that of g1).
  • the shell requires Si-OR’ for bonding such that the shell of the core-shell polymer can be attached to the surface of the particle via an R-O-Si bond.
  • the shell chemistry is related to g2) such that g2) may be required.
  • the at least one shell polymer is independently the polymerization reaction product of the second monomer mixture described above including the a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that 47 PCT PATENT APPLICATION 364.1746PC3 has 8 or greater carbon atoms.
  • any of the above may be used to form the at least one shell polymer.
  • g1) or g2) may be used or omitted so long as at least one of g1) and g2) is utilized.
  • any of the above description relative to the components or amounts thereof utilized in forming the at least one core polymer may also apply to the at least one shell polymer, in various non-limiting embodiments.
  • any one or more of the amounts of any one of a1)-f1) above may also be independently utilized for any one or more of a2)-f2) in the second monomer mixture wherein the weight basis would be the second monomer mixture.
  • the monomers used to form the at least one shell polymer may be chosen from a), b), c), d), e), f), and combinations thereof. In one embodiment, only a) and b) are utilized to form the at least one core polymer.
  • the at least one shell polymer is at least partially cross-linked and includes from about 0.01 mol % to about 10 mol % of the residue of the one or more crosslinking monomers. In various embodiments, this amount is from about 0.05 to about 10, about 0.1 to about 10, about 1 to about 10, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc.
  • the one or more shell polymers can have any mole percent of residues of the crosslinking agent, as long as the at least one core polymer has a mole percent of residues of the crosslinking agent less than the at least one shell polymer.
  • the residue of the one or more optional associative monomers is present in an amount of greater than zero and up to about 1.5 mol % in the at least one core polymer and/or the at least one shell polymer, e.g.
  • the at least one core polymer includes from about zero mol % of the residue of the one or more crosslinking monomers up to an amount of less than about 25 mol % of the amount of the residue of the one or more crosslinking monomers present in the at least one shell polymer. In various embodiments, this amount is from about 0.05 to about 25, about 0.1 to about 25, about 1 to about 25, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc.
  • the at least one core polymer includes about zero mol % of the residue of the one or more crosslinking monomers and further includes the residue of the one or more associative monomers in an amount of greater than zero mol %.
  • This amount may be any amount greater than zero.
  • this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc.
  • the at least one core polymer includes about zero mol % of the residue of the one or more crosslinking monomers and the at least one shell polymer includes the 49 PCT PATENT APPLICATION 364.1746PC3 residue of the one or more associative monomers in an amount of greater than zero mol %. This amount may be any amount greater than zero.
  • this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the at least one core polymer includes about zero mole % of the residue of the one or more crosslinking monomers and the at least one shell polymer is at least partially cross-linked and includes greater than about 0.05 mol % of the residue of the one or more crosslinking monomers. This amount may be any amount greater than about 0.05 mol%.
  • this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the at least one core polymer includes from about 1% to about 95% by weight of one or more shell polymers, based on the total weight of the at least one core polymer.
  • the at least one core polymer includes about 5 wt% to about 60 wt% of the one or more shell polymers, based on the total weight of the at least one core polymer.
  • the at least one shell polymer accounts for greater than about 5 wt% and less than about 90 wt% of a total weight of the monomer residues in the core-shell polymer. This value may be about 5 to about 85, about 10 to about 80, about 15 to about 75, about 20 to about 70, about 25 to about 65, about 30 to about 60, about 35 to about 55, about 40 to about 50, or about 45 to about 55, wt%.
  • this value is from about 15 to about 40, about 20 to about 35, or about 25 to about 30, wt%.
  • the amount is greater than about 90, the shell is too heavy and desired expansion/swelling is limited. This is not desirable.
  • the wt % of the shell is about 75 wt% and the amount of residue of the cross-linking monomer/agent is about 0.1 mol %. Similar ratios of shell weight and molar % of crosslinking monomer are also contemplated for use herein.
  • the core-shell polymer will not be complete and undesirable mixtures of side-products (polymers) will tend to form.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the at least one core polymer includes about 10 wt% to about 40 wt% or about 15 to about 35 wt % of the one or more shell polymers based on the total weight of the at least one core polymer.
  • the at least one core polymer is present in an amount that is greater than about 60 wt% and up to about 95 wt% based on the total weight of the at least one core polymer.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • at least one shell polymer includes a mol % of residue of the d2) one or more crosslinking monomers that is greater than a mol % of residue of the d1) one of more cross-linking monomers in aid at least one core polymer.
  • this mol% may be 1, 2, 3, 4, 5, 10, 15, 20, 25...up to about 100 mol% greater.
  • the core shell polymer includes two or more shell polymers and at least one shell polymer includes a mol % of residue of the d2) one or more crosslinking monomers that is less than a mol % of residues of the d1) one of more cross-linking monomers in the at least one core polymer.
  • the at least core shell polymer accounts for greater than 5 wt % and less than about 90 wt % of a total weight of the core shell polymer, e.g.
  • b1) and/or f1) is present in the first monomer mixture in at least about 1 mol% based on a total number of moles of monomers in the first monomer mixture and the a1) anionic ethylenically unsaturated monomer is present in the first monomer mixture in 10 mol% or less based on a total number of moles of monomers in the first monomer mixture; and b2) and/or f2) is present in the second monomer mixture in at least about 1 mol% based on a total number of moles of monomers in the second monomer mixture and the a2) anionic ethylenically unsaturated monomer is present in the second monomer mixture in 10 mol% or less based on a 51 PCT PATENT APPLICATION 364.1746PC3 total number of moles of monomers in the second monomer mixture.
  • the at least one core polymer is the reaction product of a1) and b1) and the at least one shell polymer is the reaction product of a2), b2), and d2); or the at least one core polymer is the reaction product of a1), b1) and e1) where a1) is present in an amount of less than about 20 mol% of the first monomer mixture and e1) is present in an amount of greater than about 5 mol% of the first monomer mixture and the at least one shell polymer is the reaction product of a2), b2), d2) and e2) wherein a2) is present in an amount of less than about 20 mol% of the second monomer mixture and e2) is present in an amount of greater than about 5 mol% of the second monomer mixture.
  • any of a2), b2), c2), d2), e2), f2), and g2) may independently be present in any of the amounts or ranges of amounts that are described above relative to a1), b1), c1), d1), e1), f1), and g1) even if one or more of a1), b1), c1), d1), e1), f1), and g1) is not used or even if the amount of one or more of a1), b1), c1), d1), e1), f1), and g1) is different from the amount of one or more of a2), b2), c2), d2), e2), f2), and/or g2).
  • the core-shell polymer includes a first shell polymer (12) and a second shell polymer (14) wherein the first shell polymer (12) is disposed on and in direct contact with the at least one core polymer (10) and the second shell polymer (14) is disposed on and in direct contact with the first shell polymer (12). Examples are shown in the Figures. [00166] In one embodiment, e.g. as shown in FIG.
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross- link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is greater than the cross-link density of the first shell polymer (12) and greater than the cross-link density of the at least one core polymer (10).
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross-link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is less than the cross-link density of the first shell polymer (12) and greater than the cross-link density of the at least one core polymer (10).
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is greater than the cross-link density of the at least one core polymer (10) and greater than the cross-link density of the first shell polymer (12).
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross-link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and less than the cross-link density of the first shell polymer (12).
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and greater than the cross-link density of the first shell polymer (12).
  • each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density
  • the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10)
  • the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and less than the cross-link density of the first shell polymer (12).
  • outermost describes an embodiment wherein the layer is disposed such that it forms an exterior layer of the core shell polymer that is exposed to the environment and does not include another layer disposed on its exterior.
  • inner layer describes that the layer has another layer disposed on at least one surface/side thereof. The inner layer is not exposed to the environment and is not an outer layer.
  • intervening polymers may be any known in the art and any described herein.
  • the core shell polymer is further defined as an alkali swellable core shell polymer.
  • alkali swellable means that, in these embodiments, the core shell polymer can swell when exposed to alkali conditions, e.g. in water, in a composition etc.
  • the swelling of the composition can be measured via laser diffraction, e.g. using a particle size analyzer such as a Malvern Mastersizer. Any method can be used, e.g. ASTM E3340-22, ASTM D1921-18, International Standard ISO 13320-1, etc.
  • diameters may be reported as x 10 (D v 10), x 50 (D v 50), x 90 (D v 90), and D[4,3] (volume moment mean), etc.
  • any one or more of Dv10 and/or Dn10, Dv50 and/or Dn50, Dv90 and/or Dn90 may be used to report and evaluate particle size.
  • any type of instrument type, software version, light scattering model applied, real and imaginary part of complex refractory index if Mie theory is applied, etc. may be used as specified in such methods.
  • particle size can be calculated as follows using a Malvern Zetasizer Nano S. For example, three measurements are performed in succession, with the number of runs per measurement automatically determined by the instrument. Measuring position and attenuation are set automatically by the instrument. The measurement sequence is performed at 25°C after a 120 second equilibration time.
  • the preset values for water viscosity (0.8872 centipoise) and refractive index (1.330) are used for the dispersant parameters.
  • a refractive index and absorption for the samples are set at 1.590 and 0.010, respectively.
  • cumulants and distribution analyses are performed by the instrument software (Malvern Zetasizer Software, version 7.10).
  • the reported z-average (in nm) is used as the measure of particle size.
  • the particle size distribution can be such 54 PCT PATENT APPLICATION 364.1746PC3 that a cumulants analysis is not successful (as indicated by instrument software quality reports) and therefore the z-average, while reported, may not be reliably calculated.
  • the core shell polymer has a first diameter measured at a pH of from about 3 to about 5, and has a second diameter measured at a pH of about 8, wherein the second diameter is larger than the first diameter.
  • the second diameter may be about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50...up to about 100% or more, larger than the first diameter.
  • the core-shell polymer may be formed using any method in the art. More specifically, the core-shell polymer includes at least two polymers (i.e., the at least one core polymer and the at least one shell polymer) which may be synthesized using any methods known in the art. For example, the polymerization may occur sequentially via free radical emulsion polymerization techniques known to the art.
  • the at least one core polymer is synthesized in a first emulsion polymerization step from the first monomer mixture including one or more of a1)-f1) and optionally g1) described above.
  • a chain transfer agent also can be used, as described in greater detail below.
  • a first monomer pre-emulsion may be utilized wherein the first monomer mixture can be emulsified in a water and surfactant mixture in a first vessel before being added to a reactor where emulsion polymerization takes place.
  • the first monomer mixture has no added water or surfactant before being added to the reactor where emulsion polymerization takes place.
  • the monomers a1)-f1) and optionally g1) may be polymerized in the presence of a suitable free radical forming initiator, e.g. to provide an emulsion of the at least one core polymer.
  • a suitable free radical forming initiator e.g. to provide an emulsion of the at least one core polymer.
  • the polymerization typically begins with a “seed” process in which seed polymer particles are formed that serve as loci for subsequent polymerization.
  • seed seed
  • free radical initiators that generate a free radical during the polymerization process are utilized.
  • the initiating system may be any free radical initiating system.
  • the free radical initiators are typically present in an amount of from about 0.01 wt% to about 3 wt% based on total monomer weight.
  • the initiating system is soluble in water to at least 0.1 weight percent at 25°C.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as hydrogen peroxide and erythorbic acid, and metal ion based initiating systems.
  • Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide.
  • the inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate, are typical.
  • the initiators include metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides.
  • Organic peracids such as peracetic acid can be used.
  • Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • reducing agents such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • Azo initiators especially water soluble azo initiators, may also be used.
  • Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'- Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis ⁇ 2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane ⁇ dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1- pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Azobi
  • emulsion polymerization additives and processing aids which are well known in the emulsion polymerization art, such as auxiliary emulsifiers, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides, antifoam agents, and pH adjusting agents can be included in the polymerization system.
  • the primary emulsifier is typically an anionic surfactant and these such as sodium lauryl sulfate are well known in the art.
  • an auxiliary emulsifying aid chosen from an ethoxylated C10 to C22 fatty alcohol (or their mixtures) can be added to the reactor.
  • the fatty alcohol includes from about 5 to about 250 moles of ethoxylation, from about 8 to 100 moles in another aspect, and from about 10 to 50 moles in a further aspect.
  • Exemplary ethoxylated fatty alcohols include lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and behenyl alcohol ethoxylate.
  • suitable ethoxylated fatty alcohols include Ceteth- 20, Ceteareth-20, and Steareth-20, Behenth-25, and mixtures thereof.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the amount of ethoxylated fatty alcohol can be from about 0.01% to 10% by weight in one embodiment, from about 0.1% to about 5% by weight in another aspect, and from about 0.3% to about 3% by weight in a further aspect, based on a total weight of emulsion basis.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • Two-Stage Polymerization [00186] The following describes a typical two-stage polymerization which may be utilized or omitted.
  • a first monomer mixture including one or more of a1)-f1) and optionally g1) described above and an optional chain transfer agent are added to a first vessel with mixing and are combined with a solution of emulsifying surfactant (e.g., anionic surfactant) in water to prepare a monomer pre-emulsion.
  • emulsifying surfactant e.g., anionic surfactant
  • Optional processing aids can be added as desired (e.g., auxiliary emulsifier(s)).
  • the monomers may be introduced to an aqueous charge that optionally includes a surfactant in a reactor either as a monomer pre-emulsion or a separate monomer mixture and aqueous surfactant solution.
  • an aqueous surfactant 57 PCT PATENT APPLICATION 364.1746PC3 solution can be added to the reactor at the same time as or directly after the addition of the first monomer mixture.
  • the reactor contents can be stirred and a small amount of free-radical initiator can be added to the reactor to initiate the formation of seed particles, which is known as a seed stage.
  • the first monomer mixture can be added as a as a monomer mixture or monomer pre-emulsion concurrent with an initiator feed, or as a first monomer mixture added concurrently with an aqueous surfactant solution feed and an initiator feed, to the reactor.
  • the initiator can be added prior to the addition of the monomer mixture to the reactor.
  • core polymer or polymer emulsion has a total polymer solids content of from about 10 to about 45 weight percent. While the at least one core polymer is synthesized in an emulsion, it should be recognized that the at least one core polymer can be supplied in dried powder form if desired. This is particularly useful for adhesives that are re- dispersible powders. [00188] Next, the at least one shell polymer is formed in a second polymerization step.
  • the second monomer mixture of a2)-f2) and optionally g2) may be added as a monomer mixture or as a monomer pre-emulsion concurrent with an initiator feed, or as a second monomer mixture added concurrently with an aqueous surfactant solution feed and an initiator feed.
  • the initiator can be added prior to the addition of the second monomer mixture to the reactor.
  • the end- product is a two stage polymer including the at least one core polymer surrounded or partially surrounded by the at least one shell polymer.
  • a portion of the full amount of surfactant to be used is initially present in the reactor, and the remainder is added as a concurrent stream along with the stream of monomer mixture and the stream of initiator, during all steps of the polymerization.
  • further successive free radical emulsion polymerization stages can be run to obtain multi-layer polymer morphologies such that successive polymer stages differ at least by the mole percent of crosslinking agent utilized in that stage.
  • a monomer mixture can be used that is devoid of crosslinking agent.
  • the monomer mixture will include a crosslinking agent.
  • the core-shell polymer can be synthesized by successive emulsion polymerization steps to yield an aqueous polymer emulsion, it should be recognized that the core-shell polymer can ultimately be supplied in dried powder form if desired.
  • the emulsion polymerization can be carried out in a staged batch process, in a staged semi-batch monomer addition process or multi-step continuous process, or the polymerization can be initiated as a batch process and then the bulk of the monomers can be continuously staged into the reactor (seeded semi-batch process), as described above.
  • the emulsion polymerization reactions are carried out at a reaction temperature of from about 20 to about 99°C.
  • the emulsion polymerization reactions can be performed in an aqueous or aqueous alcohol medium.
  • the surfactant can be added to the first and/or second monomer mixtures to form a pre- emulsion. Alternatively, the surfactant can be added directly to the reactor during the emulsion polymerization. Alternatively, both methods can be utilized.
  • Suitable anionic surfactants for facilitating emulsion polymerizations include, but are not limited to, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium (C6-C16) alkyl phenoxy benzene sulfonate, disodium (C6-C16) alkyl phenoxy benzene 59 PCT PATENT APPLICATION 364.1746PC3 sulfonate, disodium (C6-C16) di-alkyl phenoxy benzene sulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butyl naphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfo
  • Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art, and include, without limitation, linear or branched alcohol ethoxylates, C8 to C 12 alkylphenol alkoxylates, such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like.
  • linear alcohol alkoxylates include polyethylene glycol ethers of cetearyl alcohol (a mixture of cetyl and stearyl alcohols) sold under the trade names PLURAFAC® C-17, PLURAFAC® A-38 and PLURAFAC® A-39 by BASF Corp.
  • polyoxyethylene polyoxypropylene block copolymers include copolymers sold under the trade names PLURONIC® F127, and PLURONIC® L35 by BASF Corp.
  • suitable nonionic surfactants include, but are not limited to, Ethoxylated linear fatty alcohols such as DISPONIL® A 5060 (Cognis), Ethal LA-23 and Ethal LA-50 (Ethox Chemicals), branched alkyl ethoxylates such as GENAPOL® X 1005 (Clariant Corp.), secondary C 12 to O 14 alcohol ethoxylates such as TERGITOL® S15-30 and S15-40 (Dow Chemical Co.), ethoxylated octylphenol-based surfactants such as TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887, and 897 (Rhodia, Inc.), ICONOL® OP 3070 and
  • Suitable polymeric stabilizers for the emulsion 60 PCT PATENT APPLICATION 364.1746PC3 polymerization process of this disclosure are water-soluble polymers, including, for example, synthetic polymers, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers and the like; water-soluble natural polymers, such as gelatin, pectins, alginates, casein, starch, and the like; and modified natural polymers, such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl modified hydroxyethylcellulose, and the like.
  • synthetic polymers such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers and the like
  • polymeric stabilizers can be utilized in amounts up to about 10 weight percent based on the total emulsion weight, or up to about 7.5 weight percent, or up to about 5 weight percent, or up to about 2.5 weight percent, or up to about 2 weight percent based on the total emulsion weight.
  • a polymeric stabilizer when utilized, is included in an amount of from about 0.001 weight percent to about 10 weight percent, or from about 0.01 weight percent to about 7.5 weight percent, or from about 0.1 weight percent to about 5 weight percent, or from about 0.5 weight percent to about 2.5 weight percent, or even from about 1 weight percent to about 2 weight percent, based on the total emulsion weight. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00204] In various embodiments, a polymerization reactor is charged with a desired amount of water, additional surfactant and optional processing aids.
  • the polymerization reactor is equipped with attached inert gas inlet and feed pumps, and the reactor contents are maintained under inert atmosphere and heated with mixing agitation.
  • the contents of the reactor are brought to a temperature of from about 55 to 98°C, and are maintained at those conditions for about one hour.
  • a seed stage can then be performed in a manner consistent with the addition of monomer and surfactant via a pre-emulsion as described above.
  • the desired amount of core stage monomer pre-emulsion is fed subsurface into the reactor, and a free radical initiator solution is fed separately and concurrently with the core stage monomer mixture into the reactor contents over a period of about one half to two hours. During this time, the reaction temperature is controlled at from about 45 to about 95°C.
  • the feed may be stopped and, if desired, an additional quantity of free radical initiator can optionally be added to the reactor.
  • the resulting reaction mixture can be held at a temperature of about 45 to 95°C for a time period sufficient to complete or substantially complete the polymerization reaction and obtain a first stage core-shell polymer emulsion.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the second monomer mixture used for forming the at least one shell polymer can be mixed in a separate vessel following the same procedures as described above.
  • a crosslinking agent can be added and mixed with agitation to form the second monomer mixture. Additional monomers can be added if desired.
  • monomers used to form the at least one shell polymer are metered into the reactor at a constant rate and mixed with aforementioned emulsion used to form the at least one core polymer.
  • a free radical initiator solution in an amount sufficient to reinitiate polymerization can be metered into the reaction mixture, such that the monomers are polymerized in the presence of the at least one core polymer.
  • the temperature is then typically maintained at about 85°C for about one half to two and a half hours or until polymerization is complete. Unreacted monomer can be eliminated by completing a monomer chase step, such as addition of more initiator and/or by adjusting and maintaining temperature for a period of time to maintain radical flux from thermal initiator residues, as is well known in the emulsion polymerization art.
  • chain transfer agents can be used in any stage of the polymerization process for any one or more monomers described above or can be omitted.
  • the chain transfer agent can be any chain transfer agent known in the art.
  • Suitable chain transfer agents include, but are not limited to, thio and disulfide containing compounds, such as C1-C18 alkyl mercaptans, C1-C18 alkyl mercaptoalcohols, mercaptocarboxylic acids, mercaptocarboxylic esters, thioesters, C1-C18 alkyl 62 PCT PATENT APPLICATION 364.1746PC3 disulfides, aryldisulfides, polyfunctional thiols such as trimethylolpropane-tris-(3- mercaptopropionate), pentaerythritol-tetra-(3-mercaptopropionate), pentaerythritol-tetra- (thioglycolate), and pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioglycolate), and the like; phosphites and
  • the chain transfer agent is chosen from n-dodecyl mercaptan, methyl mercaptopropionate, and 3-mercaptopropionic acid, 2-mercaptoethanol, combinations thereof and the like, octyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, isooctyl 3-mercaptopropionate, butyl 3-mercaptopropionate, butyl thioglycolate, isooctyl thioglycolate, and dodecyl thioglycolate.
  • the chain transfer agent can be utilized an amount less than about 0.75, about 0.5, about 0.25, or about 0.1, mol% based on the monomers present typically not including the crosslinking agent.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • Additional Embodiments [00212]
  • the weight proportion of the at least one shell polymer to the at least one core polymer and the amount of crosslinking agent in each of the at least one shell polymer and the at least one core polymer are selected to provide typical rheological properties for a particular end-use application.
  • the at least one core polymer is greater than 5, 10, 20, 30, 40, 50,6070, 80, 90 wt% of the core-shell polymer.
  • the core-shell polymer includes at least one core polymer including zero mol% of a residue of a crosslinking agent.
  • the core-shell polymer includes at least one core polymer including a residue of C1-C6 alkyl (meth)acrylate monomers.
  • the at least one core polymer includes both at least one residue of a C1-C6 alkyl acrylate monomer and at least one residue of a C1-C6 alkyl methacrylate monomer.
  • the binder is chosen from acrylate, vinyl acrylate, styrene acrylate, and combinations thereof.
  • the binder is chosen from acrylics, vinyl -acrylic, styrene acrylics, ethylene-vinyl acetate, vinyl acetate, alkyd, vinyl chloride, styrene-butadiene, vinyl versatate, vinyl acetate-maleate, and combinations thereof.
  • the at least one core polymer includes a residue of the one or more crosslinking monomers in an amount that is less than an amount of the residue of the one or more crosslinking monomers in the shell by about 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, or 0.1, mol % of that amount or less.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the at least one core polymer is the reaction product of a) and b) and the at least one shell polymer is independently the reaction product of a), b), and d).
  • a1 or a2 is present in an amount of less than about 10 mol%, then e1 or e2, respectively, is present in an amount of greater than about 10 mol% and up to any amount described above relative to e1 and/or e2.
  • one or more method steps, process steps, components, etc. may be used herein as is described in WO 2019/096976 and/or U.S. 8,673,277, each of which is expressly incorporated herein in its entirety by reference in non-limiting embodiments.
  • Method of Forming the Composite Particle [00221] This disclosure also provides various methods of forming the composite particle.
  • the method may include, consist essentially of, or consist of, the steps of: introducing at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent into a polymerization reactor; polymerizing the at least one acrylate monomer and the silane monomer, silanol monomer, and/or silane or silanol chain transfer agent in the polymerization reactor to form the acrylate polymer; combining the acrylate polymer and the silica particle; and 64 PCT PATENT APPLICATION 364.1746PC3 reacting the acrylate polymer and the silica particle via a condensation reaction to form the composite particle wherein the acrylate polymer is attached to the
  • the step of introducing may be any known in the art.
