WO2025147580A1 - Block copolymers comprising repeating units obtained by polymerizing cyclic diester and acrylic monomers and applications thereof - Google Patents

Abstract

The invention provides block copolymers comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof. The invention further provides compositions comprising such block copolymers and applications thereof in various industrial areas, particularly as emulsifiers and more particularly as Pickering emulsifiers. Subscripts m and n are as described herein.

Description

BLOCK COPOLYMERS COMPRISING REPEATING UNITS OBTAINED BY POLYMERIZING CYCLIC DIESTER AND ACRYLIC MONOMERS AND APPLICATIONS THEREOF

BACKGROUND

Field of the Invention

[0001] The disclosed and/or claimed inventive concept(s) provides block copolymers comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof, compositions comprising these polymers, and industrial applications of these compositions.

Description of Related Art

[0002] It is well-known that block copolymers undergo self-assembly both in the solid state and in solution. In the latter case, a diverse range of copolymer morphologies has been reported, including spheres, worms, or vesicles. Typically, the copolymer chains are first prepared in a non- selective solvent and then subjected to either a gradual change in solvency or a pH switch in a separate step, which is typically undertaken in dilute solution.

[0003] In recent years, polymerization-induced self-assembly (PISA) of block copolymers in a solvent that is selective for the growing second block has become increasingly popular. PISA offers two decisive advantages over traditional processing methods: (i) syntheses can be conducted at up to 50% w/w solids and (ii) diblock copolymer nanoparticles are obtained directly, without requiring any post-polymerization processing steps. When combined with PISA, controlled radical polymerization techniques such as atom transfer radical polymerization (ATRP) or reversible addition-fragmentation chain transfer (RAFT) polymerization has enabled the preparation of a wide range of well-defined nanoparticles. RAFT dispersion polymerization is known to allow the efficient synthesis of spherical, worm-like or vesicular morphologies in aqueous, alcoholic, or nonpolar media as well as ionic liquids.

[0004] U.S. published application 2022/0298284 discloses a core-satellite micelle including a core, a shell surrounding the core, and a plurality of satellite domains positioned inside the shell. The core-satellite micelle includes a tetrablock copolymer represented by Structural Formula Al - B1-A2-B2 wherein Al is a first-monomcr first block, Bl is a sccond-monomcr first block, A2 is a first-monomer second block, and B2 is a second-monomer second block. The first-monomer first block Al and the first-monomer second block A2 may be each independently include any one segment selected from the segment group consisting of a polyvinylpyrrolidone segment, a polylactic acid segment, a polyvinylpyridine segment, a polystyrene segment, a polytrimethylsilylstyrene segment, a C1-C9 polyalkylene oxide segment, a polybutadiene segment, a polyisoprene segment, a polyolefin segment, and a C1-C5 polyalkyl(meth)acrylate segment.

[0005] PCT published application 2020/117170 discloses a biosensor comprising a polyphosphonoundecyl acrylate -co-polyvinylimidazole-co-polyvinylferrocene-co-polyglycidyl methacrylate tetra block copolymer as an electron transmitter between the glucose oxidase and redox centre of the electrode for measuring glucose from sweat.

[0006] U.S. published application 2005/0256265 discloses an article comprising S1-B1-S2-B2 tetrablock copolymer and at least one other component selected from the group consisting of olefin polymers, styrene polymers, tackifying resins, polymer extending oils and engineering thermoplastic resins, wherein SI, Bl, S2, and B2 are polymer blocks, and Bl is a block of polymerized conjugated diene comprising at least 50 mole percent isoprene having an apparent molecular weight of from about 150,000 to about 400,000; SI and S2 are blocks of polymerized monovinyl aromatic hydrocarbon having a weight average molecular weight of about 12,000 to about 40,000; and B2 is a block of polymerized conjugated diene comprising at least 50 mole percent isoprene having an apparent molecular weight of from about 15,000 to about 60,000.

[0007] U.S. patent 10,905,636 discloses block copolymers comprising repeating units derived from monomers comprising lactam and acryloyl moieties and hydrophobic monomers, compositions, and applications thereof.

[0008] U.S. published application 2020/0407470 discloses methods of synthesis of homopolymers and non-homopolymers comprising repeating units derived from monomers comprising lactam and acryloyl moieties in an aqueous medium. [0009] U.S. published application 2019/0382519 discloses cross-linked block copolymers comprising repeating units derived from monomers comprising lactam and acryloyl moictics, compositions, and applications thereof.

[0010] U.S. published application 2019/0375875 discloses high molecular weight block copolymers comprising repeating units derived from monomers comprising lactam and acryloyl moieties and hydrophilic monomers, compositions, and applications thereof.

[0011] Yu in University of Warwick Ph.D. thesis (2019) describes the crystallization driven selfassembly of polyester based triblock copolymers.

[0012] Bromley in University of Surrey Ph.D. thesis (2020) describes the synthesis of triblock copolymers from A'-2-hydroxypropyl methacrylamide and homotelechelic caprolactone with terminal RAFT functionalities as therapeutic polymer nanocarriers for drug delivery applications.

[0013] Kim, Mays et al. in Polymer (2018), 158: 198-203 describe porous poly(£-caprolactone) microspheres via UV photodegradation of block copolymers prepared by RAFT polymerization.

[0014] Bian, Xiao et al. in Journal of Polymer Science Part A Polymer Chemistry (2011), 50: 571-580 describe a RAFT approach for polymerization of A'-isopropylacrylamidc with a star poly(£-caprolactone) core.

[0015] Jeong et al. in ACS Sustainable Chemistry and Engineering (2023), 11 (12), 4871-4884 describe the preparation and pressure-sensitive adhesive and elastomer properties of renewable and degradable triblock copolymers with an ABA-type triblock structure derived from renewable resources.

[0016] Ning et al. in Polymers (2018), 10(2), 214 describe the synthesis of well-defined novel, linear, biodegradable, amphiphilic thermo-responsive ABA-type triblock copolymers via a combination of ring-opening polymerization of £-caprolactone and RAFT polymerization of a combination of methacrylate monomers.

[0017] It has been found that block copolymer compositions comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof have unique physicochemical properties such as the ability to act as emulsifiers and enhanced degradability.

Accordingly, these polymers have several industrial applications.

SUMMARY

[0018] In a first aspect, the disclosed and/or claimed inventive concept(s) provides a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0019] In a second aspect, the disclosed and/or claimed inventive concept(s) provides a composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0020] In a third aspect, the disclosed and/or claimed inventive concept(s) provides an emulsifier composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0021] In a fourth aspect, the disclosed and/or claimed inventive concept(s) provides a method for preparing a block copolymer, the method comprising: (a) initiating ring-opening polymerization of at least one cyclic diester monomer by including in the polymerization medium a reversible addition-fragmentation chain transfer agent and a catalyst resulting in a moiety having repeating units derived from said cyclic diester monomer, (b) dissolving the moiety in at least one acrylate and/or acrylamide monomer(s), (c) polymerizing the acrylate and/or acrylamide monomer(s) in bulk at a temperature ranging from about 40° C to about 90° C until a conversion from about 5% to about 80% of the acrylate and/or acrylamide monomer(s) is achieved, (d) adding water at a temperature ranging from about 40° C to about 90° C to the polymerization medium to obtain an aqueous dispersion, and optionally (e) continuing polymerization of the acrylate and/or acrylamide monomer(s) until a conversion of at least about 95% of the acrylate and/or acrylamide monomer(s) is achieved. DETAILED DESCRIPTION

[0022] Before explaining at least one aspect of the disclosed and/or claimed inventive concept(s) in detail, it is to be understood that the disclosed and/or claimed inventive concept(s) is not limited in its application to the details of construction and the arrangement of the components or steps or methodologies set forth in the following description or illustrated in the drawings. The disclosed and/or claimed inventive concept(s) is capable of other aspects or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0023] Unless otherwise defined herein, technical terms used in connection with the disclosed and/or claimed inventive concept(s) shall have the meanings that are commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0024] All patents, published patent applications, and non-patent publications referenced in any portion of this application are herein expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference.

[0025] All articles and/or methods disclosed herein can be made and executed without undue experimentation based on the present disclosure. While the articles and methods of the disclosed and/or claimed inventive concept(s) have been described in terms of aspects, it will be apparent to those of ordinary skill in the art that variations may be applied to the articles and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the disclosed and/or claimed inventive concept(s). All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the disclosed and/or claimed inventive concept(s).

[0026] As utilized in accordance with the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

[0027] The use of the word “a” or “an” when used in conjunction with the term “comprising” may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” is used to mean “and/or” unless explicitly indicated to refer to alternatives only if the alternatives arc mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.”

[0028] Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the quantifying device, the method being employed to determine the value, or the variation that exists among the study subjects. For example, but not by way of limitation, when the term “about” is utilized, the designated value may vary by plus or minus twelve percent, or eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent.

[0029] The use of the term “at least one” will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term “at least one” may extend up to 100 or 1000 or more depending on the term to which it is attached. In addition, the quantities of 100/1000 are not to be considered limiting as lower or higher limits may also produce satisfactory results. In addition, the use of the term “at least one of X, Y, and Z” will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z. The use of ordinal number terminology (i.e., “first”, “second”, “third”, “fourth”, etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not meant to imply any sequence or order or importance to one item over another or any order of addition.

[0030] As used herein, the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The term “or combinations thereof’ as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, Bxn, Bxn+i, or combinations thereof’ is intended to include at least one of: A, Bx_n, Bxn+i, ABxn, ABxn+i, BxnBxii+1, or ABxiiBxn+i and, iforderis important in a particular context, also Bx_nA, Bxn+iA, Bxn+iBxn, Bxn+iBxnA, BxiiBxn+iA, ABxn+iBxn, BxnABxn+i, or Bxn+iABxn. Continuing with this example, expressly included are combinations that contain repeats of one or more item Or term, SUCh aS BxnBxn, AAA, MBxn, BxnBxnBxn+1, AAABxnBxn+lBxn+lBxn+lBxn+1, Bxn+iBxnBxnAAA, Bxn+iA BxnABxiiBxn, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.

[0031 ] The term “each independently selected from the group consisting of’ means when a group appears more than once in a structure, that group may be selected independently each time it appears.

[0032] The term “hydrocarbyl” includes straight-chain and branched-chain alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl groups, and combinations thereof with optional heteroatom(s). A hydrocarbyl group may be mono-, di- or polyvalent.

[0033] The term “alkyl” refers to a functionalized or unfunctionalized, monovalent, straightchain, branched-chain, or cyclic hydrocarbyl group optionally having one or more heteroatoms. Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, u-butyl, isobutyl, tert- butyl, 77-pentyl, isopentyl, n-hexyl, n-hcptyl, /7-octyl, 2-ethylhexyl, Ze/7-octyl, iw-norbornyl, n- dodecyl, tert-dodecyl, u-tetradecyl, n-hexadecyl, /7-octadccyl, w-eicosyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The definition of “alkyl” also includes groups obtained by combinations of straight-chain, branched-chain and/or cyclic structures.

[0034] The term “aryl” refers to a functionalized or unfunctionalized, monovalent, aromatic hydrocarbyl group optionally having one or more heteroatoms. The definition of aryl includes carbocyclic and heterocyclic aromatic groups. Non-limiting examples of aryl groups include phenyl, naphthyl, indenyl, indanyl, azulenyl, fluorenyl, anthracenyl, furyl, thienyl, pyridyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,3,5-trithianyl, indolizinyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furanyl, 2,3-dihydrobenzofuranyl, benzo [b]thiophenyl, IH-indazolyl, benzimidazolyl, bcnzthiazolyl, purinyl, 4H-quinolizinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxyazinyl, pyrazolo[l,5-c]triazinyl, and the like.

[0035] The term “aralkyl” refers to an alkyl group comprising one or more aryl substituent(s) wherein "aryl" and "alkyl" are as defined above. Non-limiting examples of aralkyl groups include benzyl, 2-phenyl-ethyl, 3 -phenyl -propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4- bcnzylcyclohcxyl, 4-phcnylcyclohcxylmcthyl, 4-bcnzylcyclohcxylmcthyl, and the like.

[0036] The term “alkylene” refers to a functionalized or unfunctionalized, divalent, straightchain, branched-chain, or cyclic hydrocarbyl group optionally having one or more heteroatoms. Non-limiting examples of alkylene groups include:

[0037] The term “arylene” refers to a functionalized or unfunctionalized, divalent, aromatic hydrocarbyl group optionally having one or more heteroatoms. The definition of arylene includes carbocyclic and heterocyclic groups. Non-limiting examples of arylene groups include phenylene, naphthylene, pyridinylene, and the like.

[0038] The term “heteroatom” refers to oxygen, nitrogen, sulfur, silicon, phosphorous, or halogen. The heteroatom(s) may be present as a part of one or more heteroatom-containing functional groups. Non-limiting examples of heteroatom-containing functional groups include ether, hydroxy, epoxy, carbonyl, carboxamide, carboxylic ester, carboxylic acid, imine, imide, amine, sulfonic, sulfonamide, phosphonic, and silane groups. The hctcroatom(s) may also be present as a part of a ring such as in heterocycloalkyl, heteroaryl, and heteroarylene groups.

[0039] The term “halogen” or “halo” refers to Cl, Br, I, or F.

[0040] The term “ammonium” includes protonated NFb and protonated primary, secondary, and tertiary organic amines.

[0041] The term “functionalized” with reference to any moiety refers to the presence of one or more functional groups in the moiety. Various functional groups may be introduced in a moiety by way of one or more functionalization reactions known to a person having ordinary skill in the art. Non-limiting examples of functionalization reactions include alkylation, epoxidation, sulfonation, hydrolysis, amidation, esterification, hydroxylation, dihydroxylation, amination, ammonolysis, acylation, nitration, oxidation, dehydration, elimination, hydration, dehydrogenation, hydrogenation, acetalization, halogenation, dehydrohalogenation, Michael addition, aldol condensation, Canizzaro reaction, Mannich reaction, Clasien condensation, Suzuki coupling, and the like. In one non-limiting embodiment, the term “functionalized” with reference to any moiety refers to the presence of one more functional groups selected from the group consisting of alkyl, alkenyl, hydroxyl, carboxyl, halogen, alkoxy, amino, imino, and combinations thereof, in the moiety.

[0042] The term “monomer” refers to a small molecule that chemically bonds during polymerization to one or more monomers of the same or different kind to form a polymer.

[0043] The term “polymer” refers to a large molecule comprising one or more types of monomer residues (repeating units) connected by covalent chemical bonds. By this definition, polymer encompasses compounds wherein the number of monomer units may range from very few, which more commonly may be called as oligomers, to very many. Non-limiting examples of polymers include homopolymers, and non-homopolymers such as copolymers, terpolymers, tetrapolymers and the higher analogues. The polymer may have a random, block, and/or alternating architecture.

[0044] The term “homopolymer” refers to a polymer that consists essentially of a single monomer type. [0045] The term “non-homopolymer” refers to a polymer that comprises more than one monomer types.

[0046] The term “copolymer” refers to a non-homopolymer that comprises two different monomer types.

[0047] The term “terpolymer” refers to a non-homopolymer that comprises three different monomer types.

[0048] The term “branched” refers to any non-linear molecular structure. The term includes both branched and hyper-branched structures.

[0049] The term “block copolymer” refers to a polymer comprising at least two blocks of polymerized monomers. Any block may be derived from either a single monomer resulting in a homopolymeric subunit, or two or more monomers resulting in a copolymeric (or non- homopolymeric) subunit in the block copolymer. The block copolymers may be diblock copolymers (i.e., polymers comprising two blocks of monomers), triblock copolymers (i.e., polymers comprising three blocks of monomers), tetrablock copolymers (i.e., polymers comprising four blocks of monomers), or multiblock copolymers (i.e., polymers comprising more than four blocks of monomers), and combinations thereof. The block copolymers may be linear, branched, star or comb like, and have structures such as [A][B], [A][B][A], [A][B][C], [A][B][A][B], [A][B][C][B], etc. An exemplary representation of block copolymer is [A]_x[B]_y or [A]_x[B]y[C]z, wherein x, y and z are the degrees of polymerization (DP) of the monomers A, B, and C in the corresponding blocks [A], [B], and [C]. Additional insight into the chemistry, characterization and applications of block copolymers may be found in the book ‘Block Copolymers: Synthetic Strategies, Physical Properties, and Applications', by Nikos Hadjichristidis, Stergios Pispas, and George Floudas, John Wiley and Sons (2003), the contents of which are herein incorporated in its entirety by reference.

[0050] The term “controlled radical polymerization” refers to a specific radical polymerization process, also denoted by the term of “living radical polymerization”, in which use is made of control agents, such that the block copolymer chains being formed are functionalized by end groups capable of being reactivated in the form of free radicals by virtue of reversible transfer or reversible termination reactions. [0051 ] The term “addition-fragmentation” refers to a two-step chain transfer mechanism during polymerization leading to homopolymers and block copolymers wherein a radical addition is followed by fragmentation to generate a new radical species.

[0052] The term RAFT refers to reversible addition-fragmentation chain transfer.

[0053] The term “free radical addition polymerization initiator” refers to a compound used in a catalytic amount to initiate a free radical addition polymerization. The choice of initiator depends mainly upon its solubility and its decomposition temperature.

[0054] The term "alkyl acrylate" refers to an alkyl ester of acrylic acid.

[0055] The term "alkyl acrylamide" refers to an alkyl amide of acrylic acid.

[0056] The term "alkyl (meth)acrylate" refers to an alkyl ester of methacrylic acid.

[0057] The term "alkyl (meth)acrylamide" refers to an alkyl amide of methacrylic acid.

[0058] The term “moiety” refers to a part or a functional group of a molecule.

[0059] The term “coating composition” refers to a composition that is capable of application to a substrate for imparting certain performance attributes to the substrate.

[0060] The terms “personal care composition” refers to a composition intended for use on or in a human subject for imparting certain benefits to the subject.

[0061 ] The term “nutrition composition” refers to a composition intended to provide complete or supplemental nutrition to a subject such as a human or an animal.

[0062] The term “pharmaceutical composition” refers to a composition intended to provide certain health benefits to a subject such as a human or an animal. Pharmaceutical compositions typically comprise one or more pharmaceutically active ingredients and one or more additives (or excipients). The definition of pharmaceutical compositions includes biotechnological compositions.