  • the at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent may be mixed or combined in one or more parts, in a batch or semi-batch or continuous process. This step may occur under any conditions chosen by one of skill in the art.
  • the at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent may be any described herein or any known in the art.
  • the silane is typically converted to a silanol.
  • the step of polymerizing may also be any known in the art and occur under temperature, pressure, and time conditions as chosen by the skilled person.
  • the polymer and the silica particle may be combined in one or more portions and in a batch, semi-batch or continuous process. This step will typically occur in the coating manufacturing process but may also occur in the Silica slurry manufacturing process. This step may occur under any conditions chosen by one of skill in the art.
  • Relative to the step of reacting, the polymer and the silica particle may be reacted under any conditions chosen by the skilled person.
  • the step of reacting occurs at a pH of about 7 to about 10, e.g.7, 7.5, 8, 8.5, 9, 9.5 or 10.
  • the polymer and the silica particle may be reacted via a condensation reaction to form the composite particle wherein the polymer is attached to the surface of the silica particle via an O-Si bond.
  • This reaction may occur using any mechanism, procedure, and conditions known in the art.
  • all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.
  • the method further includes a step of hydrolyzing the silane monomer to form a silanol monomer in the presence of water or at least one acidic monomer or acid before, during or after the step of polymerizing, and the step of polymerizing occurs at a pH of about 1 to about 7, e.g. about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7.
  • This disclosure also provides a second method of forming the composite particle wherein the method may include, consist essentially of, or consist of, the steps of: combining the comb polymer, the acrylate polymer, and/or the core shell polymer, and the silica particle having the surface that is functionalized with the least one R-OH group; and reacting the comb polymer and the silica particle via a condensation reaction to form the composite particle wherein the polymer is attached to the surface of the silica particle via an O-Si bond.
  • the step of reacting occurs at a pH of about 5 to about 11, e.g.
  • a condensation reaction occurs much more quickly at a pH of about 9 as compared to a pH of about 4 which would suggest that it is desirable to conduct the condensation reaction at a pH of about 8 to about 9 because the condensation reaction is much faster than the hydrolysis react at that pH.
  • storage of the polymer may be done at a low pH, e.g. about 4 to about 5, because condensation is slower than hydrolysis at that pH. This gives the polymer storage stability and then the condensation reaction can take place at a higher pH of about 8 to about 9 to form the composite particle.
  • the reaction to form the composite particles may occur at any point.
  • silanol groups of any of the polymers herein may react with the Silica thereby forming the composite particles during any step of a method to form a paint, a coating composition, cosmetics, sunscreens, etc. or any composition described herein.
  • the composite particles may be formed during the formation of the paint, coating composition, cosmetics, sunscreens, etc. or may be formed entirely independently and later added to the paint, coating composition, cosmetics, sunscreens, etc. or any composition described herein.
  • the reaction to form the composite particles occurs entirely independently from the formation of the composition.
  • compositions/Formulations [00232] This disclosure also provides a composition or formulation that includes the composite particle.
  • the composition is not particularly limited and may be any known in the art.
  • the composition may be a paint or coating.
  • the composite particle may be included in the paint or coating in an amount of from about 1 to about 60 about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 5 to about 50, about 10 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, weight percent based on a total weight of the composition.
  • the formulation is a paint composition that includes (1) water and/or an organic solvent; (2) an optional binder; (3) an optional pigment; and (4) the composite particle.
  • the water may be included in an aqueous paint composition.
  • the composition may be a solvent based composition and include the organic solvent, which itself may be any known in the art of solvent based paints.
  • the paint composition may be further described as water borne flat, semi-flat, semi-gloss, or gloss paint compositions.
  • the components of paint compositions include typically a solvent, typically water, for latex paints, binder, pigment and extenders and additives.
  • binders are typically latex binders such as all acrylate systems, polyvinyl acetate, copolymers of vinyl acetate and acrylate, copolymers of vinyl acetate and ethylene, copolymers of vinyl acetate, ethylene, and vinyl chloride, and copolymers of styrene and acrylate.
  • the latex binders are often stabilized with anionic surfactants.
  • Extenders are paint additives that are insoluble in the binder and water. They are added to modify the flow and mechanical properties of the paint as well as the permeability, gloss and leveling characteristics of the paint film. White extender pigments are added to paints to lower their cost or improve their properties.
  • Additives include rheology modifiers and opaque polymers.
  • the rheology modifiers include cellulosic derivatives, hydrophobically modified alkali swellable polymers, inorganic 67 PCT PATENT APPLICATION 364.1746PC3 material such as clays, Nonionic Synthetic Associative Thickeners (NSAT’s), and Nonionic Polyurethane Associative Thickeners (HEUR’s) and similar materials.
  • the composition may optionally include other known additives, such as additional dispersing agents, anti-foaming agents, biocides, pH control agents, wetting agents, materials to improve freeze thaw stability, leveling aids, coalescing agents and/or polymeric or oligomeric binders.
  • additional dispersing agents such as additional dispersing agents, anti-foaming agents, biocides, pH control agents, wetting agents, materials to improve freeze thaw stability, leveling aids, coalescing agents and/or polymeric or oligomeric binders.
  • the paint composition may also include one or more pigments or be free of one or more pigments. Suitable pigments include inorganic pigments like titanium dioxide (independent of the type of this disclosure), coated titanium dioxide (also independent of the type of this disclosure), titania, iron oxides (red, yellow, brown and black), zinc oxide, chrome pigment, ultramarine pigments, cobalt pigments (cobalt blue) and organic pigments like e.g.
  • azo pigments examples include: monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36, 38, 64, and 67; C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:, 53, 53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191:1, 208, 210, 245, 247, and 251; C.I.
  • suitable inorganic color pigments are: white pigments: titanium dioxide (C.I.
  • Pigment White 6 zinc white, pigment grade zinc oxide; zinc sulfide, litho-pone; black pigments: iron oxide black (C.I. Pigment Black 11), iron manganese black, spinel black (C.I. Pigment Black 27); carbon black (C.I. Pigment Black 7); chromatic pigments: chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green 50); ultramarine green; cobalt blue (C.I. Pigment Blue 28 and 36; C.I. Pigment Blue 72); ultramarine blue; manganese blue; ultramarine violet; cobalt violet; manganese violet; red iron oxide (C.I.
  • Pigment Red 101 cadmium sulfoselenide (C.I. Pigment Red 108); cerium sulfide (C.I. Pigment Red 265); molybdate red (C. I. Pigment Red 104); ultramarine red; brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown, spinel phases and corundum phases (C.I. Pigment Brown 29, 31, 33, 34, 35, 37, 39, and 40), chromium titanium yellow (C.I. Pigment Brown 24), chrome orange; cerium sulfide (C.I. Pigment Orange 75); yellow iron oxide (C.I. Pigment Yellow 42); nickel titanium yellow (C.I. Pigment Yellow 53; C.I.
  • the pH of the composition can be adjusted with any combination of acidic and/or basic pH adjusting agents known to the art.
  • an alkaline material is incorporated into the composition and can be referred to as a neutralizing agent or pH adjusting agent.
  • inorganic bases include but are not limited to the alkali metal hydroxides (especially sodium, potassium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like; and 69 PCT PATENT APPLICATION 364.1746PC3 mixtures thereof.
  • organic bases include but are not limited to triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L- arginine, aminomethyl propanol, 2-amino 2-hydroxymethyl-1,3-propanediol, and PEG-15 cocamine.
  • TAA triethanolamine
  • diisopropanolamine triisopropanolamine
  • aminomethyl propanol aminomethyl propanol
  • dodecylamine cocamine
  • oleamine morpholine
  • triamylamine triethylamine
  • tetrakis(hydroxypropyl)ethylenediamine L- arginine
  • aminomethyl propanol 2-amino 2-hydroxymethyl-1,3-propanedio
  • any material capable of increasing the pH of the composition is suitable.
  • Various acidic materials can be utilized as a pH adjusting agent.
  • Such acidic materials include organic acids and inorganic acids, for example, acetic acid, citric acid, tartaric acid, alpha- hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof.
  • the addition of the acidic pH adjusting agent can be incorporated after the addition of the basic pH adjusting agent in the composition.
  • Buffering agents can also be used. Suitable buffering agents include, but are not limited to, alkali or alkali earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates, and the like, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate, and sodium carbonate. Phosphates such as sodium or potassium tripolyphosphate may be particularly useful.
  • the pH adjusting agent and/or buffering agent can be utilized in any amount necessary to obtain and/or maintain a desired pH value in the composition.
  • the composition may include, or be free of, other ingredients, for example, fluidizing agents, anti-sedimentation agents, plasticizers, surfactants, anti-foam agents, rheology modifiers, levelling agents, gloss modifiers, preservatives, pH adjustors such as organic amines, biocides, and the like, and combinations thereof.
  • Conventional additives may include, but are not limited to, dispersants, antioxidants, UV stabilizers and absorbers, surfactants, wetting agents, leveling agents, antifoaming agents, anti-cratering agents, or combinations thereof.
  • one or more organic liquids which may be used as film-forming resins can be used.
  • the composition may further include, or be free of, a non-ionic synthetic associative thickener (NSAT).
  • NSAT non-ionic synthetic associative thickener
  • Non-ionic synthetic associative thickeners can be used to provide viscosity and rheological control. These thickeners are typically non-ionic, meaning they do not carry any net charge in solution. These thickeners typically work by forming associations or interactions with other molecules, such as water or polymer chains, to increase viscosity.
  • Hydrophobically Modified Ethoxylated Urethanes (HEUR) thickeners typically include a polyethylene oxide (PEO) backbone with hydrophobic groups (such as alkyl chains) attached via urethane linkages. These hydrophobic groups interact with each other and with the hydrophobic domains of other molecules, leading to thickening.
  • PEO polyethylene oxide
  • hydrophobic groups such as alkyl chains
  • the composition includes less than about 2, 1.5, 1, 0.5, or 0.1, weight % actives of a hydrophobically modified ethoxylated polyurethane (HEUR) based on a total weight of the composition.
  • HEUR hydrophobically modified ethoxylated polyurethane
  • the composition may be free of such a polyurethane.
  • Hydrophobically Modified Cellulosics (HMHECs) thickeners are cellulose derivatives modified with hydrophobic groups, such as alkyl or alkylaryl moieties, attached to the cellulose backbone. These hydrophobic groups facilitate the association of cellulose chains, leading to increased viscosity.
  • Hydrophobically Modified Polyacrylic Acid (HMPAA) thickeners are based on polyacrylic acid (PAA) or its derivatives modified with hydrophobic groups. These hydrophobic modifications allow the polymer chains to associate with each other and with other molecules in the system, resulting in thickening.
  • Hydrophobically Modified Polyurethanes (HMPU) thickeners are polyurethane-based polymers modified with hydrophobic groups. Similar to other associative thickeners, the hydrophobic groups facilitate the association of polymer chains, leading to viscosity enhancement.
  • inclusion of one or more non-ionic synthetic associative thickeners can build KU to unacceptable levels without a corresponding increase in ICI to desired levels.
  • the non-ionic synthetic associative thickener is present in an amount of from about 0.01 to about 5, about 0.05 to about 2%, or about 0.1 to about 1, weight percent, based on a total weight of the composition.
  • this amount is from about 0.01 to about 0.09, about 0.02 to about 0.08, about 0.03 to about 0.07, about 0.04 to about 0.06, about 0.04 to about 0.05, from about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.4 to about 0.5, about 1 to about 5, about 2 to about 4, or about 2 to about 3, weight percent, based on a total weight of the composition.
  • all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the composition exhibits an ICI viscosity of greater than about 0.5 Poise and exhibits a KU viscosity of less than about 140 Krebs units. In other embodiments, the composition exhibits an ICI viscosity of greater than about 0.6 Poise and exhibits a KU viscosity of less than about 140 Krebs units. In various embodiments, the ICI viscosity is from about 0.6 to about 2, about 0.7 to about 2, about 0.8 to about 2, about 0.9 to about 1.9, about 1 to about 1.8, about 1.2 to about 1.7, about 1.3 to about 1.6, about 1.4 to about 1.5, Poise.
  • the ICI viscosity is greater than about 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9, Poise. In still other embodiments, the ICI viscosity is from about 1.2 to about 1.7, about 1.2 to about 1.6, about 1.2 to about 1.5, about 1.5 to about 2, about 1.6 to about 1.9, about 1.6 to about 1.8, about 1.5 to about 1.8, etc., Poise, typically measured at about 25°C. ICI viscosity can be determined using methods in accordance with ASTM D4287, ISO 2884 and BS 2900.
  • ICI viscosity is typically obtained using a Brookfield CAP 2000+ ICI cone and plate viscometer, high torque model, available from AMETEK Brookfield with USA headquarters in Middleboro, MA. The model is in compliance with ASTM D4287, ISO 2884 and BS 2900. Samples are typically analyzed for ICI viscosity at 25°C, 900 RPM, with a number 1 spindle. Sample temperature is first allowed to equilibrate between the cone and plate for 60 seconds, and then the measurement is run over 30 seconds.
  • the viscosity value is obtained using a Cone/Plate Type Viscometer and gives information about the flow properties of the material under high-shear conditions similar to those encountered during application: brushing, spraying, electrostatic disk, or roll coating.
  • all whole and fractional values and ranges of whole and fractional 72 PCT PATENT APPLICATION 364.1746PC3 values including and between each value set forth above, are hereby expressly contemplated for use herein.
  • the composition can exhibit a KU viscosity of less than about 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, or 90, Krebs units.
  • the KU viscosity is from about 90 to about 140, about 95 to about 135, about 100 to about 130, about 105 to about 125, about 110 to about 120, about 115 to about 120, about 100 to about 110, about 100 to about 105, or about 105 to about 110, Krebs units typically measured at about 23°C.
  • KU viscosity is determined using ASTM D562.
  • KU viscosity is typically reported in Krebs units (KU), which tend to be unique to Stormer viscometers and the like. Vibrating viscometers, such as resonant or vibrational viscometers, can also be used.
  • Pigment volume concentration is used to describe the volume (not weight) of pigment in a paint film.
  • PVC denotes how much of the volume of the paint film is made up of pigment versus the amount made up of binder.
  • Critical pigment volume concentration or CPVC is the pigment concentration where the pigments are packed as close as possible and the binder is exactly the amount required to fill the space between the pigments.
  • the PVC is typically lower than the CPVC.
  • the PVC is typically higher than the CPVC.
  • a KU viscosity of from about 95 to about 105 and an ICI viscosity of about 1.2 to about 1.5 is desirable.
  • the KU viscosity typically is from about 95 to about 120 while the ICI viscosity is typically about 0.6 or greater. In certain geographies the contractor will dilute the formulation such that a lower drop in KU viscosity can be useful.
  • the composition may be formed using any method chosen by one of skill in the art. For example, the method may include the steps of combining one or more of the aforementioned 73 PCT PATENT APPLICATION 364.1746PC3 components with one another in one or more parts and in a batch or continuous process.
  • Example 1 - Comb Polymer of Formula (I) for the Composite Particle [00259] 247 grams of water and 7.58 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1-liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 80 °C with overhead stirring and nitrogen sparge for at least 1 hr.
  • a monomer pre-emulsion mixture was prepared as follows: 240 grams water and 7.58 grams 30% sodium lauryl sulfate solution in water (Stanfax 234), 79.9 grams of methoxy polyethylene glycol 750 methacrylate, 17.8 grams methacrylic acid, 135.4 grams methyl methacrylate, 2.7 grams of vinyl trimethoxy silane and 3.4 grams of dodecyl mercaptan, was added to the contents of the graduated cylinder with agitation.
  • a seed stage was then performed as follows: 24 grams of the monomer pre-emulsion mixture was added over a period of two minutes, subsurface, to the reactor contents. This was agitated for 15 minutes, and then a seed stage initiator solution including 0.21 grams ammonium persulfate dissolved in 17.5 grams water was added as a shot to the reactor contents. This was allowed to stir at 80 °C for an additional 15 minutes. [00262] The remaining monomer pre-emulsion mixture was slowly added to the reactor contents, subsurface, for 120 minutes.
  • the colloidal silica has a density at 20°C of about 1.075 to about 1.099 g/cm3, SiO2 content of about 13.0 - 16.0 wt%, a pH at 20°C of about 9.0 - 11.4, a Viscosity at 20°C ⁇ about 8 cP, an ethanol content of about 2.5 wt%, and an average particle size of about nm.
  • 20% NaOH and then 10% NaOH was added to adjust the pH to about 8-10. This mixture was stirred for 50 oC for 12 hours.
  • the final solids and pH of these composite materials are listed in the tables below: Polymer Silica of 20% 10%
  • the final products were clear water white solutions and have the structure generally shown in FIG. 9.
  • Example 3 Dirt Pick up resistance of Composite Particles of Examples 2A and 2B: [00267] Dirt Pick up resistance (DPUR) testing was done in a commercial paint formulation by adding 1.5wt% active of composite particles of Examples 2A and 2B and comparing results to the same formulation without any of the Examples 2A and 2B. Films were then drawn on aluminum substrates and dried for two days at room temperature followed by curing via UV exposure for 48 hours. A synthetic carpet dirt was applied to one half of the drawdown and left overnight.
  • DPUR Dirt Pick up resistance
  • Example 4 - Core Shell Polymer For The Composite Particle [00269] 273.5 grams of water and 5.63 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1-liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions.
  • a “core” mixture was prepared by adding 37.7 grams methacrylic acid and 3.4 grams C16-1820EO associative monomer to a solution of 276.9 grams water and 5.72 grams 30% sodium lauryl sulfate solution in water (Stanfax 234) in a beaker. The contents were dispensed into a graduated cylinder with overhead agitation. A monomer solution was prepared by adding 24.08 grams methyl methacrylate, 78.8 grams ethyl acrylate, 96.73 grams hydroxypropyl acrylate, and 0.301 grams n-dodecyl mercaptan to a glass beaker.
  • the monomer solution was added to the contents of the graduated cylinder with agitation, and the remnants in the beaker were rinsed out into the graduated cylinder with 10.69 grams water.
  • a seed stage was then performed as follows: 27 milliliters of the core monomer mixture were added to the reactor contents over a 2-minute period. This was agitated for 15 minutes, and then a seed stage initiator solution comprising 0.3 grams ammonium persulfate dissolved in 21.4 grams water was added as a shot to the reactor contents. This was allowed to stir for an additional 15 minutes.
  • the “shell” monomer solution was prepared by mixing 0.62 grams C16-18 20EO associative monomer, 4.03 grams methyl methacrylate, 13.2 grams ethyl acrylate, 25.72 grams hydroxypropyl acrylate, 0.0504 grams n-dodecyl mercaptan, 0.31 methacrylic acid, 0.54 grams vinyltrimethoxysilane, 3.0378 grams trimethylolpropane triacrylate, and then the contents were mixed thoroughly. [00274] An initiator feed comprising 30 milligrams ammonium persulfate dissolved in 2.68 grams water was also added over the same 20 minutes as the shell monomer mixture.
  • Example 5 Core Shell Polymer For The Composite Particle: [00276] 278.1 grams of water and 5.7 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1 liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 85 °C with overhead stirring and nitrogen sparge for at least 1 hour.
  • a “core” mixture was prepared by adding 75.9 grams methacrylic acid and 1.2 grams C16-1820EO associative monomer to a solution of 292.4 grams water and 5.72 grams 30% sodium lauryl sulfate solution in water (Stanfax 234) in a beaker. The contents were dispensed into a graduated cylinder with overhead agitation. A monomer solution was prepared by adding 75.2 grams methyl methacrylate, 87.5 grams ethyl acrylate, and 0.135 grams n-dodecyl mercaptan to a glass beaker.
  • the monomer solution was added to the contents of the graduated cylinder with 77 PCT PATENT APPLICATION 364.1746PC3 agitation, and the remnants in the beaker were rinsed out into the graduated cylinder with 10.9 grams water.
  • a seed stage was then performed as follows: 5 weight percent of the core monomer mixture were added to the reactor contents over a 2-minute period. This was agitated for 15 minutes, and then a seed stage initiator solution comprising 0.3 grams ammonium persulfate dissolved in 21.4 grams water was added as a shot to the reactor contents. This was allowed to stir for an additional 15 minutes.
  • the “shell” monomer solution was prepared by mixing 0.24 grams C16-18 20EO associative monomer, 15.2 grams methacrylic acid, 15.04 grams methyl methacrylate, 17.5 grams ethyl acrylate, 0.75 grams vinyltrimethoxysilane, 0.099 grams ethylene glycol dimethacrylate, and then mixing the contents thoroughly. [00281] At the completion of the shell monomer mixture addition, 0.21 grams of ammonium persulfate dissolved in 16.1 grams water was fed into the reactor over a period of 50 minutes. Then the reactor contents were cooked at 90 C for one hour.
  • Examples 6A-6B Composite Particles Using Core Shell Polymers: [00282] The following composite polymers are produced by mixing the amount of the polymers of Example 4 and 5 with the amount of the colloidal silica from Examples 2, as shown below. Next a 10% NaOH is added to adjust the pH in the 8-10 range. This mixture is stirred for 50 oC for 12 hours.
  • a monomer pre-emulsion of 152.4 grams of water, 7.7 grams of 30% sodium lauryl sulfate solution in water, 83.9 grams of methyl methacrylate, 119 .6 grams butyl acrylate, and 1.6 grams of methacrylic acid was added over 72 minutes.
  • An initiator solution comprising 0.47 grams sodium persulfate dissolved in 26.75 grams water was added at a rate of 0.26 grams per minute over 72 minutes with some of the solution leftover for the next stage.
  • the reactor contents was held at 84 °C for 30 minutes.
  • a second monomer pre-emulsion of 56.2 grams of water, 3.2 grams of 30% sodium lauryl sulfate solution in water, 27.4 grams of methyl methacrylate, 50.0 grams butyl acrylate, 1.54 grams of vinyl trimethoxy silane and 0.7 rams of methacrylic acid was added over 28 minutes. Simultaneously, the rest of the initiator solution was added over 28 minutes. The reactor contents was held at 84 °C for 30 minutes. The final product was a water white emulsion with a solid content of 32.5%.
  • Example 8 Composite Particle Using Acrylate Polymer: [00285] The following composite polymers are produced by mixing the amount of the polymer of Example 7 with the amount of the colloidal silica from Examples 2, as shown below. Next a 10% NaOH is added to adjust the pH in the 8-10 range. This mixture is stirred for 50 oC for 12 hours. Polymer of Polymer of Colloidal Silica Example 7 (g) Example 5 (g) (178% solution) [00286] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way.

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Abstract

A composite particle includes the reaction product of: A. a silica particle; and B. a polymer that includes at least one Si-OR' group wherein R' is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: a comb polymer; an acrylate polymer comprising the at least one Si-OR' group, a core-shell polymer; and combinations thereof.