[0063] The term “agricultural composition” refers to a composition that is capable of application to subjects such as plants, trees, shrubs, weeds, landscapes, grass, and pastures either in their entirety or to any living or nonliving part thereof to confer certain benefits to these subjects. Agricultural compositions typically include one or more active ingredients and one or more additives.

[0064] The term “adhesive composition” refers to a composition comprising at least one agent that promotes adhesion between two or more predetermined surfaces.

[0065] The term “battery composition” refers to a composition intended for use in electrochemical devices that convert chemical energy into electrical energy.

[0066] The term “oilfield composition” refers to a composition intended for use in the exploration, extraction, recovery, and/or completion of any mineral oil or hydrocarbon.

[0067] The term “metal working fluid” refers to any fluid which may be used in a metal working process for one or more functions, which may include cooling, lubrication, debris removal, reducing or inhibiting corrosion, reducing or inhibiting material build up on workpieces and/or metal working tools, etc. Metal working fluids may also be referred to interchangeably as a “cutting fluid,” a “cutting oil,” a “cutting compound,” etc.

[0068] The term “emulsifying agent” refers to a compound that stabilizes an emulsion, i.e. a mixture of two or more liquids. The emulsifying agent can be a single compound or a combination of two or more compounds. The emulsifying agent can be anionic, cationic, or non-ionic, or can include a combination of anionic, cationic, and non-ionic compounds.

[0069] The term “emulsifier composition” refers to a composition that is capable of stabilizing an emulsion because of the presence of one or more emulsifying agents therein.

[0070] The term “colloidal” refers to the state of matter having nanometer dimensions.

[0071] The term “Pickering emulsion” refers to an emulsion comprising a first liquid phase dispersed in a second continuous liquid phase that is stabilized by solid particles (for example colloidal particles like silica) which adsorb onto the interface between the two phases. More details on Pickering emulsions can be found in the article titled ‘Emulsions stabilized with solid nanoparticles: Pickering emulsions ’ in Colloids and Surfaces A : Physicochemical and Engineering Aspects, Volume 439, 2013, Pages 23-34, by Chevalier, Y. and Bolzinger, M. A. [0072] All percentages, ratio, and proportions used herein are based on a weight basis unless specified otherwise.

[0073] In a first aspect, the disclosed and/or claimed inventive concept(s) provides a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0074] In a specific embodiment, the cyclic diester monomer in the block copolymer is selected from the group consisting of lactides, glycolides, and combinations thereof.

[0075] In a specific embodiment, the lactide is selected from the group consisting of L-lactidc, D-lactide, and combinations thereof.

[0076] In a specific embodiment, the second monomer is a functionalized or unfunctionalized Ci -Ci s alkyl acrylate or Ci-Cis alkyl (meth)acrylate.

[0077] In a specific embodiment, the second monomer is selected from the group consisting of functionalized or unfunctionalized acrylamide, (meth)acrylamide, N-C 1-C 18 alkyl acrylamide, N- C1-C18 alkyl (meth)acrylamide, 7V,7V'-diCl-C18 alkyl acrylamide, A/7V'-diCl-C18 alkyl (meth)acrylamide, and combinations thereof.

[0078] Particular, yet non-limiting examples of the second monomer include acrylamide, (meth)acrylamide, /V-mcthyl acrylamide, /V-mcthyl (meth)acrylamide, TV, N '-dimethyl acrylamide, /V,/V '-dimethyl (meth)acrylamide, TV-acryloyl morpholine, and combinations thereof.

[0079] In specific embodiments, the block copolymer according to the disclosed and/or claimed inventive concept(s) has a structure selected from the group consisting of:

wherein each m ranges from about 5 to about 100 and each n ranges from about 10 to 5,000. [0080] Particularly, each m ranges from about 10 to about 100 and each n ranges from about 25 to 1,000. More particularly, each m ranges from about 10 to about 75 and each n ranges from about 50 to 500.

[0081] In a second aspect, the disclosed and/or claimed inventive concept(s) provides a composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0082] In one specific embodiment, the composition comprising a block copolymer according to the disclosed and/or claimed inventive concept(s) is in the form of an aqueous dispersion. In another specific embodiment, the composition according to the disclosed and/or claimed inventive concept(s) is in the form of a Pickering emulsion.

[0083] In a specific embodiment, the block copolymer in the composition according to the disclosed and/or claimed inventive concept(s) is in the form of colloidal particles. Further insight into the structure and properties of colloidal particles may be found in the publication J. Am. Chem. Soc., 2014, volume 136, 10174-10185, the contents of which are herein incorporated in its entirety be reference.

[0084] In a specific embodiment, the colloidal particles are nanoparticles.

[0085] In a specific embodiment, the nanoparticles have semicrystalline cores.

[0086] In a third aspect, the disclosed and/or claimed inventive concept(s) provides an emulsifier composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

[0087] In a specific embodiment, the composition comprising a block copolymer according to the disclosed and/or claimed inventive concept(s) is a coating composition, a personal care composition, a nutrition composition, a pharmaceutical composition, a home care composition, an agricultural composition, an adhesive composition, a battery composition, an oilfield composition, or a metal working fluid composition. [0088] Tn a specific embodiment, the composition further comprises at least one additive selected from the group consisting of solubilizers, binders, lubricants, surfactants, oils, waxes, solvents, secondary emulsifiers, preservatives, antioxidants, antiradical protecting agents, vitamins, perfumes, dyes, pigments, humectants, fillers, thickeners, film formers, stabilizers, buffers, spreading agents, electrolytes, acids, bases, structuring agents, abrasives, and combinations thereof.

[0089] Non-limiting examples of personal care compositions include sun care compositions, face care compositions, lip care compositions, eye care compositions, skin care compositions, after-sun compositions, body care compositions, nail care compositions, anti-aging compositions, insect repellants, oral care compositions, deodorant compositions, hair care compositions, conditioning compositions, color cosmetic compositions, color-protection compositions, selftanning compositions, and foot care compositions.

[0090] The personal care compositions may further comprise at least one additive selected from the group consisting of UV actives, UV active solubilizers, oils, waxes, solvents, emulsifiers, preservatives, antioxidants, antiradical protecting agents, vitamins, perfumes, insect repellants, dyes, pigments, humectants, fillers, thickeners, film formers, stabilizers, buffers, spreading agents, pearlizing agents, electrolytes, acids, bases, crystalline structuring agents, abrasives, pharmaceutically or cosmetically acceptable excipients, and combinations thereof.

[0091] Non-limiting applications of hair care compositions include hairstyle retention at high relative humidity, hair styling, hair setting, hair sculpting, hair curling, hair holding, hair waving, hair fixing, hair maintaining, hair shaping, hair straightening, hair volumizing, hair relaxing, shampooing, hair conditioning, hair cleansing, promoting hair style durability, imparting humidity resistance to hair and hair styles, enhancing hair shine, repairing split ends of hair, enhancing hair manageability such as lightness, smoothness, softness, disentangling and/or suppleness of hair, modulating hair stylability, protecting hair from thermal damage, hair dyeing, hair coloring, hair bleaching, oxidation dyeing of hair, limiting hair color bleeding, protecting hair color, hair treating (e.g., anti-dandruff), anti-hair fall, and/or protecting hair from UV radiation.

[0092] Non-limiting examples of hair care compositions include shampoos, conditioners, aerosols, mousses, sprays, mists, gels, waxes, creams, lotions, glues, pomades, spritzes, solutions, oils, liquids, solids, W/O emulsions, O/W emulsions, suspensions, multiple emulsions, microcmulsions, microencapsulated products, sticks, balms, tonics, pastes, rcconstitutablc products, nanoemulsions, solid lipid nanoparticles, liposomes, cubosomes, neosomes, putties, lacquers, serums, perms, volumizers, packs, flakes, 2-in-l shampoo/conditioner products, and 3- in-1 shampoo/conditioner/styling products.

[0093] Non-limiting examples of suitable UV actives include: octyl salicylate; pentyl dimethyl PABA; octyl dimethyl PABA; benzophenone- 1 ; benzophenone-6; 2-(2H-benzotriazole-2-yl)-4,6- di-te/7-pcntylphcnol; ethyl-2-cyano-3, 3 -diphenylacrylate; homomenthyl salicylate; bisethylhexyloxyphenol methoxyphenyl triazine; methyl-(l,2,2,6,6-pentamethyl-4-piperidyl)- sebacate; 2-(2H-benzotriazole-2-yl)-4-methylphenol; diethylhexyl butamido triazone; amyl dimethyl PABA; 4,6-bis(octylthiomethyl)-o-cresol; CAS number 65447-77-0; red petroleum; ethylhexyl triazone; octocrylene; isoamyl-p-mcthoxycinnamatc; drometrizole; titanium dioxide; 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol; 2-hydroxy-4- octyloxybenzophenone; benzophenone-2; diisopropyl methylcinnamate; PEG-25 PABA; 2 -(1,1- dimethylethyl)-6-[[3-(l , 1 -demethylethyl)-2-hydroxy-5-methylphenyl]methyl-4-methylphenyl acrylate; drometrizole trisiloxane; menthyl anthranilate; butyl methoxydibenzoylmethane; 2- ethoxyethyl p-mclhoxycinnamatc; benzylidene camphor sulfonic acid; dimethoxyphenyl-[l- (3,4)]-4,4-dimethyl 1,3 -pentanedione; zinc oxide; M.V'-hcxanc-l ,6-diylbis[3-(3,5-di-te/V-butyl-4- hydroxyphenylpropionamide)]; pentaerythritol tetrakis[3-(3,5-di-teA-butyl-4- hydroxyphenyl)propionate]; 2,6-di-ter/-butyl-4-[4,6-bis(octylthio)-l ,3,5-triazin-2-ylamino] phenol; 2-(2H-benzotriazole-2-yl)-4,6-bis(l-methyl-l-phenylethyl)phenol; trolamine salicylate; diethylanolamine /j-methoxycinnamate; polysilicone- 15; CAS number 152261-33-1; 4- methylbenzylidene camphor; bisoctrizole; n-phenyl-benzenamine; reaction products with 2,4,4- trimethylpentene; sulisobenzone; (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; digalloyl trioleate; polyacrylamide methylbenzylidene camphor; glyceryl ethylhexanoate dimethoxycinnamate; 1,3- bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{[(2'-cyano-bis-(2,2,6,6-tetramethyl-4- piperidyl)-sebacate; benzophenone-5; 1 ,3,5-tris(3,5-di-Z€/7-butyl-4-hydroxybenzyl)-l ,3,5- triazine-2,4,6(lH,3H,5H)-trione; hexamethylendiamine; benzophenone-8; ethyl-4- bis(hydroxypropyl) aminobenzoate; 6-ter^-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4- methylphenol; /?-aminobenzoic acid; 3,3^f,3",5,5^f,5"-hexa-/eA-butyl-a-a'-a"-(mesitylene-2,4,6- triy 1 )tri-/?-crcsol ; lawsone with dihydroxyacetone; benzophenone-9; benzophenone-4; ethylhexyl dimethoxy benzylidene dioxoimidazoline propionate; A,/V'-bisrormyl-MA'-bis-(2,2,6.6- tctramcthyl-4-pipcridinyl)-; 3-bcnzylidcnc camphor; tcrcphthalylidcnc dicamphor sulfonic acid; camphor benzalkonium methosulfate; bisdisulizole disodium; etocrylene; ferulic acid; 2-(2H- benzotriazole-2-yl)-4-(l , 1 ,3,3-tetramethylbutyl )-phenol; 4,6-bis(dodecylthiomethyl)-o-cresol; (3- 2-glucopyranoxy propyl hydroxy benzophenone; phenylbenzimidazole sulfonic acid; benzophenone-3; di ethylamine hydroxybenzoyl hexylbenzoate; 3 ',3'- diphenylacryloyl)oxy]methyl} -propane; ethylhexyl p-mcthoxycinnamatc. and blends thereof.

[0094] Non-limiting examples of suitable antioxidants and/or antiradical protecting agents include: BHA (teH-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-/?-cresol), TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodic oligomers, flavonoids, hindered amines such as tetra amino piperidine, erythorbic acid, polyamines such as spermine, cysteine, glutathione, superoxide dismutase, lactoferrin, and blends thereof.

[0095] Any range of composition pH may be used. In aspects wherein the composition may be applied to keratinous material, the pH may range from about 2 to 12. The pH may be adjusted to a desired value by means of adding one or more acidifying or alkalinizing agents that are well- known in the state of the art. For example, the composition can contain at least one alkalizing or acidifying agent in amounts from about 0.01% to about 30% based on the total weight of the composition.

[0096] Non-limiting examples of acidifying or acidic pH adjusting agents include organic acids, such as citric acid, acetic acid, carboxylic acids, cc-hydroxyacids, (3-hydroxyacids, a, [3- hydroxyacids, salicylic acid, tartaric acid, lactic acid, glycolic acid, natural fruit acids, and combinations thereof. In addition, inorganic acids, for example hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof can be utilized.

[0097] Non-limiting examples of alkalizing or alkaline pH adjusting agents include ammonia, alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide), ammonium hydroxide, alkanolamines (such as mono-, di- and triethanolamine), diisopropylamine, dodecylamine, diisopropanolamine, aminomethyl propanol, cocamine, oleamine, morpholine, triamylamine, triethylamine, tromethamine (2-amino-2-hydroxymethyl)-l,3-propanediol), and tetrakis(hydroxypropyl)ethylenediamine, hydroxyalkylamines and ethoxylated and/or propoxylated ethylenediamines, alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof.

[0098] Non-limiting examples of alkalizing agent can be chosen from ammonia, alkali carbonates, alkanolamines, like mono-, di- and triethanolamines, as well as their derivatives, sodium or potassium hydroxides and compounds of the following formula:

wherein Ri may be a propylene residue that may be optionally substituted with an hydroxyl group or a C1-C4 alkyl radical; R2, R3, R4 and Rs are identical or different and represent a hydrogen atom, a C1-C4 alkyl radical or C1-C4 hydroxyalkyl radical.

[0099] The personal care compositions may additionally comprise one or more buffers. Suitable buffering agents include, but are not limited to alkali or alkali earth carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates and the like, such as sodium phosphate, citrate, borate, acetate, bicarbonate, and carbonate.

[00100] The personal care compositions may be formulated in any of the product forms known to a person of ordinary skill in the art. Non-limiting product forms are described below.

Product Forms

[00101] Non-limiting sun care product forms include: solutions, liquids, creams, powders, lotions, gels, pastes, waxes, aerosols, sprays, mists, roll-ons, sticks, milks, emulsions, and wipes.

[00102] Non-limiting skin care product forms include: solutions, oils, lotions, creams, ointments, liquids, gels, solids, W/O emulsions, O/W emulsions, milks, suspensions, microemulsions, dispersions, microencapsulated products, sticks, balms, tonics, pastes, mists, reconstitutable products, peels, soaps, aerosols, mousses, waxes, glues, pomades, spritzes, putties, lacquers, serums, perms, powders, pencils, flakes, blush, highlighters, bronzers, concealers, and 2- way cake products. [00103] The compositions may also take the form of skin-washing compositions, and in the form of solutions or gels for the bath or shower, or of make-up removal products.

[00104] The six skin care product categories that follow next may be considered a subset of the skin and sun care products:

[00105] (1) Eye care

[00106] Non-limiting eye care product forms include: mascaras, eye liners, eye shadows, curlers of eye lashes, eyebrow pencils, and eye pencils.

[00107] (2) Lip care

[00108] Non-limiting lip care product forms include: lipsticks, lip balms, lip pencils, lip glosses, lip sprays, transparent lip bases, tinted lip moisturizers, and multi-functional color sticks that can also be used for cheeks and eyes.

[00109] (3) Nail care

[00110] Non-limiting nail care product forms include: nail polishes, nail varnishes, enamels, nail varnish removers, home-manicure products such as cuticle softeners and nail strengtheners, and artificial nails.

[00111] (4) Face care

[00112] Non-limiting face care product forms include: creams, lotions, solutions, oils, liquids, peels, scrubs, emulsions, suspensions, microcmulsions, microencapsulated product, pastes, reconstitutable product, aerosols, mousses, gels, waxes, glues, pomades, spritzes, facial wet-wipes, putties, lacquers, serums, perms, powders, blush, highlighters, bronzers, masks, and concealers.

[00113] (5) Body care

[00114] Non-limiting body care product forms include: foams, peels, masks, gels, sticks, aerosols, lotions, salts, oils, balls, liquids, powders, peels, pearls, bar soaps, liquid soaps, body washes, cleansers, scrubs, creams, flakes, other bath and shower products, shaving products, waxing products, and sanitizers. [00115] (6) Foot care

[00116] Non-limiting foot care product fomis include: mousses, creams, lotions, powders, liquids, sprays, aerosols, gels, flakes, and scrubs.

[00117] Non-limiting oral care product forms include: toothpastes, adhesives, gums, gels, powders, creams, solutions, lotions, liquids, dispersions, suspensions, emulsions, tablets, capsules, rinses, flosses, aerosols, strips, fdms, pads, bandages, microencapsulated products, syrups, and lozenges.

[00118] Also contemplated are personal care compositions comprising polymer(s) described herein complexed with iodine. These compositions may be used in treating skin conditions, nonlimiting examples of which include dermatitis, wounds, bacterial infections, bums, rashes, and herpes. These complexed compositions may be staining, substantially non-staining, or essentially non-staining.

[00119] Examples of related personal care compositions are disclosed in U.S. Pat. Nos. 5,599,800; 5,650,166; 5,916,549; and 6,812,192; U.S. patent application 2009/0317432; EP556660; EP661037; EP661038; EP662315; EP676194; EP796077; EP970682; EP976383; EP1415654; and EP2067467; and W02005/032506; each of which is herein incorporated in its entirety by reference.

[00120] It is also contemplated that the personal care compositions may be used in products for male and/or female personal grooming and/or toiletry such as: sanitary napkins, baby diapers, adult diapers, feminine products, products for incontinence, and other related products.