Description

PCT PATENT APPLICATION 364.1746PC3 COMPOSITE PARTICLE CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 63/675,431 filed on July 25, 2024; U.S. Provisional Application No. 63/675,433 filed on July 25, 2024; U.S. Provisional Application No. 63/762,782 filed on February 25, 2025; and U.S. Provisional Application No. 63/813,355 filed on May 28, 2025, each of which is incorporated herein by reference in its entirety. TECHNICAL FIELD [0002] The present disclosure generally relates to composite particles. More particularly, this disclosure relates to a silica particle having a surface and a particular polymer attached to the surface via an O-Si bond. BACKGROUND [0003] Per- and polyfluoroalkyl substances (PFAS) have traditionally been used in paint formulations due to their excellent performance characteristics, particularly in providing dirt pickup resistance (DPUR) and block resistance. Dirt pickup resistance helps maintain the aesthetic quality of painted surfaces by preventing the accumulation of dust, grime, and pollutants, while block resistance prevents painted surfaces from sticking to one another, especially under pressure or elevated temperatures. These properties have made PFAS valuable additives in both architectural and industrial coatings. [0004] However, PFAS are increasingly recognized as undesirable because of its persistency in the environment and is a “forever chemical”. Therefore, there is a need to replace PFAS additives in paint formulations with sustainable alternatives. Developing PFAS-free paints that maintain the same high standards of performance as their predecessors —especially in dirt pickup and block resistance—is technically challenging. Therefore, there remains room for improvement. BRIEF SUMMARY [0005] This disclosure provides a composite particle that includes the reaction product of: A. a silica particle; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: 1 PCT PATENT APPLICATION 364.1746PC3 (1) a comb polymer having the formula (I): a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5 is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9 is H or CH3; 2 PCT PATENT APPLICATION 364.1746PC3 (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1; (2) an acrylate polymer comprising the at least one Si-OR’ group, (3) a core shell polymer comprising: at least one core polymer that is the polymerization reaction product of a first monomer mixture comprising: a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; and f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; g1) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a1) is not present in said first monomer mixture then e1) is present in said first monomer mixture; wherein if f1) is not present in said first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said first monomer mixture; wherein if f1) is present in said first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said first monomer mixture; wherein at least one of b1) and f1) is present in said first monomer mixture; and 3 PCT PATENT APPLICATION 364.1746PC3 at least one shell polymer disposed about said at least one core polymer wherein said at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture comprising: a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; g2) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a2) is not present in said second monomer mixture then e2) is present in said second monomer mixture; wherein if f2) is not present in said second monomer mixture then a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said second monomer mixture; wherein if f2) is present in said second monomer mixture then a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said second monomer mixture; wherein at least one of b2) and f2) is present in said second monomer mixture; and wherein at least one of said first monomer mixture and said second monomer mixture comprises a1) or a2) in an amount greater than zero mol %, respectively; wherein at least one of g1) and g2) is utilized; and (4) combinations thereof. Surprisingly, it was discovered that the composite particles of this disclosure provide dirt pickup resistance (DPUR) and block resistance. 4 PCT PATENT APPLICATION 364.1746PC3 BRIEF DESCRIPTION OF THE DRAWINGS [0006] The present disclosure will hereinafter be described in conjunction with the following drawing figures, wherein: [0007] FIG. 1 is a drawing of a silica particle without any polymer bonded thereto; [0008] FIG.2 is a drawing of an embodiment of the composite particle that shows both attachment of the comb polymer and the acrylate polymer, even though only one or neither polymer is required to be present; [0009] FIG. 3 is a cross-sectional view of one embodiment of the core shell polymer wherein each of an at least one core polymer, a first shell polymer, and a second shell polymer has a cross- link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is greater than the cross-link density of the first shell polymer and greater than the cross-link density of the at least one core polymer; [0010] FIG. 4 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the first shell polymer and greater than the cross- link density of the at least one core polymer; [0011] FIG. 5 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is greater than the cross-link density of the at least one core polymer and greater than the cross-link density of the first shell polymer; [0012] FIG. 6 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is greater than the cross-link density of the at least one core polymer, and the cross-link density of the second 5 PCT PATENT APPLICATION 364.1746PC3 shell polymer is less than the cross-link density of the at least one core polymer and less than the cross-link density of the first shell polymer; [0013] FIG. 7 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the at least one core polymer and greater than the cross-link density of the first shell polymer; [0014] FIG. 8 is a cross-sectional view of one embodiment of the core shell polymer of this disclosure wherein each of the at least one core polymer, the first shell polymer, and the second shell polymer has a cross-link density, the cross-link density of the first shell polymer is less than the cross-link density of the at least one core polymer, and the cross-link density of the second shell polymer is less than the cross-link density of the at least one core polymer and less than the cross-link density of the first shell polymer; and [0015] FIG. 9 is a drawing of a composite particle of the Examples 2A-2B. DETAILED DESCRIPTION [0016] The following detailed description is merely exemplary in nature and is not intended to limit the current composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description. [0017] Embodiments of the present disclosure are generally directed to polymer composites with silica, compositions including the same, and methods for forming the same. For the sake of brevity, conventional techniques related to making polymers and such compositions may not be described in detail herein. Moreover, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein. In particular, various steps in the manufacture of polymers and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details. [0018] In this disclosure, the terminology “about” can describe values ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%, in various embodiments. Moreover, it is contemplated that, in various non-limiting 6 PCT PATENT APPLICATION 364.1746PC3 embodiments, it is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited. It is also contemplated that all isomers and chiral options for each compound described herein are hereby expressly contemplated for use herein in various non-limiting embodiments. Moreover, in this disclosure, the subscripts of non-chemical elements, e.g. (R1, R2, etc.) do not indicate that more than 1 group (e.g. R group) is present. They are used merely to differentiate between groups. However, the subscripts for chemical elements such as carbon (e.g. C1-C22) are indicative of the total number of atoms of that chemical element. [0019] Throughout this disclosure, the terminology percent "actives" is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person. [0020] In various embodiments, the terminology “free of” describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of” describes embodiments that have zero weight percent of the compound or element at issue. [0021] The terminology “consists essentially of” may describe various non-limiting embodiments that are free of one or more optional compounds described herein and/or free of one or more polymers, surfactants, additives, solvents, etc. [0022] It is to be understood that the subscripts of polymers are typically described as average values because the synthesis of polymers typically produces a distribution of various individual molecules. [0023] The polymer, particles, and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein. Composite Particle [0024] This disclosure provides a composite particle that includes the reaction product of: 7 PCT PATENT APPLICATION 364.1746PC3 A. a silica particle; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: (1) a comb polymer having the formula (I): a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; 8 PCT PATENT APPLICATION 364.1746PC3 (vii) R5 is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1; (2) an acrylate polymer comprising the at least one Si-OR’ group, (3) a core shell polymer comprising: at least one core polymer that is the polymerization reaction product of a first monomer mixture comprising: a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; and f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; g1) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a1) is not present in said first monomer mixture then e1) is present in said first monomer mixture; wherein if f1) is not present in said first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said first monomer mixture; 9 PCT PATENT APPLICATION 364.1746PC3 wherein if f1) is present in said first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said first monomer mixture; wherein at least one of b1) and f1) is present in said first monomer mixture; and at least one shell polymer disposed about said at least one core polymer wherein said at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture comprising: a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; g2) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a2) is not present in said second monomer mixture then e2) is present in said second monomer mixture; wherein if f2) is not present in said second monomer mixture then a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said second monomer mixture; wherein if f2) is present in said second monomer mixture then a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said second monomer mixture; wherein at least one of b2) and f2) is present in said second monomer mixture; and wherein at least one of said first monomer mixture and said second monomer mixture comprises a1) or a2) in an amount greater than zero mol %, respectively; 10 PCT PATENT APPLICATION 364.1746PC3 wherein at least one of g1) and g2) is utilized; and (4) combinations thereof. [0025] The terminology “composite particle”, as used herein, typically describes a particle that includes, or is made up of, smaller particles or parts or pieces. For example, in this disclosure, the composite particle includes the silica particle (e.g. a first part of the composite particle), e.g. as shown in FIG.1, and a polymer (e.g. a second part of the composite particle) attached to the surface of the silica particle, e.g. as shown in FIG. 2. In this type of example, the composite particle includes the first and second “parts” attached or bonded together. However, the composite particle may alternatively be described as a single particle that is formed from two or more substituents, e.g. the silica particle and the polymer. [0026] The composite particle is not particularly limited in size or shape. For example, the size of the composite particle may be approximately the size of the silica particle itself (e.g. plus a percentage that is greater than about zero and up to about 1%) because the polymer attached thereto does not add appreciable physical size to the overwhelmingly larger physical size of silica particle itself. Accordingly, any particle size or shape described herein may describe the silica particles themselves or the composite particle. [0027] Silica Particle [0028] Crystalline silica is a form of silicon dioxide (SiO₂) that has a well-ordered, repeating atomic structure, distinguishing it from amorphous silica, which lacks such organization. In this disclosure, crystalline and/or amorphous silica may be used. Crystalline silica exists in several polymorphs, with the most common being quartz, which is the most abundant and stable form under normal environmental conditions. Quartz is naturally present in sand, soil, and rock, and is widely used in construction and industrial materials. Cristobalite is another form of crystalline silica that develops at high temperatures, often during industrial processes like ceramic firing or the calcination of diatomaceous earth. It is considered more chemically reactive and potentially more hazardous than quartz. Tridymite, also formed at elevated temperatures, is less common and found mainly in high-temperature industrial environments or volcanic rocks. There are also rarer high-pressure forms of crystalline silica, such as coesite and stishovite, which typically form under extreme pressure conditions like those found in meteorite impact sites. Any of the above may be used. 11 PCT PATENT APPLICATION 364.1746PC3 [0029] The silica particle has a surface, i.e., an outer surface. The smoothness or roughness of the surface is not particularly limited and can be any known in the art. Similarly, the porosity of the surface is not particularly limited and also may be any known in the art. Moreover, the surface charge (e.g. zeta potential) of the surface is also not particularly limited and also may be any known in the art. [0030] The silica utilized herein may be in any form known in the art. The preferred type of silica is colloidal silica. Colloidal silicas are suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase. [0031] In various embodiments, the silica is utilized as a sol including colloidal silica, e.g. also known as a silica sol. Herein, the terminology “sol” typically describes a stable dispersion of colloidal silica (SiO2) particles in a liquid, such as water. The silica sol may also be described as a colloidal silica dispersion. [0032] The sol includes colloidal silica, e.g. silica particles. In various embodiments, the terms “silica sol” and “colloidal silica” have the same meaning. In other embodiments, the term “colloidal silica” refers to a dispersion comprising about 1 to about 50 wt% silica particles dispersed in an aqueous medium. The aqueous medium may comprise organic solvent, but where it does so it typically comprises less than 10 wt% organic solvent. If an organic solvent is present, the aqueous medium more typically includes no more than about 5 wt% organic solvent. Typical organic solvents, when present, are water- miscible, for example being chosen from one or more of C1-4 alkyl alcohols, C1-4 aldehydes, C1-4 ketones, C1-4 carboxylic acids their C1-4 alkyl esters, and combinations thereof. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0033] It is contemplated that the sol may include one or more individual types of colloidal silica. In such embodiments, at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both. Moreover, it is contemplated that the composition as a whole may include one or more independent sols. In such embodiments, at least one is of the type described herein and one or more additional types may be of the type described herein or of the type not described herein or may be a mixture of both. [0034] The sol itself is not particularly limited and can have a SiO2 content of from about 5 to 12 PCT PATENT APPLICATION 364.1746PC3 about 60 wt% depending on particle size. In various embodiments, this content is from about 10 to about 55, about 15 to about 50, about 20 to about 45, about 25 to about 40, or about 30 to about 35, weight % based on a total weight of the sol. The sol may or may not be diluted for use herein. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0035] Aqueous silica sols can be basic, having a pH of from about 2.0 to about 11 or 12, for example from about, 4.0 to about 11.0 or 6.0 to about 10.0. Other optional components of such sols include the presence of alkali metals, typically one or more of lithium, sodium and potassium. Typically sodium is the sole or predominant alkali metal. The alkali metals can be derived from soluble silicate solutions (e.g. water glass) that can be used to make the colloidal silica using conventional processes. Examples of suitable aqueous alkali metal silicates or water glass that can be used to make aqueous silica sols include lithium, sodium and potassium silicates, typically sodium silicate. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0036] The silica particles are typically amorphous nanoparticles, and most typically have a particle diameter of from about 2 to about 170 nm. In various embodiments, the colloidal silica particles typically have an average particle diameter of from about 2 to about 100 nm or from about 3 to about 75 nm. In further embodiments, the particle diameter is from about 4 to about 50 nm, from about 5 to about 30 nm or from about 7 to about 25 nm. In other embodiments, the particle diameter is from about 5 to about 25, about 10 to about 20, about 10 to about 15, etc. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0037] The particle diameter can be calculated from the titrated specific surface area using a method described in "The Chemistry of Silica", by Iler, K. Ralph, page 465, John Wiley & Sons (1979). Based on the assumption that the silica particles have a density of 2.2 g cm-3, and that all particles are of the same size, have a smooth surface area and are spherical, then the particle diameter (PD) can be calculated from Equation 1: PD (nm) = 2727/Surface Area (m2g-1) Equation 1 [0038] Other ways of measuring average particle diameters include ES-DMA (electro-spray 13 PCT PATENT APPLICATION 364.1746PC3 differential mobility analysis), CLS (centrifugal liquid analysis), SEM (scanning electron microscopy) and TEM (transmission electron microscopy). [0039] In other embodiments, e.g. for unmodified colloidal silica, the colloidal silica has an S value of from about 20 to about 95 %, for example from about 30% to about 90% or from about 50 to about 85% The S-value is measured and calculated as described by Iler & Dalton (Iler & Dalton; J. Phys. Chem. 60(1956), 955-957). The S-value indicates a degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0040] In various embodiments, the colloidal silica is made from particle growth from a soluble silicate or a polysilicic acid solution, and is not prepared by creating a dispersion from a solid form of silica nanoparticle. For example, in some embodiments, the colloidal silica is not derived from solid forms of silica such as amorphous forms of fumed silica, silica fume and precipitated silica. [0041] Optionally, the colloidal silica is not derived from crystalline forms of silica, such as micro-quartz or nano-quartz, which suffer the additional disadvantage of potential health risks. Soluble silicate-derived colloidal silicas tend to have less aggregation of the silica particles compared to dispersions made from solid forms of silica. This is because, in general, solid forms of silica nanoparticles tend to be in the form of agglomerates of the primary nanoparticles, and it is not usually possible to disperse such silicas to create a colloidal silica comprising predominantly the discrete primary particles because larger agglomerates tend to remain. The silica particles in such colloidal silicas therefore tend to settle (precipitate) relatively rapidly. In contrast, colloidal silicas made from particle growth from a soluble silicate or a polysilicic acid solution do not include such large silica agglomerates. They tend to be stable and do not typically noticeably gel or precipitate for many months, typically for greater than 12 months. [0042] In various embodiments, the colloidal silica is made by converting soluble alkali metal silicate to polysilicic acid (with a pH typically of from about 1 to about 3) by ion exchange or treatment with acid, and raising the pH to about 7 or more, typically about 8 to about 1112, for example about 9 to about 11, using a basic alkali metal salt such as alkali metal hydroxide or alkali metal silicate. The content of alkali metals in the starting silica sol can be of from about 0.1 to about 5.0 wt%, expressed as alkali metal oxide. In some embodiments, this content is from about 14 PCT PATENT APPLICATION 364.1746PC3 0.2 to about 3.0 wt%. In other embodiments, the silica concentration in the colloidal silica is of from about 1 to about 40 wt%, for example from about 2 to about 35 wt% or from about 3 to about 30 wt%. As used here, silica concentrations are typically expressed as SiO2. A typical minimum concentration is about 5 wt%, and most typical ranges are therefore about 5 to about 50 wt%, and more typically about 5 to about 40 wt%, for example about 5 to about 35 wt% or about 5 to about 30 wt%. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0043] In various embodiments, the colloidal silica particles typically have a surface area of from about 30 to about 1000 m2g-1, for example of from about 40 to about 700 m2g-1, such as of from about 60 to about 550 m2g-1 and more typically from 90 to about 400 m2g-1 and most typically from about 120 to about 250 m2g-1. The specific surface area of colloidal silica particles in a silica sol can be calculated from NaOH titration following the method of Sears (Sears; Anal. Chem., 1956, 28(12), 1981-1983). In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0044] The density of the silica sol is at least in part dependent on the silica content, and is typically of from about 1.01 to about 1.45 g cm-3, and typically of from about 1.01 to about 1.30 g cm-3. As an example, a silica sol of density 1.2 g cm-3 has typically a silica content of 30 wt-% SiO2 while a silica sol of density 1.4 g cm-3 has typically a silica content of 50-wt% SiO2. Density can be determined using ASTM D4052-18a. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0045] The viscosity of the silica sol is typically less than about 40, 35, 30, 25, or 20, 15, 10, or 5 cP, measured at about 20°C. Viscosities of silica sols, including those described herein, can be measured using a conventional rotational viscometer. A method that can be used is ASTM D4016-14. In various additional non-limiting embodiments, all values and ranges of values, both whole and fractional, including and between those described above are hereby expressly contemplated for use herein. [0046] In aqueous systems, the colloidal silica particles can be dispersed in the presence of stabilizing cations, which can be chosen from alkali metals (e.g. K+, Na+, Li+), ammonium 15 PCT PATENT APPLICATION 364.1746PC3 (NH4+), organic cations, quaternary amino, tertiary amino, secondary amino, and primary amino, or mixtures thereof. Typically, they are selected from alkali metals and ammonium. Examples of sols that can be used as starting aqueous silica sols include silica sols marketed under the name Levasil™ or Bindzil™ from Nouryon. Polymer [0047] Referring back to the polymer, the polymer includes the at least one Si-OR’ group wherein R’ is an alkyl group or H. The alkyl group is not particularly limited and may be any in the art. In various embodiments, R’ is a C1-C32 linear, branched, or cyclic alkyl group. In various embodiments, R’ has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0048] The polymer is attached to the surface of the silica particle via an O-Si bond. The O- Si bond may be formed by any reaction known in the art. Typically, the reaction is a condensation reaction such that an Si-O-Si bond is formed, e.g. as shown in the Figures. The polymer can be chosen from the comb polymer, the acrylate polymer, the core shell polymer, and combinations thereof. [0049] The reaction may occur at any point to form the composite particles. As just one example, reactive groups of any of the polymers herein may react with the silica thereby forming the composite particles during any step of a method to form a paint, a coating composition, cosmetics, sunscreens, etc. or any composition described herein. For example, the composite particles may be formed during the formation of the paint, coating composition, cosmetics, sunscreens, etc. or may be formed entirely independently and later added to the paint, coating composition, cosmetics, sunscreens, etc. or any composition described herein. Comb Polymer [0050] The comb polymer has the formula (I): 16 PCT PATENT APPLICATION 364.1746PC3 a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5 is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; 17 PCT PATENT APPLICATION 364.1746PC3 (xiii) R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1. [0051] As set forth above, a + b + c + d + e = 100 mol%. The particular amount of any one of a, b, c, d, and e is not particularly limited. For example, any one of a, b, c, d, and/or e can each independently be about 1 to about 99 mol percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0052] In various embodiments, a is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, a is from about 1 to about 25, about 2 to about 24, about 3 to about 23, about 4 to about 24, about 5 to about 25, about 6 to about 24, about 7 to about 23, about 8 to about 22, about 9 to about 21, about 10 to about 20, about 11 to about 19, about 12 to about 18, about 13 to about 17, about 14 to about 16, or about 15 to about 16, mol%. In another embodiment, a is from 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, or about 10 to about 11, mol %. In a further embodiment, a is about 6 to about 14, about 7 to about 13, about 8 to about 12, or about 9 to about 11, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0053] In various embodiments, b is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, b is from about 0 to about 95 mol%. In another embodiment, b is from about 60 to about 90, about 65 to about 85, about 70 to about 80, or about 75 to about 80, mol %. In another embodiment, b is from about 70 to about 85, about 70 to about 75, or about 80 to about 85, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between 18 PCT PATENT APPLICATION 364.1746PC3 those set forth above, are hereby expressly contemplated for use herein. [0054] In various embodiments, c is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, c is from about zero to about 90 mol%. In another embodiment, c is from about 2 to about 20, about 3 to about 19, about 4 to about 18, about 5 to about 17, about 6 to about 16, about 7 to about 15, about 8 to about 14, about 9 to about 13, about 10 to about 12, or about 11 to about 12, mol %. In another embodiment, c is about 5 to about 15, about 6 to about 14, about 7 to about 13, about 8 to about 12, about 9 to about 11, or about 10 to about 11, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0055] In various embodiments, d is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, d is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0056] In various embodiments, e is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, e is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, 19 PCT PATENT APPLICATION 364.1746PC3 including and between those set forth above, are hereby expressly contemplated for use herein. [0057] In the comb polymer, each of d and e is optional so long as at least one of d and e is greater than zero. For example, the comb polymer can have d without e or can have e without d, or can have d and e, but cannot be lacking both d and e. [0058] In still other embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, of each of a, b, c, d, and e, independently, are hereby expressly contemplated for use with each other herein. In other words, in various non-limiting embodiments, all combinations of amounts of a, b, c, d, and e, set forth above, such that a+b+c+d+e = 100%, are hereby expressly contemplated for use herein, even though each combination is not expressly set forth herein. [0059] In other embodiments, it is contemplated that an additional monomer, apart from a, b, c, d, and e, could be used. This monomer may be any known in the art, e.g. those that may react with acrylate monomers, any of the monomers described herein, the acrylate polymer, the comb polymer, etc. In such embodiments, then the total of a+b+c+d+e+additional monomer(s) = 100%. Just as above, all values and ranges thereof, both whole and fractional, including and between those set forth above, of each of a, b, c, d, e, and any additional monomer(s), independently, are hereby expressly contemplated for use with each other herein. In other words, in various non- limiting embodiments, all combinations of amounts of a, b, c, d, e, and any additional monomer(s) set forth above, such that a+b+c+d+e+additional monomer(s) = 100%, are hereby expressly contemplated for use herein, even though each combination is not expressly set forth herein. [0060] In other embodiments, n is about 1 to about 300. In various embodiments, n is about 1. In other embodiments, n is greater than 1. When n is > 1, then the individual -O-CHR6-CHR7- groups are the same or different. In still other embodiments, n is from 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6. In further embodiments, n is about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55. In other embodiments, n is about 10 to about 90, about 20 to about 80, about 30 to about 70, about 40 to about 60, or about 50. In further embodiments, n is about 25 to about 100, about 25 to about 50, about 50 to about 75, about 50 to about 100, about 25 to about 75, or about 75 to about 100. In other embodiments, n is from about 100 to about 300, about 110 to about 290, about 120 to about 280, about 130 to about 270, about 140 to about 260, about 150 20 PCT PATENT APPLICATION 364.1746PC3 to about 250, about 160 to about 240, about 170 to about 230, about 180 to about 220, about 190 to about 210, or about 200 to about 210. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0061] In a further embodiment, R6 and R7, which is referenced in the -O-CHR6-CHR7-group described above, is H or a C1-10 hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0062] Each of X, X1, and X2 may independently be O or NH. [0063] Moreover, R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R1 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0064] In other embodiments, R2 is -S-R11-Si(OR’)3. In various embodiments, if R2 is not that group then it may be any number of groups that are common to solution polymers including, but not limited to, H, CH3, or an end group derived from an initiator, an alcohol or glycol or non Si containing mercaptans. Relative to R11, in various embodiments, this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g.1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In other embodiments, R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R11 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0065] In further embodiments, R3 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R3 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, 21 PCT PATENT APPLICATION 364.1746PC3 this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0066] In other embodiments, each of R4 and R5 is independently H or CH3. [0067] R6 is H or a C1-10 hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0068] R7 is H or a C1-10 hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0069] In further embodiments, each of R8 and R9 is independently H or CH3. [0070] Relative to R10, this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein. [0071] Moreover, m is 0 or 1. [0072] In still other embodiments, one or more Si(OH)3 groups is optional meaning that one or more may be included or may be excluded from the comb polymer. [0073] In one embodiment: a is 1-25 mol%; b is 0-95 mol%; c is 0-90 mol%; and d is 0.05-10 mol%. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0074] In one embodiment: a is 0.5-75 mol%; 22 PCT PATENT APPLICATION 364.1746PC3 b is 0-99 mol%; c is 0-99 mol%; d is 0 -10 mol%; and e is 0-10 mol%. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0075] In one embodiment: a is 1-50 mol%; b is 10-90 mol%; c is 10-90 mol%; d is 0-10 mol%; e is 0-10 mol%; n is 1-200, wherein the -O-CHR6-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7 is H or CH3. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0076] In one embodiment: a is 2-10 mol%; b is 15-85 mol%; c is 15-85 mol%; d is 0.05-10 mol%; n is 5-150, wherein the -O-CH2-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7 is H or CH3. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0077] It is contemplated that the polymer itself, and for example, the composite particle as a whole, may be free of, or include less than, 5, 4, 3, 2, 1, 0.5, or 0.1, mol% of one or more other 23 PCT PATENT APPLICATION 364.1746PC3 polymers not described herein. For example, such polymers may be graft (co)polymers, (co)polymers, graft comb polymers, comb polymers that are not the comb polymer of this disclosure, or acrylate polymers that are not the acrylate polymer of this disclosure, etc. The composite particle may also include just a single type of comb polymer or a single type of acrylate polymer or both a single type of a comb polymer and a single type of an acrylate polymer, and thus be free of second types of comb polymers and/or acrylate polymers. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. Acrylate Polymer [0078] Referring now to the acrylate polymer, the acrylate polymer includes the at least one Si-OR’ group. The acrylate polymer is not limited in itself and may be any known in the art. For example, the acrylate polymer may be a homopolymer or a copolymer. The acrylate polymer may be or include the reaction product of any one or more acrylate monomers known in the art so long as the acrylate polymer includes the at least one Si-OR’ group. Non-limiting examples of suitable acrylate monomers include C1-C32 alkyl esters of acrylic and methacrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 10-hydroxydecyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-hexyldecyl (meth)acrylate, 2- octyldodecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, behenyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate; and C4-C32 alkyl amides of acrylic and methacrylic acid, including tertiary butyl (meth)acrylamide, t-octyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, n-octyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, and behenyl (meth)acrylamide. Other suitable co monomers include styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, iso-propyl styrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprylate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, butadiene, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene 24 PCT PATENT APPLICATION 364.1746PC3 acrylic acid, maleic acid, methacrylic acid, itaconic acidallyl methacrylate; and combinations thereof. Any one or more of the above monomers may be free or, or include, the at least one Si- OR’ group In other words, any one or more of the above monomers, each which may itself include, or be free of, the at least one Si-OR’ group, may be used to form the acrylate polymer of this disclosure so long as the acrylate polymer includes the at least one Si-OR’ group. [0079] The acrylate polymer can be formed using any method known in the including, but not limited to, free radical polymerization; emulsion polymerization; solution polymerization; suspension polymerization; bulk polymerization; radiation-induced polymerization; anionic polymerization; and/or controlled/living radical polymerization. Alternatively, the acrylate polymer can be provided from any commercial source. In the acrylate polymer that includes the at least one Si-OR’ group, the R’ group is as described above. [0080] In one embodiment, the polymer may be, include, consist essentially of, or consist of, the acrylate polymer to the exclusion of the comb polymer. Alternatively, the polymer may be, include, consist essentially of, or consist of, a combination of the comb polymer and the acrylate polymer. Moreover, the polymer may be, include, consist essentially of, or consist of, the comb polymer to the exclusion of the acrylate polymer. The terminology “consist essentially of” describes embodiments wherein the polymer is free of, or includes less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight or mole percent, of one or more polymers, elements, compounds, solvents, etc. that are not the polymer of this disclosure, i.e., that are extraneous polymers. [0081] In various embodiments, the acrylate polymer is the reaction product of an acrylate monomer that does not include the at least one Si-OR’ group and one or more silicon containing monomers, e.g. a silane and/or a silanol, that provide the at least one Si-OR’ group. [0082] In one embodiment, the acrylate polymer is the reaction product of a single acrylate monomer and one or both of a silane and a silanol. [0083] In another embodiment, the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, and one or both a silane and a silanol. In a further embodiment, the silane is vinyl trimethoxy silane and the silanol is vinyl trimethoxy silanol. [0084] In another embodiment, the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, styrene, 2-ethylhexyl acrylate and one or both a silane and a silanol. In a further embodiment, the silane is vinyl trimethoxy silane and the silanol is vinyl trimethoxy silanol. 25 PCT PATENT APPLICATION 364.1746PC3 [0085] In other embodiments, the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, and one or both of vinyl trimethoxy silane and vinyl trimethoxy silanol. [0086] In further embodiments, the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, and vinyl trimethoxy silanol. [0087] In yet another embodiment, the acrylate polymer is the reaction product of a first acrylate monomer, a second acrylate monomer, and one or both of a silane and a silanol. For example, any one or more of the following silanes and/or corresponding silanols may be utilized: trimethoxysilane/trimethylsilanol; triethoxysilane/triethylsilanol; vinyltrimethoxysilane/ vinyltrimethylsilanol; vinyltriethoxysilane/ vinyltriethylsilanol; (3-methacryloxypropyl) trimethoxysilane/(3-methacryloxypropyl)trimethylsilanol; (3-methacryloxypropyl) triethoxysilane/(3-methacryloxypropyl)triethylsilanol; (3-acryloxypropyl) trimethoxysilane/(3- acryloxypropyl) trimethylsilanol; (3-acryloxypropyl) triethoxysilane/(3-acryloxypropyl) triethylsilanol; (3-glycidoxypropyl)trimethoxysilane/(3-glycidoxypropyl)trimethylsilanol; (3- glycidoxypropyl)triethoxysilane/ (3-glycidoxypropyl)triethylsilanol; gamma- mercaptopropyltrimethoxy silane, mercaptopropyltriethoxy silane, mercapto silane oligomer from Momentive, 3-octanoylthio-1 propyltriethoxysilane and combinations thereof. [0088] In still other embodiments, the acrylate polymer may be formed using one or more monomers, e.g. a (meth)acrylic ester monomer including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ureido-functional (meth)acrylates and acetoacetates, acetamides or cyanoacetates of (meth)acrylic acid; styrene or substituted styrenes; vinyl toluene; butadiene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrollidone; (meth)acrylonitrile; and N-alkylol (meth)acrylamide. Optional multiethylenically unsaturated monomers include, for example, allyl (meth)acrylate, diallyl phthalate, butadiene, 1,4-butylene glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and divinyl benzene. The use of the term “(meth)” followed by another term such as (meth)acrylate or (meth)acrylamide, as used throughout the disclosure, refers to both acrylates or acrylamides and methacrylates and methacrylamides, respectively. In still other embodiments, the acrylate polymer may be formed, without a phosphate monomer, as described in one or more of US20080146724A1 and US8710133B2, each of which 26 PCT PATENT APPLICATION 364.1746PC3 is expressly incorporated herein by reference in its entirety in various non-limiting embodiments. Method of Making the Comb Polymer [0089] This disclosure also provides a method of forming the comb polymer that includes the step of (a) mixing monomers A, B, C, D, and/or chain transfer agent E, with water, and preferably an acid which may be any known in the art, to hydrolyze a silane to a silanol and form a mixture. Any method known in the art may be utilized to effect the above reactions. [0090] The method also includes the step of (b) introducing this mixture along with an initiator to a reactor under starve-fed conditions. [0091] The individual monomers may be any described herein or known in the art to be used form the comb polymer. In various non-limiting embodiments, Monomers A, B, and C have the following formulas: (Monomer C); and wherein each substituent is as described above. In addition, in other non-limiting embodiments, monomer D has the formula: 27 PCT PATENT APPLICATION 364.1746PC3 (Monomer D). In addition, and in one embodiment, Chain Transfer Agent E has the formula: (Chain Transfer Agent E). [0092] In other embo chain transfer agents are thiols such as 3- mercaptopropionic acid or 2-mercaptoethanol or lower secondary alcohols, typically isopropanol, can be used. In various embodiments, the chain transfer agent is chosen from mercaptans (e.g., n- dodecyl mercaptan); thiols (e.g., 2-mercaptoethanol); carbon tetrachloride (CCl4); alcohols (e.g., ethanol, isopropanol); sulfides (e.g., dimethyl disulfide); trithiocarbonates (e.g., ethyl xanthate); organic halides (e.g., bromoform); organic acids (e.g., acetic acid); nitro compounds (e.g., nitroethane); silicon-based compounds; and combinations thereof. [0093] In still other embodiments, the chain transfer agent is a silanol, e.g. -S-R11-Si(OH)3; - S-R11-Si(OCH3)3; -S-R11-Si(OCH2CH3)3, or combinations thereof. For example, the chain transfer agent may be gamma-mercaptopropyl trimethoxy silane or mercaptopropyl trimethoxy silanol or combinations thereof. [0094] In the above, each of the Monomers is introduced to the reactor in whatever molar ratio is desired. For example, the molar ratio of Monomers A:B:C:(D and/or E) may each independently be from (about 1:about 99). In various embodiments, the molar ratio of Monomers A:B:C:(D and/or E) is (about 1 to about 25) : (about 50 to about 95) : (about 1 to about 25) : (about 1 to about 25). Alternatively, any one or more of Monomers A, B, C, and D and/or E may be utilized as 28 PCT PATENT APPLICATION 364.1746PC3 described anywhere in this disclosure in terms of identity and amount. Typically, e.g. at all times of the process, whatever molar ratio that is chosen is substantially unchanging and a total molar ratio of a + b + c + d and/or e = 100 mol%. The method then also includes the step of reacting Monomers A, B, C, and (D and/or E) to form the comb polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0095] The comb polymer is typically prepared from a polymerization mixture in an aqueous medium in the presence of any initiator or initiating system capable of liberating free radicals under the reaction conditions employed. The free radical initiators can be present in an amount of from about 0.01% to about 10 mol% based on total moles of monomer. In a typical embodiment, an initiating system is soluble in water to at least 0.1 weight percent, typically to at least 1 weight percent and most typically to at least 10 weight percent at 25°C. Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as erythorbic acid, and metal ion based initiating systems. Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide. In an embodiment, the inorganic peroxides, such as sodium persulfate, potassium persulfate and ammonium persulfate, are typical. In another embodiment, the initiators comprise metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides. Organic peracids such as peracetic acid can be used. Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like. A typical system is persulfate alone such as sodium or ammonium persulfate or a redox system with iron and persulfate with hydrogen peroxide. Azo initiators, especially water-soluble azo initiators, may also be used. Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'- Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1- pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)- 2-hydroxyethl]propionamide}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and 29 PCT PATENT APPLICATION 364.1746PC3 others. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0096] The molecular weight of the comb polymer may be controlled by various compounds used in the art including, for example, chain transfer agents such as mercaptans, ferric and cupric salts, bisulfites, and lower secondary alcohols, typically isopropanol. Typically, the comb polymer starts to be more and more water insoluble as the content of monomer b increases over 75 mol%. Higher molecular weight comb polymers tend to acerbate the water insolubility. Therefore, a chain transfer agent can be used to minimize the effect on water insolubility by lowering the molecular weight of the comb polymer, e.g. when b is > 75 mol% or 79 mol%. As described above, typical chain transfer agents are thiols such as 3-mercaptopropionic acid or 2-mercaptoethanol or lower secondary alcohols, typically isopropanol. In various embodiments, the chain transfer agent is chosen from mercaptans (e.g., n-dodecyl mercaptan); thiols (e.g., 2-mercaptoethanol); carbon tetrachloride (CCl4); alcohols (e.g., ethanol, isopropanol); sulfides (e.g., dimethyl disulfide); trithiocarbonates (e.g., ethyl xanthate); organic halides (e.g., bromoform); organic acids (e.g., acetic acid); nitro compounds (e.g., nitroethane); silicon-based compounds; and combinations thereof. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0097] The terminology “starve-fed” as used herein typically means introducing monomers gradually to a reactor at a rate sufficiently slow enough that the majority of each monomer introduced is consumed by the reaction before additional monomer is added. In a typical embodiment, at least 50% of the monomers are consumed by the reaction before more monomers are added, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%, or at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, or at least 86%, or at least 87%, or at least 88%, or at least 89%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% of the monomers are consumed by the reaction before more monomers are added to the reactor. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. 30 PCT PATENT APPLICATION 364.1746PC3 [0098] The terminology that describes that the feed molar ratio of monomers is “substantially unchanging” typically means that the feed moles of each monomer is at all times within about 10% by moles, typically about 5% by moles, more typically about 2% by moles, most typically about 0.5% by moles of the anticipated final molar amount of that monomer in the final polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [0099] The acrylate polymer can be formed using any method known in the art. Typically, the acrylate polymer is formed using a free-radical polymerization, more specifically emulsion polymerization. The specific parameters and conditions of the formation of the acrylate polymer can be chosen by the person of skill in the art. Core Shell Polymer [00100] The core-shell polymer may include any polymer or co-polymer described herein. In the context of the disclosure, the term “(co)polymer” indicates polymer or copolymer. The term “polymer” and the term “copolymer” can be used herein interchangeably, as understood by one of skill in the art. In various embodiments, the core shell polymer may be any as is described in PCT/EP2024/058374, which is expressly incorporated herein by reference in its entirety in various non-limiting embodiments. [00101] As used herein and throughout the specification, the terms “core-shell morphology”, “core-shell structure”, “core polymer”, “staged core polymer” and “two-staged polymer” or “multi-staged polymer” may be used interchangeably and mean a polymer or polymer particle prepared by a sequential or staged polymerization process wherein each sequence or stage of monomer repeating units is added to the polymerization reactor, in a batch or continuous process, and begins to undergo polymerization which may be before, or concurrently with, the addition and polymerization of the subsequent sequence or stage of repeating units is commenced. In some embodiments, the polymerization of one stage will be substantially complete before the monomers of the next stage are added to the polymerization reactor. In other embodiments, the polymerization of one stage may be only partially complete before the monomers of the next stage are added to the polymerization reactor. [00102] The core shell polymer itself includes at least one core polymer and at least one shell polymer that is disposed about the at least one core polymer. The at least one core polymer is the polymerization reaction product of a first monomer mixture. The first monomer mixture 31 PCT PATENT APPLICATION 364.1746PC3 includes a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; and f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 8 or greater carbon atoms. In this first monomer mixture, if a1) is not present, then e1) is present in the first monomer mixture. Moreover, if f1) is not present in the first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in the first monomer mixture. Furthermore, if f1) is present in the first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the first monomer mixture. However, at least one of b1) and f1) is present in the first monomer mixture. Referring now to the at least one shell polymer, the at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture. The second monomer mixture includes a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 8 or greater carbon atoms. In this second monomer mixture, if a2) is not present, then e2) is present in the second monomer mixture. Moreover, if f2) is not present in the second monomer mixture then a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in the second monomer mixture. Furthermore, if f2) is present in the second monomer mixture then a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the second monomer mixture. In addition, at least one of b2) and f2) is present in the second monomer mixture while at least one of the first monomer mixture and the second monomer mixture includes a1) or a2) in an amount greater than zero mol %, respectively. Moreover, at least one of g1) and g2) is utilized. 32 PCT PATENT APPLICATION 364.1746PC3 At Least One Shell Polymer [00103] The at least one shell polymer may be disposed about all of the at least one core polymer or only about a portion of the at least one core polymer, e.g. disposed about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95+% of an outer surface of the at least one core polymer. For example, the core shell polymer can be in a form in which a core portion (e.g. core polymer) is completely coated or encapsulated, or non-completely coated or encapsulated, within or by a shell portion (e.g. shell polymer). It is also to be understood that in describing the “core polymer” and the “shell polymer”, there can be a significant amount of interpenetration of these polymers. Thus, the “core polymer” can extend somewhat into the at least one shell polymer and vice versa. The terms “core polymer” and “shell polymer” and like terminology are employed herein to describe the polymeric material in a general way without attempting to identify any particular polymers as strictly “shell” or strictly “core” polymers. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00104] In various embodiments, core-shell polymers have a structure in which a polymer(s) forming the core portion, sequence or stage (e.g. core polymer) and the polymer(s) forming the shell portion, sequence or stage (e.g. shell polymer) are physically and/or chemically bonded and/or attracted to each other. The structure and/or chemical composition (e.g. monomer mixture and/or amount) of the core-shell polymer can change from the inside to the outside (i.e., from the at least one core polymer to the at least one shell polymer) and, as a result, may form gradient zones that can have different physical and chemical properties from each other. These gradient zones can be somewhat gradual, yielding a morphology having a gradient of polymeric structure or composition along any radius thereof. Alternatively, the gradient zones can be relatively well defined when moving outward along a radius from the center of the core-shell polymer, yielding a morphology having a relatively distinct core portion including one polymeric composition, and a relatively distinct shell portion including a different polymeric composition. The terminology “gradient” typically describes a pattern with a progressive change (e.g. increase or decrease) in a characteristic at issue. For example, the core-shell polymer can change when considered from the inside to the outside, or when considered from the outside to the inside, relative to a progressive change in physical and/or chemical properties, e.g. an amount of cross-linking. 33 PCT PATENT APPLICATION 364.1746PC3 [00105] The core-shell morphology can include multiple layers or zones of differing polymeric composition. A rate of change in polymeric morphology is not particularly critical as long as the polymer exhibits the desired physical properties described herein. Accordingly, as used herein in various embodiments, the terms “core” and “shell” refer to the polymeric content of the inside and the outside of the core-shell polymer, respectively, and the use of such terms should not be construed as meaning that the core-shell polymer will necessarily exhibit a distinct interface between the polymers of the inside and the outside. [00106] The core-shell polymers can include one or more core polymers and one or more shell polymers, which can be the same as or different from the at least one core polymer and from each other with respect to both the type and proportions of monomers used to form a polymer backbone. [00107] In various embodiments, one or both of the at least one core polymer and the at least one shell polymer includes an increasing gradient of cross-link density measured in an outward direction extending from a center of the at least one core polymer towards the at least one shell polymer wherein the cross-link density of the at least one core polymer is less than the cross-link density of the at least one shell polymer. [00108] Alternatively, one or both of the at least one core polymer and the at least one shell polymer includes an increasing gradient of cross-link density measured in an inward direction extending from an outermost layer of the at least one shell polymer towards a center of the at least one core polymer towards wherein the cross-link density of the at least one core polymer is greater than the cross-link density of the at least one shell polymer. [00109] The core-shell polymer may be present in the composition in any amount. Typically, the core-shell polymer is present in an amount of from about 0.01 to about 10 weight percent, about 0.05 to about 2 weight percent, or about 0.1 to about 2 weight percent, based on a total weight of the composition. In other embodiments, this amount is from about 0.1 to about 1.9, about 0.2 to about 1.8, about 0.3 to about 1.7, about 0.4 to about 1.6, about 0.5 to about 1.5, about 0.6 to about 1.4, about 0.7 to about 1.3, about 0.8 to about 1.2, about 0.9 to about 1.1, or about 1, weight percent, based on a total weigh of the composition. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. 34 PCT PATENT APPLICATION 364.1746PC3 At Least One Core Polymer [00110] Referring now to the at least one core polymer itself, the at least one core polymer is independent from the at least one shell polymer. The terminology “at least one” means that a single core polymer may be utilized. Alternatively, more than one core polymer may be utilized. For example, one or more seed polymers may be utilized and then encapsulated, either partially or entirely, by one or more other polymers, wherein the entire complex of seed polymers and encapsulating polymers may be described as a “core” polymer. Any one or more of these seeds polymers and/or encapsulating polymers may be any polymer described herein. Alternatively, the at least one core polymer may be a single core polymer. [00111] The at least one core polymer can be, include, consist essentially of, or consist of, the polymerization reaction product of monomers present in the first monomer mixture, as first introduced above. For example, the monomers used to form the at least one core polymer may be chosen from a), b), c), d), e), f), g) and combinations thereof. In one embodiment, only a) and b) are utilized to form the at least one core polymer. In other embodiments, the following combinations are utilized: (a, b, c); (a, b, c, d); (a, b, d); (a, b, c, d, e); (a, b, e); (a, b, c, e); (a, b, d, e); (a, b, c, f); (a, b, c, d, f); (a, b, d, f); (a, b, c, d, e, f); (a, b, e, f); (a, b, c, e, f); (a, b, d, e, f); (a, b, f); (a, c, f); (a, d, f); (a, e, f); (a, b, c, f); (a, b, d, f); (a, b, e, f); and all combinations thereof. Any one or more of c, d, e, f, and g may be utilized or omitted from use so long as at least one of g1) and g2) is utilized, as described in greater detail below. [00112] As used herein, the monomers typically described for use in the first monomer mixture are labeled a1), b1), c1), d1), e1), f1) and g1). The nomenclature “1” describes the potential inclusion in the first monomer mixture. Similarly, and as described in greater detail below, the monomers typically described for use in the second monomer mixture are labeled a2), b2), c2), d2), e2), f2), and g2). The nomenclature “2” describes the potential inclusion in the second monomer mixture. However, the overarching nomenclature and options described herein related to choice of a, b, c, d, e, and f applies to both the “1” and “2” designations. For example, it is contemplated that any of a1) and a2) may be any monomer described herein as “a”, any of b1) and b2) may be any monomer described herein as “b”, any of c1) and c2) may be any monomer described herein as “c”, any of d1) and d2) may be any monomer described herein as “d”, any of e1) and e2) may be any monomer described herein as “e”, any of f1) and f2) may be any monomer described herein as “f”, and any of g1) and g2) may be any monomer described herein as “g”. 