[00121] An array of additional personal care compositions, methods, and uses are contemplated. Disclosure of these compositions may be found in the following brochures by Ashland Specialty Ingredients, each of which is herein incorporated in its entirety by reference: Plasdone™ K-29/32, Advanced non-oxidative, non-abrasive teeth whitening in toothpastes, mouthwashes, and oral rinses (2010), Polymers for oral care, product and applications guide (2002), A composition guide for excellent hair styling gels and lotions (4/2003), PVP (polyvinylpyrrolidone) (no date provided), and Textile chemicals, solutions for the most challenging product environment (no date provided). [00122] Also contemplated are personal care compositions described in the publications listed below, each of which is herein incorporated in its entirety by reference: (1) Prototype Compositions - Personal Care Products (2009) from Xiameter, Dow Corning. (2) Sun care compositions under the category “Refreshing Sun”, “Younger Sun”, “Sun for Men”, and “Sunny Glow” from Dow Coming. (3) Cosmetic Nanotechnology, Polymers and Colloids in Cosmetics, 2007, ACS Symposium Series. (4) Review Paper: Lipid nanoparticles (SLN, NLC) in cosmetic and pharmaceutical dermal products, International Journal of Pharmaceutics, Volume 366, 2009.

Optional: Additional composition ingredients

[00123] It is also contemplated that the personal care compositions optionally may contain one or more additional ingredients.

[00124] Further, it is contemplated that the composition ingredients may be formulated in a single container, or the ingredients may be formulated in-part in two or more distinct containers of the same or different type, the contents of which may require mixing prior to use.

[00125] Furthermore, it also is contemplated that the compositions may be prepared in the form of concentrates that may be diluted by a suitable substance(s) prior to use. The concentrate may, in turn, be present in any of the forms as described under ‘Product Forms’ for the personal care compositions of the invention.

[00126] A non-limiting list of classes of additional ingredients that may optionally be present in different types of personal care compositions is provided below: conditioning agents, antimicrobials, protectives (for example, antiradical agents), abrasives, UV absorbers, emulsifiers (including, but not limited to ethoxylated fatty acids, ethoxylated glyceryl esters, ethoxylated oils, ethoxylated sorbitan esters, fatty esters, PEG esters, polyglycerol esters), antiperspirants (including, but not limited to aluminium chlorohydrates, aluminium zirconium chlorohydrates), antioxidants, vitamins and/or provitamins, botanicals, fixatives, oxidizing agents, reducing agents, dyes, cleansing agents, anionic, cationic, nonionic, and/or amphoteric surfactants, thickeners and/or gelling agents, perfumes, flavors, and/or fragrances, pearlizing agents, stabilizers, pH adjusters, filters, antimicrobial agents, preservatives and/or disinfectants, associative polymers, oils of vegetable, mineral, and/or synthetic origin, polyols, silicones, colorants, bleaching agents, highlighting agents, propellants (including, but not limited to hydrocarbons, dimethyl ether, fluorocarbons), styling polymers, benefit agents, skin lighteners (including, but not limited to arbutin and kojic acids), tanning agents (including, but not limited to dihydroxyacetone), solvents and/or cosolvents, diluents, essential oils, sequestrants and/or chelators, carriers, and natural extracts and/or natural products.

[00127] The amount of each ingredient in the composition varies depending on the type of composition, the function and/or physicochemical property of the ingredient, and the amount of other co-ingredients. The precise amount of each ingredient may be easily determined by any person skilled in the related arts.

[00128] It may be desirable to include one or more ingredients described in the prior art disclosures IPCOM000186541D, IPCOM000128968D, and IPCOM000109682D on www.ip.com, the contents of each of these disclosures are herein incorporated in their entirety by reference.

[00129] Further reference to formulary co-ingredients and product forms include the disclosures in US 2010/0183532, paragraphs [0096] — [0162], and WO 2010/105050, paragraphs [0053] — [0069], the contents of which are herein incorporated in their entirety by reference.

[00130] Any known conditioning agent may be used in the personal care compositions. An extensive discussion on conditioning agents may be found in the book Conditioning Agents for Skin and Hair, Cosmetic Science and Technology Series, Volume 21, 1999, Marcel Dekker Publishers. The contents of the book are herein incorporated in its entirety by reference.

[00131] Conditioning agents may be chosen from synthetic oils, mineral oils, vegetable oils, fluorinated or perfluorinated oils, natural or synthetic waxes, silicones, cationic polymers, proteins and hydrolyzed proteins, cationic surfactants, ceramide type compounds, fatty amines, fatty acids and their derivatives, as well as mixtures of these different types of compounds.

[00132] Non-limiting examples of suitable synthetic oils include: polyolefins, e.g., poly-a- olefins, such as polybutenes, polyisobutenes, polydecenes, and blends thereof. The polyolefins may be hydrogenated. [00133] Non-limiting examples of suitable mineral oils include hexadecane and oil of paraffin.

[00134] Non-limiting examples of suitable animal and vegetable oils include: sunflower oil, com oil, soy oil, avocado oil, jojoba oil, squash oil, raisin seed oil, sesame seed oil, walnut oil, fish oil, glycerol tricaprocaprylate, purcellin oil, liquid jojoba, and blends thereof. Also suitable are natural oils such as oils of eucalyptus, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, bergamot, and blends thereof.

[00135] The conditioning agent may be a fluorinated or a perfluorinated oil. The fluoridated oils may also be fluorocarbons such as fluoramines, e.g., perfluorotributylamine, fluoridated hydrocarbons such as perfluorodecahydronaphthalene, fluoroesters, fluoroethers, and blends thereof.

[00136] Non-limiting examples of suitable natural and synthetic waxes include: carnauba wax, candelila wax, alfa wax, paraffin wax, ozokerite wax, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax, absolute flower waxes such as black currant flower wax, animal waxes such as bees wax, modified bees wax (cerabellina), marine waxes and polyolefin waxes such as polyethylene wax, and blends thereof.

[00137] The conditioning agent may be any silicone known by those skilled in the art. Silicones include polyorganosiloxanes that are insoluble in the composition. The silicones may be present in the form of oils, waxes, resins, or gums. They may be volatile or non-volatile.

[00138] Non-limiting examples of suitable silicones include: polyalkyl siloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes, silicone gums and resins, polyorgano siloxanes modified by organofunctional groups, and blends thereof.

[00139] Suitable polyalkyl siloxanes include polydimethyl siloxanes with terminal trimethyl silyl groups or terminal dimethyl silanol groups (dimethiconol) and polyalkyl (C1-C20) siloxanes. Suitable polyalkyl aryl siloxanes include polydimethyl methyl phenyl siloxanes and polydimethyl diphenyl siloxanes. The siloxanes can have a linear or branched structure. [00140] Suitable silicone gums include polydiorganosiloxanes, such as those having a numberaverage molecular weight between 200,000 Da and 1,000,000 Da used alone or mixed with a solvent.

[00141] Non-limiting examples of suitable silicone gums include: polymethyl siloxane, polydimethyl siloxane/methyl vinyl siloxane gums, polydimethyl siloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxane, polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane, and blends thereof.

[00142] Non-limiting examples of suitable silicone resins include silicones with a dimethyl/trimethyl siloxane structure and resins of the trimethyl siloxysilicate type.

[00143] The organo-modified silicones suitable for use include silicones such as those previously defined and containing one or more organo functional groups attached by means of a hydrocarbon radical, and grafted silicone polymers. The organo-modified silicones may be one from the amino functional silicone family.

[00144] The silicones may be used in the form of emulsions, nano-emulsions, or microemulsions.

[00145] The cationic polymers that may be used as conditioning agents generally have a molecular weight (average number) from about 500 Da to about 5,000,000 Da. The expression “cationic polymer” as used herein indicates any polymer having at least one cationic group.

[00146] The cationic polymers may be chosen from among polymers containing primary, secondary, tertiary amine, and/or quaternary ammonium groups that may form part of the main polymer backbone and/or side chain(s).

[00147] Non-limiting examples of suitable cationic polymers include polyamines, polyaminoamides, and quaternary polyammonium classes of polymers, such as:

[00148] (1) homopolymers and copolymers derived from acrylic or methacrylic esters or amides. The copolymers may contain one or more units derived from acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyl lactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. Non-limiting, specific examples include: copolymers of acrylamide and dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide; copolymers of acrylamide and methacryloyl oxycthyl trimethyl ammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone and dialkylaminoalkyl acrylate or methacrylate, optionally quaternized, such as the products sold under the name Gafquat™ by Ashland Specialty Ingredients; terpolymers of dimethyl amino ethyl methacrylate, vinyl caprolactam, and vinyl pyrrolidone such as the product sold under the name Gaffix™ VC 713 by Ashland Specialty Ingredients; the vinyl pyrrolidone/methacrylamidopropyl dimethylamine copolymer, marketed under the name Styleze™ CC 10 by Ashland Specialty Ingredients; and the vinyl pyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymers such as the product sold under the name Gafquat™ HS 100 by Ashland Specialty Ingredients (Bridgewater, NJ).

[00149] (2) derivatives of cellulose ethers containing quaternary ammonium groups, such as hydroxy ethyl cellulose quaternary ammonium that has reacted with an epoxide substituted by a trimethyl ammonium group.

[00150] (3) derivatives of cationic cellulose such as cellulose copolymers or derivatives of cellulose grafted with a hydrosoluble quaternary ammonium monomer, as described in U.S. patent 4, 131 ,576, such as hydroxy alkyl cellulose, and hydroxymethyl-, hydroxyethyl- or hydroxypropyl - cellulose grafted with a salt of methacryloyl ethyl trimethyl ammonium, methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl ammonium.

[00151] (4) cationic polysaccharides such as described in U.S. patents 3,589,578 and 4,031,307, guar gums containing cationic trialkyl ammonium groups, and guar gums modified by a salt, e.g., chloride of 2,3-epoxy propyl trimethyl ammonium.

[00152] (5) polymers composed of piperazinyl units and alkylene or hydroxy alkylene divalent radicals with straight or branched chains, possibly interrupted by atoms of oxygen, sulfur, nitrogen, or by aromatic or heterocyclic cycles, as well as the products of the oxidation and/or quaternization of such polymers. [00153] (6) water-soluble polyamino amides prepared by polycondensation of an acid compound with a polyaminc. These polyamino amides may be reticulated.

[00154] (7) derivatives of polyamino amides resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bi-functional agents.

[00155] (8) polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dioxycarboxylic acid chosen from among diglycolic acid and saturated dicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Such polymers include those described in U.S. patents 3,227,615 and 2,961,347.

[00156] (9) cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium such as the homopolymer of dimethyl diallyl ammonium chloride and copolymers of diallyl dimethyl ammonium chloride and acrylamide.

[00157] (10) quaternary diammonium polymers such as hexadimethrine chloride.

[00158] (11) quaternary polyammonium polymers, including, for example, Mirapol® A 15, Mirapol® ADI, Mirapol® AZ1, and Mirapol® 175 products sold by Miranol.

[00159] (12) quaternary polymers of vinyl pyrrolidone and vinyl imidazole such as the products sold under the names Luviquat® FC 905, FC 550, and FC 370 by BASF Corporation.

[00160] (13) quaternary polyamines.

[00161] (14) reticulated polymers known in the art.

[00162] Other cationic polymers that may be used include cationic proteins or hydrolyzed cationic proteins, polyalkyleneimines such as polyethyleneimines, polymers containing vinyl pyridine or vinyl pyridinium units, condensates of polyamines and epichlorhydrins, quaternary polyurethanes, and derivatives of chitin.

[00163] The conditioning agent may comprise a protein or hydrolyzed cationic or non-cationic protein. Non-limiting examples of suitable compounds include: hydrolyzed collagens having triethyl ammonium groups, hydrolyzed collagens having trimethyl ammonium and trimethyl stearyl ammonium chloride groups, hydrolyzed animal proteins having trimethyl benzyl ammonium groups (bcnzyltrimonium hydrolyzed animal protein), hydrolyzed proteins having groups of quaternary ammonium on the polypeptide chain, including at least one Cl -Cl 8 alkyl, and blends thereof.

[00164] Non-limiting examples of suitable hydrolyzed cationic proteins include: Croquat® L, in which the quaternary ammonium groups include a C12 alkyl group, Croquat'' M, in which the quaternary ammonium groups include Cio-Cis alkyl groups, Croquat® S in which the quaternary ammonium groups include a Cis alkyl group, Crotein® Q in which the quaternary ammonium groups include at least one Ci-Cis alkyl group, and blends thereof. These products are sold by Croda.

[00165] The conditioning agent may also comprise quatemized vegetable protein(s) such as wheat, com, or soy proteins, non-limiting examples of which include: cocodimonium hydrolyzed wheat protein, laurdimonium hydrolyzed wheat protein, steardimonium hydrolyzed wheat protein, 2-V-stcaroyl amino-octadecane- 1,3 -diol, 2-7V-behenoyl amino-octadecane-l,3-diol, 2-N-[2- hydroxy-palmitoyl]-amino-octadecane-l,3-diol, 2-.'V-stcaroyl amino-octadecane- 1, 3, 4-triol, n- stearoyl phytosphingosine, 2-7V-palmitoyl amino-hexadecane- 1, 3-diol, bis-OV-hydroxy ethyl n- cetyl) malonamide, /?-(2-hydroxy cthyl)-.V-(3-cctoxyl-2-hydroxy propyl) amide of cetylic acid, n- docosanoyl n-methyl-D-glucamine, and blends thereof.

[00166] The conditioning agent may also comprise a cationic surfactant such as a salt of a primary, secondary, or tertiary fatty amine, optionally polyoxyalkylenated, a quaternary ammonium salt, a derivative of imadazoline, or an amine oxide. Conditioning agents may also be selected from the group consisting of: mono-, di-, and tri- alkyl amines, and quaternary ammonium compounds with a counterion such as a chloride, a methosulfate, a tosylate, etc. Non-limiting examples of suitable amines include: cetrimonium chloride, dicetyldimonium chloride, behentrimonium methosulfate, and blends thereof.

[00167] The conditioning agent may comprise a fatty amine. Non-limiting examples of suitable fatty amines include dodecyl amines, cetyl amines, stearyl amines such as stearamidopropyl dimethylamine, and blends thereof. [00168] The conditioning agent may comprise a fatty acid or derivative(s) thereof. Non-limiting examples of suitable fatty acids include: myristic acid, palmitic acid, stearic acid, bchcnic acid, oleic acid, linoleic acid, isostearic acid, and blends thereof. The derivatives of fatty acids include carboxylic ester acids including mono-, di-, tri- and tetra- carboxylic acids esters, amides, anhydrides, esteramides, imides, and mixtures of these functional groups.

[00169] Also suitable as conditioning agents are the following commercial products:

[00170] (1) Aquacat™ Clear Cationic Solution (INCI Name: guar hydroxypropyltrimonium Chloride), //-Hance™ SP-100 (INCI Name: acrylamidopropyl trimonium chloride/acrylamide copolymer), and //-Hance™ cationic guar (INCI Name: guar hydroxypropyltrimonium chloride) from Ashland Specialty Ingredients.

[00171] (2) Salcare® from BASF Corp.

[00172] (3) Softcat™ Polymers from The Dow Chemical Company.

[00173] (4) Jaguar® C500, Polycare® Boost, Mackconditioner™ Brite, and Mackine® 301 from Rhodia.

[00174] (5) Stcpanquat® ML, Stcpanquat® GA-90, Ninol®, and Ammonyx® from Stepan Company.

[00175] (6) Conditioneze™ 7 and Conditioneze™ NT-20 from Ashland Specialty Ingredients (Bridgewater, NJ).

[00176] Of course, mixtures of two or more conditioning agents may be used.

[00177] In one non-limiting embodiment, the conditioning agent(s) may be present in an amount from about 0.001% to about 20%. In another non-limiting embodiment, the conditioning agent(s) may be present in an amount from about 0.01% to about 10%. In yet another non-limiting embodiment, the conditioning agent(s) may be present in an amount from about 0.1% to about 3% by weight of the composition.

[00178] Personal care compositions may optionally comprise antimicrobial agent(s). [00179] Non-limiting examples of suitable water insoluble, non-cationic antimicrobial agents include: halogenated diphenyl ethers, phenolic compounds including phenol and its homologs, mono and poly-alkyl and aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds and halogenated salicylanilides, benzoic esters, halogenated carbanilides, and blends thereof.

[00180] Non-limiting examples of suitable water-soluble antimicrobial agents include: quaternary ammonium salts, bis-biguanide salts, triclosan monophosphate, and blends thereof.

[00181] The quaternary ammonium agents include those in which one or two of the substituents on the quaternary nitrogen has a carbon chain length (typically alkyl group) from about 8 to about 20, typically from about 10 to about 18 carbon atoms, while the remaining substituents (typically alkyl or benzyl group) have a lower number of carbon atoms, such as from about 1 to about 7 carbon atoms, typically methyl or ethyl groups.

[00182] Non-limiting examples of suitable quaternary ammonium antibacterial agents include: Dodecyl trimethyl ammonium bromide, tetradecylpyridinium chloride, domiphen bromide, n- tetradecyl-4-ethyl pyridinium chloride, dodecyl dimethyl(2-phenoxyethyl)ammonium bromide, benzyl dimethylstearyl ammonium chloride, cetyl pyridinium chloride, quaternized 5-amino-l,3- bis(2-ethyl-hexyl)-5-methyl hexahydropyrimidine, benzalkonium chloride, benzethonium chloride, methyl benzethonium chloride, and blends thereof.

[00183] Other antimicrobial compounds are bis[4-(R-amino)-l-pyridinium]alkanes as disclosed in U.S. Patent 4,206,215. Other antimicrobials such as copper salts, zinc salts and/or stannous salts may also be included. Also useful are enzymes, including endoglycosidase, papain, dextranase, mutanase, and blends thereof. Such antimicrobial agents are disclosed in U.S. Patents 2,946,725 and 4,051,234. The antimicrobial agents may also comprise chlorhexidine, triclosan, and flavor oils such as thymol. Triclosan and other agents are disclosed in U.S. Patents 5,015,466 and 4,894,220.

[00184] In non-limiting aspects, one or more preservatives may be included.

[00185] Non-limiting examples of suitable preservatives include benzoic acid, sorbic acid, dehydroacetic acid, diazolidinyl ureas, imidazolidinyl ureas, salicylic acid, piroctone olamine, DMDM hydantoin, IPBC (iodopropynyl butylcarbamate), triclosan, bronopol, formaldehyde, isothiazolinoncs, nitratcs/nitritcs, parabens, phenoxyethanol, potassium sorbate, sodium benzoate, sulphites, sulphur dioxide, and blends thereof.