35 PCT PATENT APPLICATION 364.1746PC3 Moreover, it is contemplated that the descriptions below can also apply to the second monomer mixture, in various non-limiting embodiments. [00113] Relative to the first monomer mixture, if a1) is not present in the first monomer mixture then e1) is present in the first monomer mixture. This is because there needs to be some hydrophilic monomer for the core shell polymer to swell. [00114] Moreover, if f1) is not present in the first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in the first monomer mixture. For example, this amount may be about 5 to about 55, about 10 to about 50, about 15 to about 45, about 20 to about 40, about 25 to about 35, or about 30 to about 35, mol %. In still other embodiments, the monomer mixture includes about 12 to about 60 mol % of a1) based on a total number of moles of the monomers. In other embodiments, this amount is from greater than about 0 to about 10, about 1 to about 9, about 2 to about 8, about 3 to about 7, about 4 to about 6, or about 4 to about 5, mol % of a1) based on a total number of moles of the monomers. In various embodiments, this amount is from about 15 to about 60, about 20 to about 55, about 25 to about 50, about 30 to about 45, or about 35 to about 40, mol % based on a total number of moles of monomer. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. This is because if f1 is not present a stable emulsion is not formed if a1 is substantially greater than 60 mole%. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00115] Additionally, if f1) is present in the first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in the first monomer mixture. For example, this amount may be about 5 to about 75, about 10 to about 70, about 15 to about 65, about 20 to about 60, about 25 to about 55, about 30 to about 50, about 35 to about 45, or about 35 to about 40, mol %. In other embodiments, this amount is from greater than about 0 to about 10, about 1 to about 9, about 2 to about 8, about 3 to about 7, about 4 to about 6, or about 4 to about 5, mol % of a1) based on a total number of moles of the monomers in the first monomer mixture. This is because f1 delivers a high level of hydrophobicity which allows for the formation of stable emulsion. In various non-limiting embodiments, all whole and fractional 36 PCT PATENT APPLICATION 364.1746PC3 values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00116] Moreover, at least one of b1) and f1) is present in the first monomer mixture. This is because a hydrophobic monomer is needed to form a emulsion. Moreover, at least one of g1) and g2) is utilized. a) Anionic Ethylenically Unsaturated Monomers [00117] As described above, the a) anionic ethylenically unsaturated monomer may describe a1) and/or a2). As used herein, the term "anionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer which is capable of developing a negative charge when the polymer that it is used to form is in an aqueous solution, and which anionic monomer is not an associative monomer, as described below. One or more may be used as described above. [00118] In various embodiments, the anionic ethylenically unsaturated monomer is an acid. The anionic ethylenically unsaturated monomers can include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, α-chloro-acrylic acid, α-cyano acrylic acid, β-methyl-acrylic acid (crotonic acid), α-phenyl acrylic acid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid, angelic acid, 2-carboxyethyl (meth)acrylate, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, muconic acid, 2- acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid, and vinyl phosphonic acid. Combinations of anionic ethylenically unsaturated monomers can also be used. In one embodiment, the anionic ethylenically unsaturated monomer may be methacrylic acid, maleic acid, acrylic acid, itaconic acid, 2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof. In one embodiment, most typically the anionic ethylenically unsaturated monomer is methacrylic acid or acrylic acid, or combinations thereof. As used herein, the term “(meth)acrylic” acid is meant to include both acrylic acid and methacrylic acid. Similarly, the term “alkyl (meth)acrylate” as used herein is meant to include alkyl acrylate and alkyl methacrylate. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. 37 PCT PATENT APPLICATION 364.1746PC3 b) Short Chain Hydrophobic Ethylenically Unsaturated Monomers [00119] As described above, the b) short chain hydrophobic ethylenically unsaturated monomer may describe b1) and/or b2). As used herein, the term “short chain hydrophobic ethylenically unsaturated monomer” means a monomer that has a side chain including a hydrophobe that has 7 or fewer carbon atoms. e.g., 7, 6, 5, 4, 3, 2, or 1 carbon atom. This monomer is hydrophobic and tends to enable the formation of an emulsion system when reacted with am anionic ethylenically unsaturated monomer. One or more may be used as described above. [00120] In various embodiments, the hydrophobic ethylenically unsaturated monomer can be sparingly soluble in water and have a water solubility of less than about 6, 5, 4, 3, 2, 1.6, 1, etc. grams per about 100 mls of water at about 25°C. These hydrophobic ethylenically unsaturated monomers may include linear or branched alk(en)yl, cycloalkyl, aryl, or alk(en)aryl moieties. [00121] Suitable hydrophobic ethylenically unsaturated monomers include C1-C7 alkyl esters of acrylic acid, maleic acid, itaconic acid and methacrylic acid; C1-C7 alkyl amides of acrylic acid, maleic acid, itaconic acid and methacrylic acid; benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and styrene, alpha-methyl styrene, vinyl toluene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl valerate, vinyl hexanoate, vinyl caprolactam, (meth)acrylonitrile, isobutylene, diisobutylene, isoprene, vinyl chloride, vinylidene chloride, and combinations thereof. [00122] In one embodiment, the b1) hydrophobic ethylenically unsaturated monomers are utilized in an amount such that an amount of a1) and b1) sums to about 100 mol%. In various embodiments, the amount of b1) is from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the first monomer mixture described above typically not including an amount of any crosslinking monomer or agent used. In various non- limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. c) Associative Monomers [00123] As described above, the c) associative monomer may describe c1) and/or c2). As used herein, the term “associative monomer” describes an ethylenically unsaturated monomer including 38 PCT PATENT APPLICATION 364.1746PC3 a hydrophobe and a spacer moiety which allows the hydrophobe to be sufficiently far away from the backbone of the core or shell polymer to form hydrophobic associations in aqueous solutions, and wherein the hydrophobe includes at least six carbon atoms. The spacer moieties are usually ethoxylate groups but any other group that extends the hydrophobe away from the backbone of the core and/or shell polymer may be used. One or more may be used as described above. [00124] The hydrophobes with a spacer moiety may include, but are not limited to, alcohol ethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated silicones and the like. In an embodiment, the typical hydrophobes with spacer moieties include alcohol ethoxylates and/or alkylphenoxy ethoxylates. In another embodiment, alcohol ethoxylates have carbon chain lengths of from about 6 to about 40 and from about 6 to about 100 moles of ethoxylation. In yet another embodiment, alcohol ethoxylates have carbon chain lengths of from about 12 to about 22 and from about 15 to about 30 moles of ethoxylation. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00125] The hydrophobes may be linear or branched alk(en)yl, cycloalkyl, aryl, alk(en)aryl or an alkoxylated derivative. In an embodiment, the most typical hydrophobes are linear or branched alcohols and amines that include about 12 to about 32 carbons. The associative monomer may include an ethylenically unsaturated monomer covalently linked to the hydrophobe. In an embodiment, the ethylenically unsaturated monomer part of the associative monomer typically is a (meth)acrylate, itaconate and/or maleate which includes ester linking groups. However, the associative monomer may also include amide, urea, urethane, ether, alkyl, aryl and other suitable linking groups. The hydrophobe may be an alkylamine or dialkylamine ethoxylate. In an embodiment, the (meth)acrylate group is most typical. In another embodiment, typical associative monomers are C12-32(EO)10-30 meth(acrylates) or C12-32(EO)10-30 itaconates or C12-32(EO)10-30 maleates. [00126] In one embodiment, the associative monomer has the structure of formula (I) I) 39 PCT PATENT APPLICATION 364.1746PC3 wherein: R1 is chosen from -H, -CH3, -COOH, or -CH2COOH; A is chosen from -CH2C(O)O-, -C(O)O-, -O-, –CH2O-, -CH2C(O)N-, -C(O)N-, -CH2-, -O-C(O)-, -NHC(O)O-, -NHC(O)NH-, -C6H4(R5)-NH-C(O)-O-, -C6H4(R5)-NH-C(O)-NH-, -C(O)O-CH2- CH(CH2OH)-O-, -C(O)O-CH2-CH(CH2OH)-NH-, -C(O)O-CH2-CH-CH2(OH)-O-, -C(O)O-CH2- CH-CH2(OH)-NH-, -CH2-O-CH2-CH(CH2OH)-O-, -CH2-O-CH2-CH-CH2(OH)-O-, -CH2-O- CH2-CH(CH2OH)-NH-, and -CH2-O-CH2-CH-CH2(OH)-NH-; (R3-O)n is a polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2 to C4 oxyalkylene units, wherein each R3 is independently chosen from -C2H4-, -C3H6-, - C4H8-, or a mixture thereof, and n is an integer of from about 5 to about 250, typically, n is about 5 to about 100, more typically about 10 to about 50 and most typically about 15 to about 30; R4 is chosen from C6-C36 linear or branched, saturated or unsaturated alk(en)yl or alk(en)aryl, typically C8-C32 linear or branched alk(en)yl, more typically C10-C22 linear alk(en)yl or C10-C32 branched alk(en)yl; and R5 is -CH2- or -(C)(CH3)2--. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00127] Suitable associative monomers include methacrylate and itaconate esters of a hydrophilic ethoxylate chain and a hydrophobic alkyl chain. [00128] In one embodiment, the associative monomer is an alkyl ethoxylate methacrylate ester having the structure of formula I(A): [00129] In one embo -based associative monomer such as cetyl ethoxylate itaconate, behenyl ethoxylate itaconate, or stearyl ethoxylate itaconate having the structure of formula I (B, C, D respectively) 40 PCT PATENT APPLICATION 364.1746PC3 [00130] In various embodiments, the associative monomers are utilized in an amount of from about 0.01 mol% to about 3 mol%, or from about 0.05 mol% to about 2 mol%, or from about 0.1 mol% to about 1 mol%, based on a total number of moles in the monomer mixture, In various non- limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00131] In various embodiments, the residue of the one or more optional associative monomers is not present in the at least one core polymer and/or the at least one shell polymer. In other words, in such embodiments, no associative monomers are used. For example, one or more c1) and c2) associative monomers may not be present in the first and/or second monomer mixtures. d) Cross-Linking Monomers (Cross-Linking Agents) [00132] As described above, the d) cross-linking monomers may describe d1) and/or d2). Referring now to the cross-linking monomers, one or more may be used as described above. Alternatively, these monomers may be omitted from use. In various embodiments, the at least one core polymer is not cross-linked. However, some cross-linking can be used so long as the amount of cross-linking does not overly inhibit the ability of the core-shell polymer to swell as described herein. 41 PCT PATENT APPLICATION 364.1746PC3 [00133] In one embodiment, the at least one shell polymer is formed using the cross-linking monomer/agent while the at least one core polymer is not. Alternatively, both the at least one shell polymer and the at least one core polymer may be formed using the cross-linking monomer/agent. However, if an amount of cross-linker is the same in both polymers, typically the core-shell polymer of this disclosure is not formed and instead a traditional polymer is formed. [00134] Typically, when the cross-linking monomer/agent is used, the polymer formed therefrom is or includes a partially or substantially-crosslinked network. In one embodiment, the at least one core polymer is formed using the cross-linking monomer/agent such that it is a partially or substantially-crosslinked network, as long as the mole percent of cross-linking monomer/agent used to form the at least one core polymer is less than the mole percent of the cross-linking monomer/agent used to form the at least one shell polymer. [00135] For example, in various embodiments, the at least one core polymer includes a residue of the one or more crosslinking monomers in an amount that is less than an amount of the residue of the one or more crosslinking monomers in the shell by about 5 mol % of that amount or less. In other words, the at least one core polymer can be formed using a molar amount of the cross-linking monomer/agent that is about 5 mol % less than the amount of the cross-linking monomer/agent used to form the at least one shell polymer. In other embodiments, this amount is from about 5 to about 10 mol % less. In other embodiments, this amount is about 5, 4, 3, 2, 1, or even 0.5, mol % less. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00136] The cross-linking monomer/agent can be chosen from one or more of a crosslinking monomer having two or more carbon-carbon double bonds, a polyfunctional crosslinking compound that reacts with pendant functional groups on the relevant polymer, and combinations thereof. [00137] Exemplary cross-linking monomer/agents include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6- hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,2′-bis(4-(acryloxy-propyloxyphenyl)propane, 2,2′-bis(4-(acryloxydiethoxy-phenyl)propane, and zinc acrylate (i.e., 2(C3H3O2)Zn++); tri(meth)acrylate compounds such as, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethyl(ethoxylate)propane 42 PCT PATENT APPLICATION 364.1746PC3 tri(meth)acrylate, and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate; allyl compounds such as allyl (meth)acrylate, diallyl phthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate; polyallyl ethers of sucrose having from 2 to 8 alkyl groups per molecule, polyallyl ethers of pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether; polyallyl ethers of trimethylolpropane such as trimethylolpropane diallyl ether and trimethylolpropane triallyl ethers, and combinations thereof. Other suitable compounds include divinyl glycol, divinyl benzene, and N,N'-methylenebisacrylamide, and combinations thereof. In another embodiment, suitable monomers can be synthesized via an esterification reaction of a polyol made from ethylene oxide or propylene oxide or combinations thereof with unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, or an addition reaction with unsaturated isocyanate such as 3-isopropenyl-α-α-dimethylbenzene isocyanate. [00138] Exemplary polyfunctional cross-linking monomer/agents include polyhaloalkanols such as 1,3-dichloroisopropanol and 1,3-dibromoisopropanol; sulfonium zwitterions such as the tetrahydrothiophene adduct of novolac resins; haloepoxyalkanes such as epichlorohydrin, epibromohydrin, 2-methyl epichlorohydrin, and epiiodohydrin; polyglycidyl ethers such as 1,4- butanediol diglycidyl ether, glycerine-1,3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, bisphenol A-epichlorohydrin epoxy resins and mixtures of the foregoing. e) Nonionic Ethylenically Unsaturated Monomers [00139] As described above, the e) nonionic ethylenically unsaturated monomers may describe e1) and/or e2). As used herein, the term "nonionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer which does not introduce a charge into the polymer that it is used to form, and which is neither a hydrophobic ethylenically unsaturated monomer nor an associative monomer nor a crosslinker, each as described herein. One or more may be used as described above or may be omitted. [00140] In various embodiments, nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, N-C1-C3alkyl(meth)acrylamides and N,N-C1-C3 43 PCT PATENT APPLICATION 364.1746PC3 dialkyl(meth)acrylamides such as N-methylmethacrylamide, N-ethylacrylamide, N- propylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, and N,N – dimethylmethacrylamide; vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butanoate, ethoxylated alkyl, alkaryl or aryl monomers such as methoxypolyethylene glycol (meth)acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth)acrylate, C1 to C4 hydroxyalkyl esters of (meth)acrylic acid, and others. Nonionic ethylenically unsaturated monomers include (poly) C1- C4alkoxylated (meth)acrylates such as poly(ethylene glycol)n (meth)acrylate and poly(propylene glycol)n (meth)acrylate where n = 1 to 100, typically 3 to 50, and most typically 5 to 20, ethoxylated C1-C4 alkyl, C1-C4 alkaryl or aryl monomers. In one embodiment, this monomer is methoxypolyethylene glycol (meth)acrylate. The optional C1 to C4 hydroxyalkyl esters of (meth)acrylic acid can include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (butane diol mono(meth)acrylate). In one embodiment, the monomer is chosen from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2- hydroxybutyl (meth)acrylate. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00141] In one embodiment, the optional nonionic ethylenically unsaturated monomer is utilized in an amount of from about 0 to about 85, from about 1 to about 85, from about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the monomer mixture described above typically not including an amount of any crosslinking monomer/agent used. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. f) Long Chain Hydrophobic Ethylenically Unsaturated Monomers [00142] As described above, the f) long chain hydrophobic ethylenically unsaturated monomers may describe f1) and/or f2). The one or more long chain hydrophobic ethylenically unsaturated monomers have a side chain including a hydrophobe that has 8 or greater carbon atoms. Although there is no particular upper limit for carbon atoms, in various embodiments, the upper limit is about 50, 45, 40, 35, 30, 25, 20, 15, or 10. In other embodiments, the number of carbon atoms is from about 8 to about 32, 10 to about 30, 12 to about 28, 14 to about 26, 16 to about 24, 18 to about 22, 44 PCT PATENT APPLICATION 364.1746PC3 or 20 to about 22. In various embodiments, at least one of f1) and f2) is independently chosen from C8-C32 alkyl esters of acrylic acid, maleic acid, itaconic acid and methacrylic acid; C8-C32 alkyl amides of acrylic acid, maleic acid, itaconic acid and methacrylic acid; 10-hydroxydecyl (meth)acrylate, t-butyl styrene, iso-propyl styrene, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, isobutylene, diisobutylene, isoprene, vinyl chloride, vinylidene chloride, 1 -allyl naphthalene, 2-allyl naphthalene, 1 -vinyl naphthalene, 2-vinyl naphthalene, and combinations thereof. In various non- limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00143] In other embodiments, b1) and/or b2) and/or f1) and/or f2) may be chosen from the following, where appropriate, in view of the above definitions of such monomers: C1-C32 alkyl esters of acrylic and methacrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, n- propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, hexyl (meth)acrylate,octyl (meth)acrylate, decyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6- hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2- butyloctyl (meth)acrylate, 2-hexyldecyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, 2- decyltetradecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, behenyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate; and C4-C32 alkyl amides of acrylic and methacrylic acid, including tertiary butyl (meth)acrylamide, t-octyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, n-octyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, and behenyl (meth)acrylamide, styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, iso-propyl styrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, butadiene, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene, ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, t-butyl (meth)acrylate, vinyl acetate, tertiary butyl acrylamide and combinations thereof. In various embodiments, ethyl acrylate, methyl acrylate, methyl methacrylate, vinyl acetate, butyl acrylate and combinations thereof are typical. In other embodiments, exemplary 45 PCT PATENT APPLICATION 364.1746PC3 alkyl (meth)acrylate monomers can be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, iso-amyl (meth)acrylate, and mixtures thereof. In an embodiment, ethyl acrylate is typical. [00144] In various embodiments, the amount of the f1) long chain hydrophobic ethylenically unsaturated monomers is from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer in the first monomer mixture described above typically not including an amount of any crosslinking monomer or agent used. In various non- limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. g) One Or More Monomers Or Chain Transfer Agents With A Silane Or Silanol Group [00145] As described above, the g) one or more monomers or chain transfer agents with a silane or silanol group may describe g1) and/or g2). These are optionally used herein. The one or more monomers or chain transfer agents with a silane or silanol group are not particularly limited and may be any known in the art. In various embodiments, the one or more monomers or chain transfer agents with a silane or silanol group is chosen from trimethylsilanol; dimethylsilanediol; methylsilanetriol; tetrahydroxysilane; 3-(trihydroxysilyl)propylamine; 3- (trihydroxysilyl)propionic acid; hydroxyl-terminated polydimethylsiloxane (PDMS-OH); trimethylsilane; dimethylsilane; methylsilane; phenylsilane; chlorotrimethylsilane; dichlorodimethylsilane; trichloromethylsilane; tetrachlorosilane; trimethoxysilane; triethoxysilane; methyldimethoxysilane; phenyltrimethoxysilane; 3- aminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane; vinyltrimethoxysilane; (3- glycidoxypropyl)trimethoxysilane; tris(trimethylsiloxy)silane; methyldichlorosilane; dimethylchlorosilane; tetramethyldisiloxane; silane-modified thiols; and combinations thereof. [00146] In various embodiments, the amount of the g1) and/or g2) one or more monomers or chain transfer agents with a silane or silanol group is about zero or about from about 1 to about 99, about 5 to about 95, about 10 to about 90, about 10 to about 88, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 45 to about 50, mol% based on a total number of moles of monomer 46 PCT PATENT APPLICATION 364.1746PC3 in the respective monomer mixture described above typically not including an amount of any crosslinking monomer or agent used. However, at least one of g1) and g2) is utilized such that the amounts of both g1) and g2) utilized to form the respective polymers are not both zero. Said differently, an amount of g1) that is used is greater than zero, an amount of g2) is greater than zero, or amounts of both g1) and g2) that are used are both greater than zero. In other embodiments, the molar percent of residues of g1) and/or g2) is from about 0.01 to about 10 mol%, based on a total moles of reactants, e.g. from about 0.01 to about 0.1, about 0.01 to about 0.05, about 0.1 to about 10, about 0.5 to about 10, about 0.1 to about 1, about 0.5 to about 1, about 0.5 to about 3, about 1 to about 10, about 1 to about 5, about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, mol%, or any range thereof, based on a total moles of reactants, e.g. based on a total number of moles of monomer in the respective monomer mixture described above, which may nor may not include an amount of any crosslinking monomer or agent used. In various non-limiting embodiments, all values, both whole and fractional, between and including all of the above, are hereby expressly contemplated for use herein. [00147] It is contemplated that g1) may be used without g2). Alternatively, g2) may be used without g1). Alternatively, both g1) and g2) may be used. However, both g1) and g2) may not be omitted herein. In various embodiments, g1) may be used in an amount more than that of g2). In other embodiments, g2) may be used in an amount more than that of g1). In various non-limiting embodiments, the shell requires Si-OR’ for bonding such that the shell of the core-shell polymer can be attached to the surface of the particle via an R-O-Si bond. In other embodiments, the shell chemistry is related to g2) such that g2) may be required. Shell Polymer [00148] Referring now to the at least one shell polymer, the at least one shell polymer is independently the polymerization reaction product of the second monomer mixture described above including the a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; and f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain including a hydrophobe that 47 PCT PATENT APPLICATION 364.1746PC3 has 8 or greater carbon atoms. In other words, any of the above may be used to form the at least one shell polymer. As described herein g1) or g2) may be used or omitted so long as at least one of g1) and g2) is utilized. [00149] It is contemplated that any of the above description relative to the components or amounts thereof utilized in forming the at least one core polymer may also apply to the at least one shell polymer, in various non-limiting embodiments. Moreover, any one or more of the amounts of any one of a1)-f1) above may also be independently utilized for any one or more of a2)-f2) in the second monomer mixture wherein the weight basis would be the second monomer mixture. [00150] For example, the monomers used to form the at least one shell polymer may be chosen from a), b), c), d), e), f), and combinations thereof. In one embodiment, only a) and b) are utilized to form the at least one core polymer. In other embodiments, the following combinations are utilized: (a, b, c); (a, b, c, d); (a, b, d); (a, b, c, d, e); (a, b, e); (a, b, c, e); (a, b, d, e); (a, b, c, f); (a, b, c, d, f); (a, b, d, f); (a, b, c, d, e, f); (a, b, e, f); (a, b, c, e, f); (a, b, d, e, f); (a, b, f); (a, c, f); (a, d, f); (a, e, f); (a, b, c, f); (a, b, d, f); (a, b, e, f); and all combinations thereof. Any one or more of c, d, e, and f may be utilized or omitted from use in various non-limiting embodiments. For example, as described herein g1) or g2) may be omitted so long as at least one of g1) and g2) is utilized. [00151] In various embodiments, the at least one shell polymer is at least partially cross-linked and includes from about 0.01 mol % to about 10 mol % of the residue of the one or more crosslinking monomers. In various embodiments, this amount is from about 0.05 to about 10, about 0.1 to about 10, about 1 to about 10, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00152] In various embodiments, the one or more shell polymers can have any mole percent of residues of the crosslinking agent, as long as the at least one core polymer has a mole percent of residues of the crosslinking agent less than the at least one shell polymer. [00153] In one embodiment, the residue of the one or more optional associative monomers is present in an amount of greater than zero and up to about 1.5 mol % in the at least one core polymer and/or the at least one shell polymer, e.g. about 0.05 to about 1.5, about 0.1 to about 1.5, about 0.5 to about 1.5, about 0.5 to about 1, or about 0.1 to about 0.15, mol %. In various non-limiting 48 PCT PATENT APPLICATION 364.1746PC3 embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00154] In other embodiments, the at least one shell polymer is at least partially cross-linked and includes from about 0.01 mol % to about 10 mol % of the residue of the one or more crosslinking monomers. In various embodiments, this amount is from about 0.05 to about 10, about 0.1 to about 10, about 1 to about 10, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In other embodiments, this amount is from about 0.1 to about 2.8, about 0.2 to about 2.7, about 0.3 to about 2.6, about 0.4 to about 2.5, about 0.5 to about 2.4, about 0.6 to about 2.3, about 0.7 to about 2.2, about 0.8 to about 2.1, about 0.9 to about 2, about 1 to about 1.9, about 1.1 to about 1.8, about 1.2 to about 1.7, about 1.3 to about 1.6, or about 1.4 to about 1.5, mol %. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00155] In other embodiments, the at least one core polymer includes from about zero mol % of the residue of the one or more crosslinking monomers up to an amount of less than about 25 mol % of the amount of the residue of the one or more crosslinking monomers present in the at least one shell polymer. In various embodiments, this amount is from about 0.05 to about 25, about 0.1 to about 25, about 1 to about 25, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00156] In other embodiments, the at least one core polymer includes about zero mol % of the residue of the one or more crosslinking monomers and further includes the residue of the one or more associative monomers in an amount of greater than zero mol %. This amount may be any amount greater than zero. For example, this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00157] In other embodiments, the at least one core polymer includes about zero mol % of the residue of the one or more crosslinking monomers and the at least one shell polymer includes the 49 PCT PATENT APPLICATION 364.1746PC3 residue of the one or more associative monomers in an amount of greater than zero mol %. This amount may be any amount greater than zero. For example, this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00158] In other embodiments, the at least one core polymer includes about zero mole % of the residue of the one or more crosslinking monomers and the at least one shell polymer is at least partially cross-linked and includes greater than about 0.05 mol % of the residue of the one or more crosslinking monomers. This amount may be any amount greater than about 0.05 mol%. For example, this amount may be from about 0.05 to about 100, about 0.1 to about 100, about 1 to about 100, about 0.01 to about 0.1, about 0.05 to about 0.1, about 0.1 to about 1, mol%, etc. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00159] In one embodiment, the at least one core polymer includes from about 1% to about 95% by weight of one or more shell polymers, based on the total weight of the at least one core polymer. In another embodiment, the at least one core polymer includes about 5 wt% to about 60 wt% of the one or more shell polymers, based on the total weight of the at least one core polymer. In still other embodiments, the at least one shell polymer accounts for greater than about 5 wt% and less than about 90 wt% of a total weight of the monomer residues in the core-shell polymer. This value may be about 5 to about 85, about 10 to about 80, about 15 to about 75, about 20 to about 70, about 25 to about 65, about 30 to about 60, about 35 to about 55, about 40 to about 50, or about 45 to about 55, wt%. In other embodiments, this value is from about 15 to about 40, about 20 to about 35, or about 25 to about 30, wt%. Typically, if the amount is greater than about 90, the shell is too heavy and desired expansion/swelling is limited. This is not desirable. Similarly, if there is too high of a weight percent of shell and too high of a percentage of cross-linking in the shell, then expansion/swelling is hindered which again is undesirable. In various embodiments, the wt % of the shell is about 75 wt% and the amount of residue of the cross-linking monomer/agent is about 0.1 mol %. Similar ratios of shell weight and molar % of crosslinking monomer are also contemplated for use herein. If the weight percent is too low, e.g. less than about 15, 10, or 5 wt%, 50 PCT PATENT APPLICATION 364.1746PC3 the core-shell polymer will not be complete and undesirable mixtures of side-products (polymers) will tend to form. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00160] In another embodiment, the at least one core polymer includes about 10 wt% to about 40 wt% or about 15 to about 35 wt % of the one or more shell polymers based on the total weight of the at least one core polymer. In still other embodiments, the at least one core polymer is present in an amount that is greater than about 60 wt% and up to about 95 wt% based on the total weight of the at least one core polymer. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00161] In still other embodiments, at least one shell polymer includes a mol % of residue of the d2) one or more crosslinking monomers that is greater than a mol % of residue of the d1) one of more cross-linking monomers in aid at least one core polymer. For example, this mol% may be 1, 2, 3, 4, 5, 10, 15, 20, 25…up to about 100 mol% greater. In other embodiments, the core shell polymer includes two or more shell polymers and at least one shell polymer includes a mol % of residue of the d2) one or more crosslinking monomers that is less than a mol % of residues of the d1) one of more cross-linking monomers in the at least one core polymer. In further embodiments, the at least core shell polymer accounts for greater than 5 wt % and less than about 90 wt % of a total weight of the core shell polymer, e.g. about 5 to about 90, about 10 to about 85, about 15 to about 80, about 20 to about 75, about 25 to about 70, about 30 to about 65, about 35 to about 60, about 40 to about 55, or about 50 to about 55, mol%. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00162] In other embodiments, b1) and/or f1) is present in the first monomer mixture in at least about 1 mol% based on a total number of moles of monomers in the first monomer mixture and the a1) anionic ethylenically unsaturated monomer is present in the first monomer mixture in 10 mol% or less based on a total number of moles of monomers in the first monomer mixture; and b2) and/or f2) is present in the second monomer mixture in at least about 1 mol% based on a total number of moles of monomers in the second monomer mixture and the a2) anionic ethylenically unsaturated monomer is present in the second monomer mixture in 10 mol% or less based on a 51 PCT PATENT APPLICATION 364.1746PC3 total number of moles of monomers in the second monomer mixture. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00163] In still other embodiments, the at least one core polymer is the reaction product of a1) and b1) and the at least one shell polymer is the reaction product of a2), b2), and d2); or the at least one core polymer is the reaction product of a1), b1) and e1) where a1) is present in an amount of less than about 20 mol% of the first monomer mixture and e1) is present in an amount of greater than about 5 mol% of the first monomer mixture and the at least one shell polymer is the reaction product of a2), b2), d2) and e2) wherein a2) is present in an amount of less than about 20 mol% of the second monomer mixture and e2) is present in an amount of greater than about 5 mol% of the second monomer mixture. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00164] It is contemplated that any of a2), b2), c2), d2), e2), f2), and g2) may independently be present in any of the amounts or ranges of amounts that are described above relative to a1), b1), c1), d1), e1), f1), and g1) even if one or more of a1), b1), c1), d1), e1), f1), and g1) is not used or even if the amount of one or more of a1), b1), c1), d1), e1), f1), and g1) is different from the amount of one or more of a2), b2), c2), d2), e2), f2), and/or g2). As described herein g1) and/or g2) may omitted so long as at least one of g1) and g2) is utilized. First and Second Shell Polymers [00165] In other embodiments, the core-shell polymer includes a first shell polymer (12) and a second shell polymer (14) wherein the first shell polymer (12) is disposed on and in direct contact with the at least one core polymer (10) and the second shell polymer (14) is disposed on and in direct contact with the first shell polymer (12). Examples are shown in the Figures. [00166] In one embodiment, e.g. as shown in FIG. 3, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross- link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is greater than the cross-link density of the first shell polymer (12) and greater than the cross-link density of the at least one core polymer (10). 52 PCT PATENT APPLICATION 364.1746PC3 [00167] In another embodiment, e.g. as shown in FIG. 4, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross-link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is less than the cross-link density of the first shell polymer (12) and greater than the cross-link density of the at least one core polymer (10). [00168] In another embodiment, e.g. as shown in FIG. 5, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is greater than the cross-link density of the at least one core polymer (10) and greater than the cross-link density of the first shell polymer (12). [00169] In another embodiment, e.g. as shown in FIG. 6, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross-link density of the first shell polymer (12) is greater than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and less than the cross-link density of the first shell polymer (12). [00170] In another embodiment, e.g. as shown in FIG. 7, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and greater than the cross-link density of the first shell polymer (12). [00171] In another embodiment, e.g. as shown in FIG. 8, each of the at least one core polymer (10), the first shell polymer (12), and the second shell polymer (14) has a cross-link density, the cross-link density of the first shell polymer (12) is less than the cross-link density of the at least one core polymer (10), and the cross-link density of the second shell polymer (14) is less than the cross-link density of the at least one core polymer (10) and less than the cross-link density of the first shell polymer (12). 53 PCT PATENT APPLICATION 364.1746PC3 [00172] It is also contemplated that, e.g. in any one or more of FIGS.2-6, any one of the described layers may be an outermost layer of the core shell polymer or may be an inner layer. The term “outermost” describes an embodiment wherein the layer is disposed such that it forms an exterior layer of the core shell polymer that is exposed to the environment and does not include another layer disposed on its exterior. The terminology “inner layer” describes that the layer has another layer disposed on at least one surface/side thereof. The inner layer is not exposed to the environment and is not an outer layer. [00173] Alternatively, there may be one or more intervening polymers disposed between the at least one shell polymer and the at least one core polymer. Such intervening polymers may be any known in the art and any described herein. [00174] In various embodiments, the core shell polymer is further defined as an alkali swellable core shell polymer. The terminology “alkali swellable” means that, in these embodiments, the core shell polymer can swell when exposed to alkali conditions, e.g. in water, in a composition etc. In various embodiments, the swelling of the composition can be measured via laser diffraction, e.g. using a particle size analyzer such as a Malvern Mastersizer. Any method can be used, e.g. ASTM E3340-22, ASTM D1921-18, International Standard ISO 13320-1, etc. Moreover, diameters may be reported as x10 (Dv10), x50 (Dv50), x90 (Dv90), and D[4,3] (volume moment mean), etc. Said a different way, any one or more of Dv10 and/or Dn10, Dv50 and/or Dn50, Dv90 and/or Dn90, may be used to report and evaluate particle size. Moreover, any type of instrument type, software version, light scattering model applied, real and imaginary part of complex refractory index if Mie theory is applied, etc. may be used as specified in such methods. [00175] In various embodiments, particle size can be calculated as follows using a Malvern Zetasizer Nano S. For example, three measurements are performed in succession, with the number of runs per measurement automatically determined by the instrument. Measuring position and attenuation are set automatically by the instrument. The measurement sequence is performed at 25°C after a 120 second equilibration time. The preset values for water viscosity (0.8872 centipoise) and refractive index (1.330) are used for the dispersant parameters. A refractive index and absorption for the samples are set at 1.590 and 0.010, respectively. At the completion of the sample measurement sequence, cumulants and distribution analyses are performed by the instrument software (Malvern Zetasizer Software, version 7.10). The reported z-average (in nm) is used as the measure of particle size. In some instances, the particle size distribution can be such 54 PCT PATENT APPLICATION 364.1746PC3 that a cumulants analysis is not successful (as indicated by instrument software quality reports) and therefore the z-average, while reported, may not be reliably calculated. In such cases where the cumulants analysis/z-average fails to be reliable, and if the distribution analysis passes quality checks as indicated by the instrument software, then the particle size of the highest volume fraction peak of the volume particle size distribution as reported by the instrument software can be used as the particle size. [00176] In various embodiments, the core shell polymer has a first diameter measured at a pH of from about 3 to about 5, and has a second diameter measured at a pH of about 8, wherein the second diameter is larger than the first diameter. For example, the second diameter may be about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50…up to about 100% or more, larger than the first diameter. Again, this diameter may be measured and reported using any method described above or known in the art so long as the first and second diameters are measured using the same method for accurate comparison. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00177] The core-shell polymer may be formed using any method in the art. More specifically, the core-shell polymer includes at least two polymers (i.e., the at least one core polymer and the at least one shell polymer) which may be synthesized using any methods known in the art. For example, the polymerization may occur sequentially via free radical emulsion polymerization techniques known to the art. Core Polymer Synthesis [00178] In various embodiments, the at least one core polymer is synthesized in a first emulsion polymerization step from the first monomer mixture including one or more of a1)-f1) and optionally g1) described above. A chain transfer agent also can be used, as described in greater detail below. [00179] In another embodiment, a first monomer pre-emulsion may be utilized wherein the first monomer mixture can be emulsified in a water and surfactant mixture in a first vessel before being added to a reactor where emulsion polymerization takes place. In another embodiment, the first monomer mixture has no added water or surfactant before being added to the reactor where emulsion polymerization takes place. 55 PCT PATENT APPLICATION 364.1746PC3 [00180] The monomers a1)-f1) and optionally g1) may be polymerized in the presence of a suitable free radical forming initiator, e.g. to provide an emulsion of the at least one core polymer. In one embodiment, the polymerization typically begins with a “seed” process in which seed polymer particles are formed that serve as loci for subsequent polymerization. [00181] In a free radical emulsion polymerization, free radical initiators that generate a free radical during the polymerization process are utilized. As used herein, the initiating system may be any free radical initiating system. The free radical initiators are typically present in an amount of from about 0.01 wt% to about 3 wt% based on total monomer weight. In an embodiment, the initiating system is soluble in water to at least 0.1 weight percent at 25°C. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00182] Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as hydrogen peroxide and erythorbic acid, and metal ion based initiating systems. Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide. In an embodiment, the inorganic peroxides, such as sodium persulfate, potassium persulfate and ammonium persulfate, are typical. In another embodiment, the initiators include metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides. Organic peracids such as peracetic acid can be used. Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like. Azo initiators, especially water soluble azo initiators, may also be used. Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'- Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1- pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)- 2-hydroxyethl]propionamide}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and others. 56 PCT PATENT APPLICATION 364.1746PC3 [00183] Optionally, other emulsion polymerization additives and processing aids which are well known in the emulsion polymerization art, such as auxiliary emulsifiers, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides, antifoam agents, and pH adjusting agents can be included in the polymerization system. The primary emulsifier is typically an anionic surfactant and these such as sodium lauryl sulfate are well known in the art. [00184] In one embodiment, an auxiliary emulsifying aid chosen from an ethoxylated C10 to C22 fatty alcohol (or their mixtures) can be added to the reactor. In one embodiment, the fatty alcohol includes from about 5 to about 250 moles of ethoxylation, from about 8 to 100 moles in another aspect, and from about 10 to 50 moles in a further aspect. Exemplary ethoxylated fatty alcohols include lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and behenyl alcohol ethoxylate. In another aspect, suitable ethoxylated fatty alcohols include Ceteth- 20, Ceteareth-20, and Steareth-20, Behenth-25, and mixtures thereof. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00185] If employed, the amount of ethoxylated fatty alcohol can be from about 0.01% to 10% by weight in one embodiment, from about 0.1% to about 5% by weight in another aspect, and from about 0.3% to about 3% by weight in a further aspect, based on a total weight of emulsion basis. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. Two-Stage Polymerization [00186] The following describes a typical two-stage polymerization which may be utilized or omitted. First, a first monomer mixture including one or more of a1)-f1) and optionally g1) described above and an optional chain transfer agent are added to a first vessel with mixing and are combined with a solution of emulsifying surfactant (e.g., anionic surfactant) in water to prepare a monomer pre-emulsion. Optional processing aids can be added as desired (e.g., auxiliary emulsifier(s)). [00187] The monomers may be introduced to an aqueous charge that optionally includes a surfactant in a reactor either as a monomer pre-emulsion or a separate monomer mixture and aqueous surfactant solution. When the first monomer mixture is used, an aqueous surfactant 57 PCT PATENT APPLICATION 364.1746PC3 solution can be added to the reactor at the same time as or directly after the addition of the first monomer mixture. The reactor contents can be stirred and a small amount of free-radical initiator can be added to the reactor to initiate the formation of seed particles, which is known as a seed stage. Upon completion of the seed stage, the first monomer mixture can be added as a as a monomer mixture or monomer pre-emulsion concurrent with an initiator feed, or as a first monomer mixture added concurrently with an aqueous surfactant solution feed and an initiator feed, to the reactor. Alternatively, the initiator can be added prior to the addition of the monomer mixture to the reactor. Typically, core polymer or polymer emulsion has a total polymer solids content of from about 10 to about 45 weight percent. While the at least one core polymer is synthesized in an emulsion, it should be recognized that the at least one core polymer can be supplied in dried powder form if desired. This is particularly useful for adhesives that are re- dispersible powders. [00188] Next, the at least one shell polymer is formed in a second polymerization step. The second monomer mixture of a2)-f2) and optionally g2) may be added as a monomer mixture or as a monomer pre-emulsion concurrent with an initiator feed, or as a second monomer mixture added concurrently with an aqueous surfactant solution feed and an initiator feed. Alternatively, the initiator can be added prior to the addition of the second monomer mixture to the reactor. The end- product is a two stage polymer including the at least one core polymer surrounded or partially surrounded by the at least one shell polymer. [00189] In an alternative embodiment, only a portion of the full amount of surfactant to be used is initially present in the reactor, and the remainder is added as a concurrent stream along with the stream of monomer mixture and the stream of initiator, during all steps of the polymerization. [00190] Optionally, further successive free radical emulsion polymerization stages can be run to obtain multi-layer polymer morphologies such that successive polymer stages differ at least by the mole percent of crosslinking agent utilized in that stage. In a stage where it is desired to have a linear polymer, a monomer mixture can be used that is devoid of crosslinking agent. In a stage where it is desired to have a crosslinked polymer, the monomer mixture will include a crosslinking agent. [00191] To obtain the desired properties for any particular end-use application, it is possible to adjust any of (i) the relative mole ratios of the individual monomers, (ii) the mass percent of each of the at least one core and the at least one shell polymers, (iii) the choice of monomers, 58 PCT PATENT APPLICATION 364.1746PC3 crosslinking agent, or associative monomers in any of the polymers, (iv) the addition rate of first and second monomer mixtures, surfactant solutions, and initiator solutions, and (v) the mole percentage of crosslinking monomer/agent in any of the polymers, etc. [00192] While the core-shell polymer can be synthesized by successive emulsion polymerization steps to yield an aqueous polymer emulsion, it should be recognized that the core-shell polymer can ultimately be supplied in dried powder form if desired. [00193] The emulsion polymerization can be carried out in a staged batch process, in a staged semi-batch monomer addition process or multi-step continuous process, or the polymerization can be initiated as a batch process and then the bulk of the monomers can be continuously staged into the reactor (seeded semi-batch process), as described above. [00194] Typically, the emulsion polymerization reactions are carried out at a reaction temperature of from about 20 to about 99°C. However, higher or lower temperatures can be used. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00195] The emulsion polymerization reactions can be performed in an aqueous or aqueous alcohol medium. [00196] The surfactant can be added to the first and/or second monomer mixtures to form a pre- emulsion. Alternatively, the surfactant can be added directly to the reactor during the emulsion polymerization. Alternatively, both methods can be utilized. In one embodiment, the emulsion polymerization is carried out in the presence of surfactant of in the amount of from about 0.01% to about 10% by weight, about 0.1% to about 5%, or about 0.3% to about 3% by weight, each based on a total emulsion weight basis. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00197] Suitable surfactants include anionic, nonionic, amphoteric, and cationic surfactants, as well as mixtures thereof. Most commonly, anionic and nonionic surfactants can be utilized as well as mixtures thereof. [00198] Suitable anionic surfactants for facilitating emulsion polymerizations are well known in the art and include, but are not limited to, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium (C6-C16) alkyl phenoxy benzene sulfonate, disodium (C6-C16) alkyl phenoxy benzene 59 PCT PATENT APPLICATION 364.1746PC3 sulfonate, disodium (C6-C16) di-alkyl phenoxy benzene sulfonate, disodium laureth-3 sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butyl naphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, phosphate esters of branched alcohol ethoxylates, and the like. [00199] Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art, and include, without limitation, linear or branched alcohol ethoxylates, C8 to C12 alkylphenol alkoxylates, such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like. Other useful nonionic surfactants include C8 to C22 fatty acid esters of polyoxyethylene glycol, mono and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C8 to C22 fatty acid glycol esters, block copolymers of ethylene oxide and propylene oxide having an HLB value of greater than about 12, ethoxylated octylphenols, and combinations thereof. In another embodiment, linear alcohol alkoxylates include polyethylene glycol ethers of cetearyl alcohol (a mixture of cetyl and stearyl alcohols) sold under the trade names PLURAFAC® C-17, PLURAFAC® A-38 and PLURAFAC® A-39 by BASF Corp. In still another embodiment, polyoxyethylene polyoxypropylene block copolymers include copolymers sold under the trade names PLURONIC® F127, and PLURONIC® L35 by BASF Corp. [00200] Other suitable nonionic surfactants include, but are not limited to, Ethoxylated linear fatty alcohols such as DISPONIL® A 5060 (Cognis), Ethal LA-23 and Ethal LA-50 (Ethox Chemicals), branched alkyl ethoxylates such as GENAPOL® X 1005 (Clariant Corp.), secondary C12 to O14 alcohol ethoxylates such as TERGITOL® S15-30 and S15-40 (Dow Chemical Co.), ethoxylated octylphenol-based surfactants such as TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887, and 897 (Rhodia, Inc.), ICONOL® OP 3070 and 4070 (BASF Corp.), SYNPERONIC® OP 30 and 40 (Uniqema), block copolymers of ethylene oxide and propylene oxide such as PLURONIC® L35 and F127 (BASF Corp.), and secondary C11, alcohol ethoxylates such as EMULSOGEN® EPN 407 (Clariant Corp.). Numerous other suppliers are found in the trade literature. [00201] In addition, suitable surfactants are also described in The Handbook of Industrial Surfactants (Fifth Edition, by Michael and Irene Ash) which is hereby fully incorporated by reference. [00202] The emulsion polymerization can be carried out in the presence of a suitable polymeric stabilizer. Suitable polymeric stabilizers (also known as protective colloids) for the emulsion 60 PCT PATENT APPLICATION 364.1746PC3 polymerization process of this disclosure are water-soluble polymers, including, for example, synthetic polymers, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers and the like; water-soluble natural polymers, such as gelatin, pectins, alginates, casein, starch, and the like; and modified natural polymers, such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl modified hydroxyethylcellulose, and the like. In some cases, it can be of advantage to use mixtures of a synthetic and a natural protective colloid, for example, a mixture of polyvinyl alcohol and casein. Further suitable natural polymers are mixed ethers such as methylhydroxyethylcellulose and carboxymethylmethylcellulose. [00203] Polymeric stabilizers can be utilized in amounts up to about 10 weight percent based on the total emulsion weight, or up to about 7.5 weight percent, or up to about 5 weight percent, or up to about 2.5 weight percent, or up to about 2 weight percent based on the total emulsion weight. In another embodiment, when utilized, a polymeric stabilizer is included in an amount of from about 0.001 weight percent to about 10 weight percent, or from about 0.01 weight percent to about 7.5 weight percent, or from about 0.1 weight percent to about 5 weight percent, or from about 0.5 weight percent to about 2.5 weight percent, or even from about 1 weight percent to about 2 weight percent, based on the total emulsion weight. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00204] In various embodiments, a polymerization reactor is charged with a desired amount of water, additional surfactant and optional processing aids. The polymerization reactor is equipped with attached inert gas inlet and feed pumps, and the reactor contents are maintained under inert atmosphere and heated with mixing agitation. The contents of the reactor are brought to a temperature of from about 55 to 98°C, and are maintained at those conditions for about one hour. [00205] A seed stage can then be performed in a manner consistent with the addition of monomer and surfactant via a pre-emulsion as described above. The desired amount of core stage monomer pre-emulsion is fed subsurface into the reactor, and a free radical initiator solution is fed separately and concurrently with the core stage monomer mixture into the reactor contents over a period of about one half to two hours. During this time, the reaction temperature is controlled at from about 45 to about 95°C. After a desired amount of the core monomer mixture has been added to the 61 PCT PATENT APPLICATION 364.1746PC3 reactor, the feed may be stopped and, if desired, an additional quantity of free radical initiator can optionally be added to the reactor. The resulting reaction mixture can be held at a temperature of about 45 to 95°C for a time period sufficient to complete or substantially complete the polymerization reaction and obtain a first stage core-shell polymer emulsion. In various non- limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00206] The second monomer mixture used for forming the at least one shell polymer can be mixed in a separate vessel following the same procedures as described above. Alternatively, to the first vessel including remaining material from forming the at least one core polymer, a crosslinking agent can be added and mixed with agitation to form the second monomer mixture. Additional monomers can be added if desired. [00207] In other embodiments, monomers used to form the at least one shell polymer are metered into the reactor at a constant rate and mixed with aforementioned emulsion used to form the at least one core polymer. Simultaneously with a feed used to introduce monomers used to form the at least one shell polymer, a free radical initiator solution in an amount sufficient to reinitiate polymerization can be metered into the reaction mixture, such that the monomers are polymerized in the presence of the at least one core polymer. The temperature is then typically maintained at about 85°C for about one half to two and a half hours or until polymerization is complete. Unreacted monomer can be eliminated by completing a monomer chase step, such as addition of more initiator and/or by adjusting and maintaining temperature for a period of time to maintain radical flux from thermal initiator residues, as is well known in the emulsion polymerization art. [00208] While a typical two-stage polymer process is generally described immediately above, multi-staged or multi-layered polymers can be formed through the sequential emulsion polymerization of monomer charges in the presence of polymer particles of a previously formed emulsion polymer. [00209] Chain transfer agents can be used in any stage of the polymerization process for any one or more monomers described above or can be omitted. The chain transfer agent can be any chain transfer agent known in the art. Suitable chain transfer agents include, but are not limited to, thio and disulfide containing compounds, such as C1-C18 alkyl mercaptans, C1-C18 alkyl mercaptoalcohols, mercaptocarboxylic acids, mercaptocarboxylic esters, thioesters, C1-C18 alkyl 62 PCT PATENT APPLICATION 364.1746PC3 disulfides, aryldisulfides, polyfunctional thiols such as trimethylolpropane-tris-(3- mercaptopropionate), pentaerythritol-tetra-(3-mercaptopropionate), pentaerythritol-tetra- (thioglycolate), and pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioglycolate), and the like; phosphites and hypophosphites; haloalkyl compounds, such as carbon tetrachloride, bromotrichloromethane, and the like; and catalytic chain transfer agents such as, for example, cobalt complexes (e.g., cobalt (II) chelates). [00210] In one embodiment, the chain transfer agent is chosen from n-dodecyl mercaptan, methyl mercaptopropionate, and 3-mercaptopropionic acid, 2-mercaptoethanol, combinations thereof and the like, octyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, isooctyl 3-mercaptopropionate, butyl 3-mercaptopropionate, butyl thioglycolate, isooctyl thioglycolate, and dodecyl thioglycolate. [00211] The chain transfer agent can be utilized an amount less than about 0.75, about 0.5, about 0.25, or about 0.1, mol% based on the monomers present typically not including the crosslinking agent. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. Additional Embodiments [00212] In one embodiment, the weight proportion of the at least one shell polymer to the at least one core polymer and the amount of crosslinking agent in each of the at least one shell polymer and the at least one core polymer are selected to provide typical rheological properties for a particular end-use application. [00213] In another embodiment, the at least one core polymer is greater than 5, 10, 20, 30, 40, 50,6070, 80, 90 wt% of the core-shell polymer. In another embodiment, the core-shell polymer includes at least one core polymer including zero mol% of a residue of a crosslinking agent. [00214] In some embodiments, the core-shell polymer includes at least one core polymer including a residue of C1-C6 alkyl (meth)acrylate monomers. In some embodiments, the at least one core polymer includes both at least one residue of a C1-C6 alkyl acrylate monomer and at least one residue of a C1-C6 alkyl methacrylate monomer. [00215] In other embodiments, the binder is chosen from acrylate, vinyl acrylate, styrene acrylate, and combinations thereof. 63 PCT PATENT APPLICATION 364.1746PC3 [00216] In other embodiments, the binder is chosen from acrylics, vinyl -acrylic, styrene acrylics, ethylene-vinyl acetate, vinyl acetate, alkyd, vinyl chloride, styrene-butadiene, vinyl versatate, vinyl acetate-maleate, and combinations thereof. [00217] In other embodiments, the at least one core polymer includes a residue of the one or more crosslinking monomers in an amount that is less than an amount of the residue of the one or more crosslinking monomers in the shell by about 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, or 0.1, mol % of that amount or less. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00218] In other embodiments, the at least one core polymer is the reaction product of a) and b) and the at least one shell polymer is independently the reaction product of a), b), and d). [00219] In other embodiments, if a1 or a2 is present in an amount of less than about 10 mol%, then e1 or e2, respectively, is present in an amount of greater than about 10 mol% and up to any amount described above relative to e1 and/or e2. [00220] In various non-limiting embodiments, one or more method steps, process steps, components, etc. may be used herein as is described in WO 2019/096976 and/or U.S. 8,673,277, each of which is expressly incorporated herein in its entirety by reference in non-limiting embodiments. Method of Forming the Composite Particle [00221] This disclosure also provides various methods of forming the composite particle. It is contemplated that any of the methods described below may apply to any one or more of the polymers described herein and are not necessarily limited to the comb polymer, the acrylate polymer, or the core shell polymer. [00222] In a first method of forming the composite particle, the method may include, consist essentially of, or consist of, the steps of: introducing at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent into a polymerization reactor; polymerizing the at least one acrylate monomer and the silane monomer, silanol monomer, and/or silane or silanol chain transfer agent in the polymerization reactor to form the acrylate polymer; combining the acrylate polymer and the silica particle; and 64 PCT PATENT APPLICATION 364.1746PC3 reacting the acrylate polymer and the silica particle via a condensation reaction to form the composite particle wherein the acrylate polymer is attached to the surface of the silica particle via an O-Si bond. [00223] The step of introducing may be any known in the art. The at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent may be mixed or combined in one or more parts, in a batch or semi-batch or continuous process. This step may occur under any conditions chosen by one of skill in the art. The at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent may be any described herein or any known in the art. During the step of introducing and/or polymerizing, or before the step of combining with the silica particle, the silane is typically converted to a silanol. [00224] The step of polymerizing may also be any known in the art and occur under temperature, pressure, and time conditions as chosen by the skilled person. [00225] Relative to the step of combining, the polymer and the silica particle may be combined in one or more portions and in a batch, semi-batch or continuous process. This step will typically occur in the coating manufacturing process but may also occur in the Silica slurry manufacturing process. This step may occur under any conditions chosen by one of skill in the art. [00226] Relative to the step of reacting, the polymer and the silica particle may be reacted under any conditions chosen by the skilled person. In one embodiment, the step of reacting occurs at a pH of about 7 to about 10, e.g.7, 7.5, 8, 8.5, 9, 9.5 or 10. For example, the polymer and the silica particle may be reacted via a condensation reaction to form the composite particle wherein the polymer is attached to the surface of the silica particle via an O-Si bond. This reaction may occur using any mechanism, procedure, and conditions known in the art. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00227] In another embodiment, wherein the silane monomer is utilized, the method further includes a step of hydrolyzing the silane monomer to form a silanol monomer in the presence of water or at least one acidic monomer or acid before, during or after the step of polymerizing, and the step of polymerizing occurs at a pH of about 1 to about 7, e.g. about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly 65 PCT PATENT APPLICATION 364.1746PC3 contemplated for use herein. [00228] This disclosure also provides a second method of forming the composite particle wherein the method may include, consist essentially of, or consist of, the steps of: combining the comb polymer, the acrylate polymer, and/or the core shell polymer, and the silica particle having the surface that is functionalized with the least one R-OH group; and reacting the comb polymer and the silica particle via a condensation reaction to form the composite particle wherein the polymer is attached to the surface of the silica particle via an O-Si bond. These steps may occur under any conditions chosen by one of skill in the art. [00229] In various embodiments, the step of reacting occurs at a pH of about 5 to about 11, e.g. about 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, or 11. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00230] Without intending to be limited by theory, it is believed that a hydrolysis reaction proceeds quickly at lower pH. Conversely, a condensation reaction of, for example, a hydrolyzed silane with a surface silica group, proceeds slowly at a low pH. It is also theorized that a condensation reaction occurs much more quickly at a pH of about 9 as compared to a pH of about 4 which would suggest that it is desirable to conduct the condensation reaction at a pH of about 8 to about 9 because the condensation reaction is much faster than the hydrolysis react at that pH. In various embodiments, storage of the polymer may be done at a low pH, e.g. about 4 to about 5, because condensation is slower than hydrolysis at that pH. This gives the polymer storage stability and then the condensation reaction can take place at a higher pH of about 8 to about 9 to form the composite particle. [00231] As described above, the reaction to form the composite particles may occur at any point. As just one example, silanol groups of any of the polymers herein may react with the Silica thereby forming the composite particles during any step of a method to form a paint, a coating composition, cosmetics, sunscreens, etc. or any composition described herein. For example, the composite particles may be formed during the formation of the paint, coating composition, cosmetics, sunscreens, etc. or may be formed entirely independently and later added to the paint, coating composition, cosmetics, sunscreens, etc. or any composition described herein. In one embodiment, the reaction to form the composite particles occurs entirely independently from the formation of the composition. In another embodiment, the reaction to form the composite particles 66 PCT PATENT APPLICATION 364.1746PC3 occurs in-situ, or in combination with, or simultaneously with, the formation of the composition. Compositions/Formulations [00232] This disclosure also provides a composition or formulation that includes the composite particle. The composition is not particularly limited and may be any known in the art. For example, the composition may be a paint or coating. [00233] The composite particle may be included in the paint or coating in an amount of from about 1 to about 60 about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 5 to about 50, about 10 to about 45, about 10 to about 40, about 15 to about 35, about 20 to about 30, or about 25 to about 30, weight percent based on a total weight of the composition. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. [00234] In one embodiment, the formulation is a paint composition that includes (1) water and/or an organic solvent; (2) an optional binder; (3) an optional pigment; and (4) the composite particle. The water may be included in an aqueous paint composition. Alternatively, the composition may be a solvent based composition and include the organic solvent, which itself may be any known in the art of solvent based paints. The paint composition may be further described as water borne flat, semi-flat, semi-gloss, or gloss paint compositions. [00235] In various embodiments, the components of paint compositions include typically a solvent, typically water, for latex paints, binder, pigment and extenders and additives. These binders are typically latex binders such as all acrylate systems, polyvinyl acetate, copolymers of vinyl acetate and acrylate, copolymers of vinyl acetate and ethylene, copolymers of vinyl acetate, ethylene, and vinyl chloride, and copolymers of styrene and acrylate. The latex binders are often stabilized with anionic surfactants. [00236] Extenders are paint additives that are insoluble in the binder and water. They are added to modify the flow and mechanical properties of the paint as well as the permeability, gloss and leveling characteristics of the paint film. White extender pigments are added to paints to lower their cost or improve their properties. This class includes calcium carbonate, calcium sulfate, diatomaceous silica, and china clays. [00237] Additives include rheology modifiers and opaque polymers. The rheology modifiers include cellulosic derivatives, hydrophobically modified alkali swellable polymers, inorganic 67 PCT PATENT APPLICATION 364.1746PC3 material such as clays, Nonionic Synthetic Associative Thickeners (NSAT’s), and Nonionic Polyurethane Associative Thickeners (HEUR’s) and similar materials. [00238] The composition may optionally include other known additives, such as additional dispersing agents, anti-foaming agents, biocides, pH control agents, wetting agents, materials to improve freeze thaw stability, leveling aids, coalescing agents and/or polymeric or oligomeric binders. [00239] The paint composition may also include one or more pigments or be free of one or more pigments. Suitable pigments include inorganic pigments like titanium dioxide (independent of the type of this disclosure), coated titanium dioxide (also independent of the type of this disclosure), titania, iron oxides (red, yellow, brown and black), zinc oxide, chrome pigment, ultramarine pigments, cobalt pigments (cobalt blue) and organic pigments like e.g. azo pigments. [00240] Examples of suitable organic color pigments are: monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36, 38, 64, and 67; C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:, 53, 53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191:1, 208, 210, 245, 247, and 251; C.I. Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183, and 191; C.I. Pigment Violet 32; diazo pigments: C.I. Pigment Orange 16, 34, 44, and 72; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 180, and 188; diazo condensation pigments: C.I. Pigment Yellow 93, 95, and 128; C.I. Pigment Red 144, 166, 214, 220, 221, 242, and 262; C.I. Pigment Brown 23 and 41; anthanthrone pigments: C.I. Pigment Red 168; anthraquinone pigments: C.I. Pigment Yellow 147, 177, and 199; C.I. Pigment Violet 31; anthrapyrimidine pigments: C.I. Pigment Yellow 108; quinacridone pigments: Pigment Orange 48 and 49; C.I. Pigment Red 122, 202, 206, and 209; C.I. Pigment Violet 19; quinophthalone pigments: C.I. Pigment Yellow 138; diketopyrrolopyrrole pigments: C.I. Pigment Orange 71, 73, and 81; C.I. Pigment Red 254, 255, 264, 270, and 272; dioxazine pigments: C.I. Pigment Violet 23 and 37; C.I. Pigment Blue 80; flavanthrone pigments: C.I. Pigment Yellow 24; indanthrone pigments: C.I. Pigment Blue 60 and 64; isoindoline pigments: C.I. Pigments Orange 61 and 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185; isoindolinone pigments: C.I. Pigment Yellow 109, 110, and 173; isoviolanthrone pigments: C.I. Pigment Violet 31; metal complex pigments: C.I. Pigment Red 257; C.I. Pigment Yellow 117, 129, 150, 153, and 177; C.I. Pigment Green 8; perinone pigments: C.I. Pigment Orange 43; C.I. Pigment Red 194; perylene pigments: C.I. Pigment Black 31 and 32; C.I. 68 PCT PATENT APPLICATION 364.1746PC3 Pigment Red 123, 149, 178, 179, 190, and 224; C.I. Pigment Violet 29; phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16; C.I. Pigment Green 7 and 36; pyranthrone pigments: C.I. Pigment Orange 51; C.I. Pigment Red 216; pyrazoloqui-nazolone pigments: C.I. Pigment Orange 67; C.I. Pigment Red 251; thioindigo pigments: C.I. Pigment Red 88 and 181; C.I. Pigment Violet 38; triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81:1, and 169; C.I. Pigment Violet 1, 2, 3, and 27; C.I. Pigment Black 1 (aniline black); C.I. Pigment Yellow 101 (aldazine yellow); C.I. Pigment Brown 22. [00241] Examples of suitable inorganic color pigments are: white pigments: titanium dioxide (C.I. Pigment White 6), zinc white, pigment grade zinc oxide; zinc sulfide, litho-pone; black pigments: iron oxide black (C.I. Pigment Black 11), iron manganese black, spinel black (C.I. Pigment Black 27); carbon black (C.I. Pigment Black 7); chromatic pigments: chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green 50); ultramarine green; cobalt blue (C.I. Pigment Blue 28 and 36; C.I. Pigment Blue 72); ultramarine blue; manganese blue; ultramarine violet; cobalt violet; manganese violet; red iron oxide (C.I. Pigment Red 101); cadmium sulfoselenide (C.I. Pigment Red 108); cerium sulfide (C.I. Pigment Red 265); molybdate red (C. I. Pigment Red 104); ultramarine red; brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown, spinel phases and corundum phases (C.I. Pigment Brown 29, 31, 33, 34, 35, 37, 39, and 40), chromium titanium yellow (C.I. Pigment Brown 24), chrome orange; cerium sulfide (C.I. Pigment Orange 75); yellow iron oxide (C.I. Pigment Yellow 42); nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164, and 189); chromium titanium yellow; spinel phases (C.I. Pigment Yellow 119); cadmium sulfide and cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); chrome yellow (C.I. Pigment Yellow 34); bismuth vanadate (C.I. Pigment Yellow 184). [00242] Moreover, the pH of the composition can be adjusted with any combination of acidic and/or basic pH adjusting agents known to the art. In various embodiments, an alkaline material is incorporated into the composition and can be referred to as a neutralizing agent or pH adjusting agent. Many types of neutralizing agents can be used, including inorganic and organic bases, and combinations thereof. Examples of inorganic bases include but are not limited to the alkali metal hydroxides (especially sodium, potassium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like; and 69 PCT PATENT APPLICATION 364.1746PC3 mixtures thereof. Examples of organic bases include but are not limited to triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L- arginine, aminomethyl propanol, 2-amino 2-hydroxymethyl-1,3-propanediol, and PEG-15 cocamine. Alternatively, other alkaline materials can be used alone or in combination with the above mentioned inorganic and organic bases. Such materials include surfactants, surfactant mixtures, pre-neutralized surfactants. Any material capable of increasing the pH of the composition is suitable. [00243] Various acidic materials can be utilized as a pH adjusting agent. Such acidic materials include organic acids and inorganic acids, for example, acetic acid, citric acid, tartaric acid, alpha- hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof. The addition of the acidic pH adjusting agent can be incorporated after the addition of the basic pH adjusting agent in the composition. As with the alkaline pH adjusting agents, other acidic materials can be used alone or in combination with the above mentioned inorganic and organic acids. [00244] Buffering agents can also be used. Suitable buffering agents include, but are not limited to, alkali or alkali earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates, and the like, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate, and sodium carbonate. Phosphates such as sodium or potassium tripolyphosphate may be particularly useful. The pH adjusting agent and/or buffering agent can be utilized in any amount necessary to obtain and/or maintain a desired pH value in the composition. [00245] In addition to the components above, the composition may include, or be free of, other ingredients, for example, fluidizing agents, anti-sedimentation agents, plasticizers, surfactants, anti-foam agents, rheology modifiers, levelling agents, gloss modifiers, preservatives, pH adjustors such as organic amines, biocides, and the like, and combinations thereof. Conventional additives may include, but are not limited to, dispersants, antioxidants, UV stabilizers and absorbers, surfactants, wetting agents, leveling agents, antifoaming agents, anti-cratering agents, or combinations thereof. In various embodiments, one or more organic liquids which may be used as film-forming resins can be used. Examples of such resins include polyamides and cellulose 70 PCT PATENT APPLICATION 364.1746PC3 ethers, such as ethyl cellulose and ethyl hydroxyethyl cellulose, nitrocellulose and cellulose acetate butyrate resins, including mixtures thereof. Examples of paint resins include short oil alkyd/melamine-formaldehyde, polyester/melamine-formaldehyde, thermosetting acrylic/melamine-formaldehyde, long oil alkyd, polyether polyols and multi-media resins such as acrylic and urea/aldehyde. [00246] The composition may further include, or be free of, a non-ionic synthetic associative thickener (NSAT). Non-ionic synthetic associative thickeners can be used to provide viscosity and rheological control. These thickeners are typically non-ionic, meaning they do not carry any net charge in solution. These thickeners typically work by forming associations or interactions with other molecules, such as water or polymer chains, to increase viscosity. [00247] Hydrophobically Modified Ethoxylated Urethanes (HEUR) thickeners typically include a polyethylene oxide (PEO) backbone with hydrophobic groups (such as alkyl chains) attached via urethane linkages. These hydrophobic groups interact with each other and with the hydrophobic domains of other molecules, leading to thickening. In various embodiments, the composition includes less than about 2, 1.5, 1, 0.5, or 0.1, weight % actives of a hydrophobically modified ethoxylated polyurethane (HEUR) based on a total weight of the composition. Alternatively, the composition may be free of such a polyurethane. [00248] Hydrophobically Modified Cellulosics (HMHECs) thickeners are cellulose derivatives modified with hydrophobic groups, such as alkyl or alkylaryl moieties, attached to the cellulose backbone. These hydrophobic groups facilitate the association of cellulose chains, leading to increased viscosity. [00249] Hydrophobically Modified Polyacrylic Acid (HMPAA) thickeners are based on polyacrylic acid (PAA) or its derivatives modified with hydrophobic groups. These hydrophobic modifications allow the polymer chains to associate with each other and with other molecules in the system, resulting in thickening. [00250] Hydrophobically Modified Polyurethanes (HMPU) thickeners are polyurethane-based polymers modified with hydrophobic groups. Similar to other associative thickeners, the hydrophobic groups facilitate the association of polymer chains, leading to viscosity enhancement. [00251] In some embodiments, inclusion of one or more non-ionic synthetic associative thickeners (NSAT) can build KU to unacceptable levels without a corresponding increase in ICI to desired levels. However, in other embodiments, it is preferred to include one or more non-ionic 71 PCT PATENT APPLICATION 364.1746PC3 synthetic associative thickeners (NSAT). In various embodiments, the non-ionic synthetic associative thickener is present in an amount of from about 0.01 to about 5, about 0.05 to about 2%, or about 0.1 to about 1, weight percent, based on a total weight of the composition. In other embodiments, this amount is from about 0.01 to about 0.09, about 0.02 to about 0.08, about 0.03 to about 0.07, about 0.04 to about 0.06, about 0.04 to about 0.05, from about 0.1 to about 0.9, about 0.2 to about 0.8, about 0.3 to about 0.7, about 0.4 to about 0.6, about 0.4 to about 0.5, about 1 to about 5, about 2 to about 4, or about 2 to about 3, weight percent, based on a total weight of the composition. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00252] In various embodiments, the composition exhibits an ICI viscosity of greater than about 0.5 Poise and exhibits a KU viscosity of less than about 140 Krebs units. In other embodiments, the composition exhibits an ICI viscosity of greater than about 0.6 Poise and exhibits a KU viscosity of less than about 140 Krebs units. In various embodiments, the ICI viscosity is from about 0.6 to about 2, about 0.7 to about 2, about 0.8 to about 2, about 0.9 to about 1.9, about 1 to about 1.8, about 1.2 to about 1.7, about 1.3 to about 1.6, about 1.4 to about 1.5, Poise. In other embodiments, the ICI viscosity is greater than about 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9, Poise. In still other embodiments, the ICI viscosity is from about 1.2 to about 1.7, about 1.2 to about 1.6, about 1.2 to about 1.5, about 1.5 to about 2, about 1.6 to about 1.9, about 1.6 to about 1.8, about 1.5 to about 1.8, etc., Poise, typically measured at about 25°C. ICI viscosity can be determined using methods in accordance with ASTM D4287, ISO 2884 and BS 2900. More specifically, ICI viscosity is typically obtained using a Brookfield CAP 2000+ ICI cone and plate viscometer, high torque model, available from AMETEK Brookfield with USA headquarters in Middleboro, MA. The model is in compliance with ASTM D4287, ISO 2884 and BS 2900. Samples are typically analyzed for ICI viscosity at 25°C, 900 RPM, with a number 1 spindle. Sample temperature is first allowed to equilibrate between the cone and plate for 60 seconds, and then the measurement is run over 30 seconds. [00253] The viscosity value is obtained using a Cone/Plate Type Viscometer and gives information about the flow properties of the material under high-shear conditions similar to those encountered during application: brushing, spraying, electrostatic disk, or roll coating. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional 72 PCT PATENT APPLICATION 364.1746PC3 values including and between each value set forth above, are hereby expressly contemplated for use herein. [00254] Moreover, the composition can exhibit a KU viscosity of less than about 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, or 90, Krebs units. In various embodiments, the KU viscosity is from about 90 to about 140, about 95 to about 135, about 100 to about 130, about 105 to about 125, about 110 to about 120, about 115 to about 120, about 100 to about 110, about 100 to about 105, or about 105 to about 110, Krebs units typically measured at about 23°C. KU viscosity is determined using ASTM D562. KU viscosity is typically reported in Krebs units (KU), which tend to be unique to Stormer viscometers and the like. Vibrating viscometers, such as resonant or vibrational viscometers, can also be used. Most typically, approximately 300 grams of the composition is added to a 12 oz, wide mouth plastic jar and then analyzed for KU viscosity using a DS Byko-visc model Stormer viscometer manufactured by BYK-Gardner Gmbh headquartered in Geretsried, Germany, in compliance with ASTM D 562 and run at 200 rpm at about 23°C using paddle spindle 8340. In various non-limiting embodiments, all whole and fractional values and ranges of whole and fractional values including and between each value set forth above, are hereby expressly contemplated for use herein. [00255] The relative importance of ICI and KU viscosities depends on the formulation typically broken down in to Do-It-Yourself (DIY) and contractor formulations. Pigment volume concentration, or PVC, is used to describe the volume (not weight) of pigment in a paint film. PVC denotes how much of the volume of the paint film is made up of pigment versus the amount made up of binder. Critical pigment volume concentration or CPVC is the pigment concentration where the pigments are packed as close as possible and the binder is exactly the amount required to fill the space between the pigments. In many DIY premium paints, the PVC is typically lower than the CPVC. In contractor formulations, the PVC is typically higher than the CPVC. [00256] In most premium DIY paint formulations, a KU viscosity of from about 95 to about 105 and an ICI viscosity of about 1.2 to about 1.5 is desirable. In contractor formulations, the KU viscosity typically is from about 95 to about 120 while the ICI viscosity is typically about 0.6 or greater. In certain geographies the contractor will dilute the formulation such that a lower drop in KU viscosity can be useful. [00257] The composition may be formed using any method chosen by one of skill in the art. For example, the method may include the steps of combining one or more of the aforementioned 73 PCT PATENT APPLICATION 364.1746PC3 components with one another in one or more parts and in a batch or continuous process. [00258] The disclosure will now be described in greater detail with reference to the following non-limiting examples. EXAMPLES Example 1 - Comb Polymer of Formula (I) for the Composite Particle: [00259] 247 grams of water and 7.58 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1-liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 80 °C with overhead stirring and nitrogen sparge for at least 1 hr. [00260] A monomer pre-emulsion mixture was prepared as follows: 240 grams water and 7.58 grams 30% sodium lauryl sulfate solution in water (Stanfax 234), 79.9 grams of methoxy polyethylene glycol 750 methacrylate, 17.8 grams methacrylic acid, 135.4 grams methyl methacrylate, 2.7 grams of vinyl trimethoxy silane and 3.4 grams of dodecyl mercaptan, was added to the contents of the graduated cylinder with agitation. [00261] After the reactor contents had been sparged with nitrogen at 80 °C for at least an hour, a seed stage was then performed as follows: 24 grams of the monomer pre-emulsion mixture was added over a period of two minutes, subsurface, to the reactor contents. This was agitated for 15 minutes, and then a seed stage initiator solution including 0.21 grams ammonium persulfate dissolved in 17.5 grams water was added as a shot to the reactor contents. This was allowed to stir at 80 °C for an additional 15 minutes. [00262] The remaining monomer pre-emulsion mixture was slowly added to the reactor contents, subsurface, for 120 minutes. Simultaneously, an initiator feed 0.21 grams ammonium persulfate dissolved in 62.8 grams water was added to the reactor contents over the same 135 minutes. The reaction was then held at 80 °C for one hour. [00263] The final reaction product (comb polymer) was an opaque white emulsion with solids of 28.5%. Examples 2A-2B - Composite Particles Using Comb Polymer of Formula (I): [00264] These composite particles were produced by mixing an amount of the polymer of Example 1 with the amount of colloidal silica listed in the table below. The colloidal silica is an alkaline, aqueous dispersion that is approximately 15% solids by weight. The silica dispersion is 74 PCT PATENT APPLICATION 364.1746PC3 sterically stabilized and the amorphous silica particles carry a negative surface charge. The silica particles are discrete, have a smooth, spherical shape, and are present in a narrow particle size distribution. The particles have also been surface modified with an epoxy silane. These silica particles have a hydroxyl number of about 0.45 mole OH/kg product. The physical appearance of the dispersion is a clear liquid, slightly more viscous than water. The colloidal silica has a density at 20°C of about 1.075 to about 1.099 g/cm³, SiO₂ content of about 13.0 - 16.0 wt%, a pH at 20°C of about 9.0 - 11.4, a Viscosity at 20°C ≤ about 8 cP, an ethanol content of about 2.5 wt%, and an average particle size of about nm. [00265] Next, 20% NaOH and then 10% NaOH was added to adjust the pH to about 8-10. This mixture was stirred for 50 ºC for 12 hours. The final solids and pH of these composite materials are listed in the tables below: Polymer Silica of 20% 10% [00266] The final products were clear water white solutions and have the structure generally shown in FIG. 9. The polymer that was used to form the composite was an emulsion polymer but the composite is a clear solution indicating that there is a reaction between the polymer and the silica to form the composite. Example 3: Dirt Pick up resistance of Composite Particles of Examples 2A and 2B: [00267] Dirt Pick up resistance (DPUR) testing was done in a commercial paint formulation by adding 1.5wt% active of composite particles of Examples 2A and 2B and comparing results to the same formulation without any of the Examples 2A and 2B. Films were then drawn on aluminum substrates and dried for two days at room temperature followed by curing via UV exposure for 48 hours. A synthetic carpet dirt was applied to one half of the drawdown and left overnight. The excess was tapped off and the ΔE, which is the color difference between the soiled and unsoiled regions, was measured. The lower the Delta E the better the DPUR performance. Composite Particle ΔE PCT PATENT APPLICATION 364.1746PC3 No Composite Particle 14.0 Exam le 2A 91 [00268] These a a e o s a e a e co pos e po y e s o s sc osu e are very good and unexpectedly good DPUR additives for paint formulations. These composite particles give a decrease of ΔE by about 5 units is noticeable by the naked eye and should translate to very good performance under real world conditions. The skilled person would expect this type of performance with a fluorinated additive but these fluorinated additives are “forever chemicals” and are no longer being used. The skilled person would not expect this excellent performance using the technology of this disclosure such that this data evidences the superior and unexpected results associated with this disclosure. Therefore, there is an urgent need for the composite polymers of this disclosure. Example 4 - Core Shell Polymer For The Composite Particle: [00269] 273.5 grams of water and 5.63 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1-liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 85 °C with overhead stirring and nitrogen sparge for at least 1 hour. [00270] A “core” mixture was prepared by adding 37.7 grams methacrylic acid and 3.4 grams C16-1820EO associative monomer to a solution of 276.9 grams water and 5.72 grams 30% sodium lauryl sulfate solution in water (Stanfax 234) in a beaker. The contents were dispensed into a graduated cylinder with overhead agitation. A monomer solution was prepared by adding 24.08 grams methyl methacrylate, 78.8 grams ethyl acrylate, 96.73 grams hydroxypropyl acrylate, and 0.301 grams n-dodecyl mercaptan to a glass beaker. The monomer solution was added to the contents of the graduated cylinder with agitation, and the remnants in the beaker were rinsed out into the graduated cylinder with 10.69 grams water. [00271] After the reactor contents had been sparged with nitrogen at 85 °C for at least an hour, a seed stage was then performed as follows: 27 milliliters of the core monomer mixture were added to the reactor contents over a 2-minute period. This was agitated for 15 minutes, and then a seed stage initiator solution comprising 0.3 grams ammonium persulfate dissolved in 21.4 grams water was added as a shot to the reactor contents. This was allowed to stir for an additional 15 minutes. 76 PCT PATENT APPLICATION 364.1746PC3 [00272] Then, the remaining core monomer solution was slowly added to the reactor contents, subsurface, for 100 minutes. Simultaneously, an initiator feed comprising 150 milligrams ammonium persulfate dissolved in 13.42 grams water was added to the reactor contents over the same 100 minutes. [00273] At the completion of the “core” monomer mixture feed, a "shell" monomer mixture was added subsurface into the reactor from a graduated cylinder over 20 minutes. The “shell” monomer solution was prepared by mixing 0.62 grams C16-18 20EO associative monomer, 4.03 grams methyl methacrylate, 13.2 grams ethyl acrylate, 25.72 grams hydroxypropyl acrylate, 0.0504 grams n-dodecyl mercaptan, 0.31 methacrylic acid, 0.54 grams vinyltrimethoxysilane, 3.0378 grams trimethylolpropane triacrylate, and then the contents were mixed thoroughly. [00274] An initiator feed comprising 30 milligrams ammonium persulfate dissolved in 2.68 grams water was also added over the same 20 minutes as the shell monomer mixture. [00275] At the completion of the shell monomer mixture addition, 180 milligrams of ammonium persulfate dissolved in 16.1 grams water was fed into the reactor over a period of 50 minutes. Then the reactor contents were cooked at 90 C for one hour. The sample was cooled to ambient temperature, and to the contents was added 2.5 grams Nalco/Exxon EC9086A mixed in 5 grams water, and the milky white emulsion product was dispensed from the reactor after brief mixing, with a pH 2.88 of and a solids content of 30.26%. Example 5 - Core Shell Polymer For The Composite Particle: [00276] 278.1 grams of water and 5.7 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1 liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 85 °C with overhead stirring and nitrogen sparge for at least 1 hour. [00277] A “core” mixture was prepared by adding 75.9 grams methacrylic acid and 1.2 grams C16-1820EO associative monomer to a solution of 292.4 grams water and 5.72 grams 30% sodium lauryl sulfate solution in water (Stanfax 234) in a beaker. The contents were dispensed into a graduated cylinder with overhead agitation. A monomer solution was prepared by adding 75.2 grams methyl methacrylate, 87.5 grams ethyl acrylate, and 0.135 grams n-dodecyl mercaptan to a glass beaker. The monomer solution was added to the contents of the graduated cylinder with 77 PCT PATENT APPLICATION 364.1746PC3 agitation, and the remnants in the beaker were rinsed out into the graduated cylinder with 10.9 grams water. [00278] After the reactor contents had been sparged with nitrogen at 85 °C for at least an hour, a seed stage was then performed as follows: 5 weight percent of the core monomer mixture were added to the reactor contents over a 2-minute period. This was agitated for 15 minutes, and then a seed stage initiator solution comprising 0.3 grams ammonium persulfate dissolved in 21.4 grams water was added as a shot to the reactor contents. This was allowed to stir for an additional 15 minutes. [00279] Then, the remaining core monomer solution was slowly added to the reactor contents, subsurface, for 75 minutes. Simultaneously, an initiator feed comprising 0.15 grams ammonium persulfate dissolved in 13.42 grams water was added to the reactor contents over 90 minutes. [00280] At the completion of the “core” monomer mixture feed, a "shell" monomer mixture was added subsurface into the reactor from a graduated cylinder over 15 minutes. The “shell” monomer solution was prepared by mixing 0.24 grams C16-18 20EO associative monomer, 15.2 grams methacrylic acid, 15.04 grams methyl methacrylate, 17.5 grams ethyl acrylate, 0.75 grams vinyltrimethoxysilane, 0.099 grams ethylene glycol dimethacrylate, and then mixing the contents thoroughly. [00281] At the completion of the shell monomer mixture addition, 0.21 grams of ammonium persulfate dissolved in 16.1 grams water was fed into the reactor over a period of 50 minutes. Then the reactor contents were cooked at 90 C for one hour. Examples 6A-6B Composite Particles Using Core Shell Polymers: [00282] The following composite polymers are produced by mixing the amount of the polymers of Example 4 and 5 with the amount of the colloidal silica from Examples 2, as shown below. Next a 10% NaOH is added to adjust the pH in the 8-10 range. This mixture is stirred for 50 ºC for 12 hours. Polymer of Polymer of Colloidal Silica Example 4 (g) Example 5 (g) (178% solution) 78 PCT PATENT APPLICATION 364.1746PC3 [00283] 348.9 grams of water and 12.4 grams of 30% sodium lauryl sulfate solution in water (Stanfax 234) were added to a 1-liter glass reactor with inlet ports for an agitator, water cooled condenser, thermocouple, nitrogen sparging and adapters for the addition of monomer and initiator solutions. The contents were heated to 84 °C with overhead stirring and nitrogen sparge for at least 1 hour. [00284] An initiator solution comprising 0.59 grams sodium persulfate dissolved in 8.7 grams water was added as a shot to the reactor contents. A monomer pre-emulsion of 152.4 grams of water, 7.7 grams of 30% sodium lauryl sulfate solution in water, 83.9 grams of methyl methacrylate, 119 .6 grams butyl acrylate, and 1.6 grams of methacrylic acid was added over 72 minutes. An initiator solution comprising 0.47 grams sodium persulfate dissolved in 26.75 grams water was added at a rate of 0.26 grams per minute over 72 minutes with some of the solution leftover for the next stage. The reactor contents was held at 84 °C for 30 minutes. A second monomer pre-emulsion of 56.2 grams of water, 3.2 grams of 30% sodium lauryl sulfate solution in water, 27.4 grams of methyl methacrylate, 50.0 grams butyl acrylate, 1.54 grams of vinyl trimethoxy silane and 0.7 rams of methacrylic acid was added over 28 minutes. Simultaneously, the rest of the initiator solution was added over 28 minutes. The reactor contents was held at 84 °C for 30 minutes. The final product was a water white emulsion with a solid content of 32.5%. Example 8 Composite Particle Using Acrylate Polymer: [00285] The following composite polymers are produced by mixing the amount of the polymer of Example 7 with the amount of the colloidal silica from Examples 2, as shown below. Next a 10% NaOH is added to adjust the pH in the 8-10 range. This mixture is stirred for 50 ºC for 12 hours. Polymer of Polymer of Colloidal Silica Example 7 (g) Example 5 (g) (178% solution) [00286] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It being understood that various changes may be made 79 PCT PATENT APPLICATION 364.1746PC3 in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims. 80

Claims

PCT PATENT APPLICATION 364.1746PC3 CLAIMS What is claimed is: 1. A composite particle comprising the reaction product of: A. a silica particle; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is chosen from: (1) a comb polymer having the formula (I): a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; 81 PCT PATENT APPLICATION 364.1746PC3 (iv) R2 is -S-R11-Si(OR’)3; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5 is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1; (2) an acrylate polymer comprising the at least one Si-OR’ group, (3) a core shell polymer comprising: at least one core polymer that is the polymerization reaction product of a first monomer mixture comprising: a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; and g1) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a1) is not present in said first monomer mixture then e1) is present in said first monomer mixture; 82 PCT PATENT APPLICATION 364.1746PC3 wherein if f1) is not present in said first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said first monomer mixture; wherein if f1) is present in said first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said first monomer mixture; wherein at least one of b1) and f1) is present in said first monomer mixture; and at least one shell polymer disposed about said at least one core polymer wherein said at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture comprising: a2) optionally one or more anionic ethylenically unsaturated monomers; b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; and g2) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a2) is not present in said second monomer mixture then e2) is present in said second monomer mixture; wherein if f2) is not present in said second monomer mixture then a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said second monomer mixture; wherein if f2) is present in said second monomer mixture then a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said second monomer mixture; wherein at least one of b2) and f2) is present in said second monomer mixture; and 83 PCT PATENT APPLICATION 364.1746PC3 wherein at least one of said first monomer mixture and said second monomer mixture comprises a1) or a2) in an amount greater than zero mol %, respectively; wherein at least one of g1) and g2) is utilized; and (4) combinations thereof. 2. The composite particle of claim 1 wherein a is 0.5-75 mol%; b is 0-99 mol%; c is 0-99 mol%; d is 0 -10 mol%; and e is 0-10 mol%. 3. The composite particle of claim 1 wherein a is 1-50 mol%; b is 10-90 mol%; c is 10-90 mol%; d is 0-10 mol%; e is 0-10 mol%; n is 1-200, wherein the -O-CHR6-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7 is H or CH3. 4. The composite particle of claim 1 wherein a is 2-10 mol%; b is 15-85 mol%; c is 15-85 mol%; d is 0.05-10 mol%; n is 5-150, wherein the -O-CH2-CHR7- groups are the same or different; X is O; R6 is H or CH3; and 84 PCT PATENT APPLICATION 364.1746PC3 R7 is H or CH3. 5. The composite particle of any preceding claim wherein the polymer is the comb polymer to the exclusion of the acrylate polymer and/or the core shell polymer. 6. The composite particle of any one of claims 1 to 4 wherein the polymer is the acrylate polymer to the exclusion of the comb polymer and/or the core shell polymer. 7. The composite particle of any one of claims 1 to 4 wherein the polymer is the core shell polymer to the exclusion of the comb polymer and/or the acrylate polymer. 8. The composite particle of any one of claims 1 to 4 or 6 wherein the acrylate polymer is the reaction product of a single acrylate monomer and one or more of a silane monomer, silanol monomer, a silane chain transfer agent, and a silanol chain transfer agent. 9. The composite particle of any one of claims 1 to 4 or 6 wherein the acrylate polymer is the reaction product of a first acrylate monomer, a second acrylate monomer, and one or more of a silane monomer, silanol monomer, a silane chain transfer agent, and a silanol chain transfer agent. 10. The composite particle of claim 8 or 9 wherein the silanol chain transfer agent is -S-R11- Si(OH)3; -S-R11-Si(OCH3)3; -S-R11-Si(OCH2CH3)3, or combinations thereof. 11. The composite particle of any one of claims 1 to 4 or 6 wherein the acrylate polymer is the reaction product of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate and one or both of a silane monomer and a silanol monomer. 12. The composite particle of any one of claims 8 to 11 wherein the silane monomer is vinyl trimethoxy silane and the silanol monomer is vinyl trimethoxy silanol. 13. The composite particle of any one of claims 1 to 4 wherein the polymer comprises a combination of the comb polymer and the acrylate polymer. 85 PCT PATENT APPLICATION 364.1746PC3 14. The composite particle of any one of claims 1 to 4 wherein the polymer comprises a combination of the comb polymer and the core shell polymer. 15. The composite particle of any one of claims 1 to 4 wherein the polymer comprises a combination of the core shell polymer and the acrylate polymer. 16. A paint composition comprising: (1) water and/or an organic solvent; (2) an optional binder; (3) an optional pigment; and (4) the composite particle of any preceding claim. 17. A method of forming the composite particle of any one of claims 1 to 4 comprising the steps of: introducing at least one acrylate monomer and at least one silane monomer, silanol monomer, and/or silane or silanol chain transfer agent into a polymerization reactor; polymerizing the at least one acrylate monomer and the silane monomer, silanol monomer, and/or silane or silanol chain transfer agent in the polymerization reactor to form the acrylate polymer; combining the acrylate polymer and the silica particle; and reacting the acrylate polymer and the silica particle via a condensation reaction to form the composite particle wherein the acrylate polymer is attached to the surface of the silica particle via an O-Si bond. 18. The method of claim 17 wherein the step of reacting occurs at a pH of about 7 to about 10. 19. The method of claim 17 or 18 wherein the silane monomer is utilized, the method further includes a step of hydrolyzing the silane monomer to form a silanol monomer in the presence of the at least one acrylic monomer or after the step of polymerizing, and the step of polymerizing occurs at a pH of about 1 to about 6. 86 PCT PATENT APPLICATION 364.1746PC3 20. A method of forming the composite particle of any one of claims 1 to 4 comprising the steps of: combining the comb polymer and the silica particle; and reacting the comb polymer and the silica particle via a condensation reaction to form the composite particle wherein the polymer is attached to the surface of the silica particle via an O-Si bond. 21. The method of claim 20 wherein the step of reacting occurs at a pH of about 5 to about 11. 22. A composite particle comprising the reaction product of: A. a silica particle; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is a comb polymer having the formula (I): 87 PCT PATENT APPLICATION 364.1746PC3 wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3 when d = 0; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5 is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1. 23. A composite particle comprising the reaction product of: A. a silica particle ; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is an acrylate polymer comprising the at least one Si-OR’ group. 24. A composite particle comprising the reaction product of: A. a silica particle ; and B. a polymer that includes at least one Si-OR’ group wherein R’ is an alkyl group or H; 88 PCT PATENT APPLICATION 364.1746PC3 wherein the polymer is attached to the surface of the silica particle via an O-Si bond; and wherein the polymer is a core shell polymer comprising: at least one core polymer that is the polymerization reaction product of a first monomer mixture comprising: a1) optionally one or more anionic ethylenically unsaturated monomers; b1) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c1) optionally one or more associative monomers; d1) optionally one or more cross-linking monomers; e1) optionally one or more nonionic ethylenically unsaturated monomers; f1) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; and g1) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a1) is not present in said first monomer mixture then e1) is present in said first monomer mixture; wherein if f1) is not present in said first monomer mixture then a1) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said first monomer mixture; wherein if f1) is present in said first monomer mixture then a1) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said first monomer mixture; wherein at least one of b1) and f1) is present in said first monomer mixture; and at least one shell polymer disposed about said at least one core polymer wherein said at least one shell polymer is at least partially cross-linked and is the polymerization reaction product of a second monomer mixture comprising: a2) optionally one or more anionic ethylenically unsaturated monomers; 89 PCT PATENT APPLICATION 364.1746PC3 b2) optionally one or more short chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 7 or fewer carbon atoms; c2) optionally one or more associative monomers; d2) one or more cross-linking monomers; e2) optionally one or more nonionic ethylenically unsaturated monomers; f2) optionally one or more long chain hydrophobic ethylenically unsaturated monomers having a side chain comprising a hydrophobe that has 8 or greater carbon atoms; and g2) optionally one or more monomers or chain transfer agents with a silane or silanol group. wherein if a2) is not present in said second monomer mixture then e2) is present in said second monomer mixture; wherein if f2) is not present in said second monomer mixture then a2) is present in an amount of from 0 to about 60 mol% based on a total number of moles of monomers in said second monomer mixture; wherein if f2) is present in said second monomer mixture then a2) is present in an amount of from 0 to about 80 mol% based on a total number of moles of monomers in said second monomer mixture; wherein at least one of b2) and f2) is present in said second monomer mixture; and wherein at least one of said first monomer mixture and said second monomer mixture comprises a1) or a2) in an amount greater than zero mol %, respectively; and wherein at least one of g1) and g2) is utilized. 25. The composite particle of claim 1 wherein said at least one shell polymer comprises a mol % of residue of said d2) one or more crosslinking monomers that is greater than a mol % of residue of said d1) one of more cross-linking monomers in said at least one core polymer. 26. The composite particle of claim 1 or 25 wherein said core shell polymer comprises two or more shell polymers and at least one shell polymer comprises a mol % of residue of said d2) one 90 PCT PATENT APPLICATION 364.1746PC3 or more crosslinking monomers that is less than a mol % of residues of said d1) one of more cross- linking monomers in said at least one core polymer. 27. The composite particle of any of claims 1, 25, or 26 wherein said at least core shell polymer accounts for greater than 5 wt % and less than about 90 wt % of a total weight of said core shell polymer. 28. The composite particle of any one of claims 1 or 25-27 wherein: b1) and/or f1) is present in said first monomer mixture in at least about 1 mol% based on a total number of moles of monomers in said first monomer mixture and said a1) anionic ethylenically unsaturated monomer is present in said first monomer mixture in 10 mol% or less based on a total number of moles of monomers in said first monomer mixture; and b2) and/or f2) is present in said second monomer mixture in at least about 1 mol% based on a total number of moles of monomers in said second monomer mixture and said a2) anionic ethylenically unsaturated monomer is present in said second monomer mixture in 10 mol% or less based on a total number of moles of monomers in said second monomer mixture. 29. The composite particle of any one of claims 1 or 25-28 wherein one or both of said at least one core polymer and said shell polymer comprises an increasing gradient of cross-link density measured in an outward direction extending from a center of said at least one core polymer towards said shell polymer wherein said cross-link density of said at least one core polymer is optionally less than said cross-link density of said shell polymer. 30. The composite particle of any one of claims 1 or 25-29 wherein said first monomer mixture is free of said d1) one or more cross-linking monomers. 31. The composite particle of any one of claims 1 or 25-30 wherein said core shell polymer comprises a first shell polymer and a second shell polymer wherein said first shell polymer is disposed on and in direct contact with said at least one core polymer and said second shell polymer is disposed on and in direct contact with said first shell polymer. 91 PCT PATENT APPLICATION 364.1746PC3 32. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is greater than said cross-link density of said at least one core polymer; and said cross-link density of said second shell polymer is greater than said cross-link density of said first shell polymer and greater than said cross-link density of said at least one core polymer. 33. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is greater than said cross-link density of said at least one core polymer; and said cross-link density of said second shell polymer is less than said cross-link density of said first shell polymer and greater than said cross-link density of said at least one core polymer. 34. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is less than said cross-link density of said at least one core polymer; and said cross-link density of said second shell polymer is greater than said cross-link density of said at least one core polymer and greater than said cross-link density of said first shell polymer. 35. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is greater than said cross-link density of said at least one core polymer; and said cross-link density of said second shell polymer is less than said cross-link density of said at least one core polymer and less than said cross-link density of said first shell polymer. 92 PCT PATENT APPLICATION 364.1746PC3 36. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is less than said cross-link density of said at least one core polymer; and said cross-link density of said second shell polymer is less than said cross-link density of said at least one core polymer and greater than said cross-link density of said first shell polymer. 37. The composite particle of claim 31 wherein each of said at least one core polymer, said first shell polymer, and said second shell polymer has a cross-link density, said cross-link density of said first shell polymer is less than said cross-link density of said core; and said cross-link density of said second shell polymer is less than said cross-link density of said at least one core polymer and less than said cross-link density of said first shell polymer. 38. The composite particle of any one of claims 1 or 25-37 wherein said one or more c1) and c2) associative monomers are not present in said first and second monomer mixtures. 39. The composite particle of any one of claims 1 or 25-38 wherein the g1) and/or g2) one or more monomers or chain transfer agents with a silane or silanol group is chosen from trimethylsilanol; dimethylsilanediol; methylsilanetriol; tetrahydroxysilane; 3- (trihydroxysilyl)propylamine; 3-(trihydroxysilyl)propionic acid; hydroxyl-terminated polydimethylsiloxane (PDMS-OH); trimethylsilane; dimethylsilane; methylsilane; phenylsilane; chlorotrimethylsilane; dichlorodimethylsilane; trichloromethylsilane; tetrachlorosilane; trimethoxysilane; triethoxysilane; methyldimethoxysilane; phenyltrimethoxysilane; 3- aminopropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane; vinyltrimethoxysilane; (3- glycidoxypropyl)trimethoxysilane; tris(trimethylsiloxy)silane; methyldichlorosilane; dimethylchlorosilane; tetramethyldisiloxane; silane-modified thiols; and combinations thereof. 40. The composite particle of any one of claims 1 or 25-39 wherein the molar percent of residues of g1) and/or g2) is from about 0.01 to about 10 mol%, based on a total moles of reactants. 93 PCT PATENT APPLICATION 364.1746PC3 41. The composite particle of any one of claims 1 or 25-39 wherein the molar percent of residues of g1) and/or g2) is from about 0.5 to about 3 mol%, based on a total moles of reactants. 94
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