[00186] In non-limiting aspects, preservative boosters/solvents may be incorporated, nonlimiting examples of which include: caprylyl glycol, hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamic acid, caprylohydroxamic acid, glyceryl caprylate, and blends thereof.

[00187] Polysaccharides, such as gum Arabic, may be included as well.

[00188] The compositions may comprise liquid or liquid-like carrier(s) that help to distribute, disperse, and/or dissolve the ingredients.

[00189] Non-limiting examples of suitable liquid carriers include water, alcohols, oils, esters, and blends thereof.

[00190] The compositions may also be in the form of aqueous or hydro-alcoholic solutions.

[00191] The physiological and cosmetically acceptable medium may consist exclusively of water, a cosmetically acceptable solvent, or a blend of water and a cosmetically acceptable solvent, such as a lower alcohol composed of Cl to C4, such as ethanol, isopropanol, t-butanol, w-butanol, alkylene glycols such as propylene glycol, and glycol ethers.

[00192] Personal care compositions may comprise vitamin(s), provitamin(s), and/or mineral(s).

[00193] Non-limiting examples of suitable vitamins include ascorbic acid (vitamin C), vitamin E, vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5, niacin, vitamin A, derivatives thereof, and blends thereof.

[00194] Non-limiting examples of suitable provitamins include: panthenol, retinol, and blends thereof.

[00195] Non-limiting examples of suitable minerals include: talc, clay, calcium carbonate, silica, kaolin, mica, and blends thereof. Further examples of minerals that may be used in the personal care compositions may be found in a brochure titled Minerals for personal care from Imerys Pcrfomiancc Minerals, the disclosure of which is herein incorporated in its entirety by reference.

[00196] Personal care compositions may comprise one or more surfactants. Surfactants serve in solubilizing, dispersing, emulsifying and/or reducing the interfacial tension. Surfactants may be chosen from anionic, nonionic, amphoteric, zwitterionic, or cationic surfactants, or blends thereof.

[00197] Anionic surfactants useful herein include the water-soluble salts of alkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical (e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonated monoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodium lauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates are non-limiting examples of anionic surfactants of this type.

[00198] Non-limiting examples of suitable anionic surfactants include: sarcosinates, taurates, isethionates, sodium lauryl sulfoacetate, sodium laureth carboxylate, and sodium dodecyl benzenesulfonate. Also suitable are alkali metal or ammonium salts of surfactants such as the sodium and potassium salts of the following: lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoyl sarcosinate.

[00199] Non-limiting examples of suitable cationic surfactants include: derivatives of aliphatic quaternary ammonium compounds having at least one long alkyl chain containing from about 8 to about 18 carbon atoms, such as, lauryl trimethylammonium chloride, cetyl pyridinium chloride, cetyl trimethylammonium bromide, di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconut alkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and blends thereof. Further suitable are quaternary ammonium fluorides having detergent properties such as compounds described in U.S. Patent 3,535,421. Certain cationic surfactants may act as germicides in the compositions disclosed herein.

[00200] Nonionic surfactants useful herein include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature.

[00201] Non-limiting examples of suitable nonionic surfactants include: poloxamers (sold under the trade name Pluronic® by BASF Corporation), polyethylene oxide condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, ethylene oxide condensates of aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides, and blends thereof.

[00202] Non-limiting examples of suitable zwitterionic surfactants include betaines and derivatives of aliphatic quaternary ammonium compounds in which the aliphatic radicals can be straight chain or branched, and which contain an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[00203] Non-limiting examples of suitable betaines include: decyl betaine or 2-(A-decyl-A,A- dimethylammonio)acetate, coco betaine or 2-(/V-coc-/V,/V-dimcthyl ammonio)acetate, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine, and blends thereof. The amidobetaines are exemplified by cocoamidoethyl betaine, cocoamidopropyl betaine, lauramidopropyl betaine, and the like. The betaines of choice include cocoamidopropyl betaines such as lauramidopropyl betaine. Suitable betaine surfactants are disclosed in U.S. patent 5,180,577.

[00204] Other surfactants such as fluorinated surfactants may also be incorporated within the compositions of the invention.

[00205] Also suitable as surfactants are the following commercial products:

[00206] (1 ) Alkanolamides, under the trade names Amidex™ and Schercomid™; amido-amines, under the trade names Katemul™ and Schercodine™; amine oxides, under the trade names Chemoxide™ and Schercamox™; amphoterics, under the trade names Chembetaine™, Schercotaine™ and Schercoteric™; imidazolines, under the trade name Schercozoline™; pearlizing agents, under the trade name Quickpearl™; performance concentrates, under the trade names Sulfochem™ and Chemoryl™; soaps (potassium cocoate and potassium soyate); specialty ethoxylates, under the trade name Chemonic™; specialty quats under the trade names Quatrex™ and Schercoquat™; sulfates, under the trade name Sulfochem™; and sulfosuccinates, under the trade name Chemccinate™ from Lubrizol.

[00207] (2) Avaniel, Cremaphore®, Jordapan®, and Pluracarc¹' from BASF Corp. [00208] (3) Miracare® SLB, Mackam® Bab, Mackanate® Ultra SI, Miranol® Ultra, and Miracarc® Plaisant from Rhodia.

[00209] (4) Stepan ^B Pearl 2, Stepan¹® Pearl 4, Stepan® Pearl Series, Neobee® M-20, Stepan® PTC, Amphosol® 2CSF, Steol®, Stepan-Mild® GCC, Stepan® SLL-FB, Stepanol® AM, Stepanol® PB, Alpha-Step® BSS-45, Bio-Terge® 804, Stepan-Mild® L3, Stepan® SLL-FB, Stepan® SSL-CG, and Stepanol® CFAS-70 from Stepan Company.

[00210] Also suitable as surfactants are those described in the book Surfactants in Personal Care Products and Decorative Cosmetics, Third Edition, 2006, CRC Press. The disclosure is herein incorporated in its entirety by reference.

[00211 ] Personal care compositions may also be formulated as detergent compositions, such as shampoos, bath gels, and bubble baths. Such compositions comprise water as a liquid carrier. The surfactant or surfactants that form the washing base may be chosen alone or in blends, from known anionic, amphoteric, zwitterionic and/or non-ionic surfactants. The quantity and quality of the washing base must be sufficient to impart a satisfactory foaming and/or detergent value to the final composition. In one non-limiting embodiment, the washing base may be present in an amount from about 4% to about 50% by weight.

[00212] Personal care compositions may comprise one or more thickcncr(s) and/or viscosifier(s).

[00213] Non-limiting examples of suitable thickeners and/or viscosifiers include: Acetamide MEA; acrylamide/ethalkonium chloride acrylate copolymer; acrylamide/ethyltrimonium chloride acrylate/ethalkonium chloride acrylate copolymer; acrylamides copolymer; acrylamide/sodium acrylate copolymer; acrylamide/sodium acryloyldimethyltaurate copolymer; acrylates/acetoacetoxyethyl methacrylate copolymer; acrylates/beheneth-25 methacrylate copolymer; acrylates/C10-C30 alkyl acrylate crosspolymer; acrylates/ceteth-20 itaconate copolymer; acrylates/ceteth-20 methacrylate copolymer; acrylates/laureth-25 methacrylate copolymer; acrylates/palmeth-25 acrylate copolymer; acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50 acrylate copolymer; acrylates/steareth-20 itaconate copolymer; acrylates/steareth-20 methacrylate copolymer; acrylates/stearyl methacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer; acrylic acid/acrylonitrogens copolymer; adipic acid/mcthyl DEA crosspolymcr; agar; agarose; alcaligcncs polysaccharides; algin; alginic acid; almondamide DEA; almondamidopropyl betaine; aluminum/magnesium hydroxide stearate; ammonium acrylates/acrylonitrogens copolymer; ammonium acrylates copolymer; ammonium acryloyldimethyltaurate/vinyl formamide copolymer; ammonium acryloyldimethyltaurate/VP copolymer; ammonium alginate; ammonium chloride; ammonium polyacryloyldimethyl taurate; ammonium sulfate; amylopectin; apricotamide DEA; apricotamidopropyl betaine; arachidyl alcohol; arachidyl glycol; arachis hypogaea (peanut) flour; ascorbyl methylsilanol pectinate; astragalus gummifer gum; attapulgite; avena sativa (oat) kernel flour; avocadamide DEA; avocadamidopropyl betaine; azelamide MEA; babassuamide DEA; babassuamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamide MEA; behenamidopropyl betaine; behenyl betaine; bentonite; butoxy chitosan; caesalpinia spinosa gum; calcium alginate; calcium carboxymethyl cellulose; calcium carrageenan; calcium chloride; calcium potassium carbomer; calcium starch octenylsuccinate; C20-40 alkyl stearate; canolamidopropyl betaine; capramide DEA; capryl/capramidopropyl betaine; carbomer; carboxybutyl chitosan; carboxymethyl cellulose acetate butyrate; carboxymethyl chitin; carboxymethyl chitosan; carboxymethyl dextran; carboxymethyl hydroxyethylcellulose; carboxymethyl hydroxypropyl guar; carnitine; cellulose acetate propionate carboxylate; cellulose gum; ceratonia siliqua gum; cetearyl alcohol; cetyl alcohol; cetyl babassuate; cetyl betaine; cetyl glycol; cetyl hydroxyethylcellulose; chimyl alcohol; cholesterol/HDI/pullulan copolymer; cholesteryl hexyl dicarbamate pullulan; citrus aurantium dulcis (orange) peel extract; cocamide DEA; cocamide MEA; cocamide MIPA; cocamidoethyl betaine; cocamidopropyl betaine; cocamidopropyl hydroxysultaine; coco-betaine; coco- hydroxysultaine; coconut alcohol; coco/oleamidopropyl betaine; coco-Sultaine; cocoyl sarcosinamide DEA; cornamide/cocamide DEA; comamide DEA; croscarmellose; crosslinked bacillus/glucose/sodium glutamate ferment; cyamopsis tetragonoloba (guar) gum; decyl alcohol; decyl betaine; dehydroxanthan gum; dextrin; dibenzylidene sorbitol; diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIP copolymer; dihydroabietyl behenate; dihydrogenated tallow benzylmonium hectorite; dihydroxyaluminum aminoacetate; dimethicone/PEG-10 crosspolymer; dimethicone/PEG-15 crosspolymer; dimethicone propyl PG-betaine; dimethylacrylamide/acrylic acid/polystyrene ethyl methacrylate copolymer; dimethylacrylamide/sodium acryloyldimethyltaurate crosspolymer; disteareth-100 IPDI; DMAPA acrylates/acrylic acid/acrylonitrogens copolymer; erucamidopropyl hydroxysultaine; cthylcnc/sodium acrylate copolymer; gelatin; gcllan gum; glyceryl alginate; glycine soja (soybean) flour; guar hydroxypropyltrimonium chloride; hectorite; hyaluronic acid; hydrated silica; hydrogenated potato starch; hydrogenated tallow; hydrogenated tallowamide DEA; hydrogenated tallow betaine; hydroxybutyl methylcellulose; hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer; hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethyl ethylcellulose; hydroxyethyl stearamide-MIPA; hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose; hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer; hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropyl methylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropyl starch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA; isobutylene/sodium maleate copolymer; isostearamide DEA; isostearamide MEA; isostearamide mIPA; isostearamidopropyl betaine; lactamide MEA; lanolinamide DEA; lauramide DEA; lauramide MEA; lauramide MIPA; lauramide/myristamide DEA; lauramidopropyl betaine; lauramidopropyl hydroxysultaine; laurimino bispropanediol; lauryl alcohol; lauryl betaine; lauryl hydroxysultaine; lauryl/myristyl glycol hydroxypropyl ether; lauryl sultaine; lecithinamide DEA; linoleamide DEA; linoleamide MEA; linoleamide MIPA; lithium magnesium silicate; lithium magnesium sodium silicate; macrocystis pyrifera (kelp); magnesium alginate; magnesium/aluminum/hydroxide/carbonate; magnesium aluminum silicate; magnesium silicate; magnesium trisilicate; methoxy PEG-22/dodecyl glycol copolymer; methylcellulose; methyl ethylcellulose; methyl hydroxyethylcellulose; microcrystalline cellulose; milkamidopropyl betaine; minkamide DEA; minkamidopropyl betaine; MIPA-myristate; montmorillonite; Moroccan lava clay; myristamide DEA; myristamide MEA; myristamide MIPA; myristamidopropyl betaine; myristamidopropyl hydroxysultaine; myristyl alcohol; myristyl betaine; natto gum; nonoxynyl hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine; octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide DEA; oleamide MEA; oleamide MIPA; oleamidopropyl betaine; oleamidopropyl hydroxysultaine; oleyl betaine; olivamide DEA; olivamidopropyl betaine; oliveamide MEA; palmamide DEA; palmamide MEA; palmamide MIPA; palmamidopropyl betaine; palmitamide DEA; palmitamide MEA; palmitamidopropyl betaine; palm kernel alcohol; palm kernelamide DEA; palm kemelamide MEA; palm kemelamide MIPA; palm kernelamidopropyl betaine; peanutamide MEA; peanutamide MIPA; pectin; PEG-800; PEG-crosspolymer; PEG-150/decyl alcohol/SMDI copolymer; PEG-175 diisostearate; PEG-190 distearate; PEG-15 glyceryl tristearate; PEG-140 glyceryl tristcaratc; PEG-240/HDI copolymer bis-dccyltctradcccth-20 ether; PEG-100/IPDI copolymer; PEG-180/laureth-50/™MG copolymer; PEG-10/lauryl dimethicone crosspolymer; PEG- 15/lauryl dimethicone crosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M; PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M; PEG- 120 methyl glucose trioleate; PEG-180/octoxynol-40/™MG copolymer; PEG- 150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide; PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed powder; polianthes tuberosa extract; polyacrylate-3; polyacrylic acid; polycyclopentadiene; polyether- 1 ; polyethylene/isopropyl maleate/MA copolyol; polyglyceryl-3 disiloxane dimethicone; polyglyceryl-3 polydimethylsiloxyethyl dimethicone; polymethacrylic acid; polyquaternium-52; polyvinyl alcohol; potassium alginate; potassium aluminum polyacrylate; potassium carbomer; potassium carrageenan; potassium chloride; potassium palmate; potassium polyacrylate; potassium sulfate; potato starch modified; PPG-2 cocamide; PPG-1 hydroxyethyl caprylamide; PPG-2 hydroxyethyl cocamide; PPG-2 hydroxyethyl coco/isostearamide; PPG-3 hydroxyethyl soyamide; PPG- 14 laureth-60 hexyl dicarbamate; PPG- 14 laureth-60 isophoryl dicarbamate; PPG- 14 palmeth-60 hexyl dicarbamate; propylene glycol alginate; PVP/decene copolymer; PVP montmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber; rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide MEA; ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic acid/adipic acid/AEEA copolymer; rosa multiflora flower wax; sclerotium gum; sesamide DEA; sesamidopropyl betaine; sodium acrylate/acryloyldimethyl taurate copolymer; sodium acrylates/acrolein copolymer; sodium acrylates/acrylonitrogens copolymer; sodium acrylates copolymer; sodium acrylates crosspolymer; sodium acrylate/sodium acrylamidomethylpropane sulfonate copolymer; sodium acrylates/vinyl isodecanoate crosspolymer; sodium acrylate/vinyl alcohol copolymer; sodium carbomer; sodium carboxymethyl chitin; sodium carboxymethyl dextran; sodium carboxymethyl beta-glucan; sodium carboxymethyl starch; sodium carrageenan; sodium cellulose sulfate; sodium chloride; sodium cyclodextrin sulfate; sodium hydroxypropyl starch phosphate; sodium isooctylene/MA copolymer; sodium magnesium fluorosilicate; sodium oleate; sodium palmitate; sodium palm kemelate; sodium polyacrylate; sodium polyacrylate starch; sodium polyacryloyldimethyl taurate; sodium polygamma-glutamate; sodium polymethacrylate; sodium polystyrene sulfonate; sodium silicoaluminate; sodium starch octenylsuccinate; sodium stearate; sodium stearoxy PG-hydroxyethylcellulose sulfonate; sodium styrene/acrylates copolymer; sodium sulfate; sodium tallowatc; sodium tauridc acrylatcs/acrylic acid/acrylonitrogcns copolymer; sodium tocopheryl phosphate; solanum tuberosum (potato) starch; soyamide DEA; soyamidopropyl betaine; starch/acrylates/acrylamide copolymer; starch hydroxypropyltrimonium chloride; stearamide AMP; stearamide DEA; stearamide DEA-distearate; stearamide DIBA- stearate; stearamide MEA; stearamide MEA-stearate; stearamide MIPA; stearamidopropyl betaine; steareth-60 cetyl ether; steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl betaine; sterculia urens gum; synthetic fluorphlogopite; tallamide DEA; tallow alcohol; tallowamide DEA; tallowamide MEA; tallowamidopropyl betaine; tallowamidopropyl hydroxysultaine; tallowamine oxide; tallow betaine; tallow dihydroxyethyl betaine; tamarindus indica seed gum; tapioca starch; TEA-alginate; TEA-carbomer; TEA-hydrochloride; trideceth-2 carboxamide MEA; tridecyl alcohol; triethylene glycol dibenzoate; trimethyl pentanol hydroxyethyl ether; triticum vulgare (wheat) germ powder; triticum vulgare (wheat) kernel flour; triticum vulgare (wheat) starch; tromethamine acrylates/acrylonitrogens copolymer; tromethamine magnesium aluminum silicate; undecyl alcohol; undecylenamide DEA; undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheat germamide DEA; wheat gemiamidopropyl betaine; xanthan gum; yeast beta-glucan; yeast polysaccharides; zea mays (corn) starch; and blends thereof.

[00214] Also suitable as thickeners and/or viscosifiers are the following commercial products:

[00215] (1) Aquaion™ carboxymethylcellulose, Benecel™ methylcellulose and hydroxypropyl methylcellulose, Blanose™ sodium carboxymethylcellulose, Klucel™ hydroxypropylcellulose, Natrosol™ hydroxyethylcellulose, Natrosol™ Plus and PolySurf™ cetyl modified hydroxyethylcellulose, n-Hancc™ cationic guar, n-Hance™ HP Series hydroxypropyl guar, n- Hance™ SP-100 conditioning polymer, and Supercol™ guar gum from Ashland Specialty Ingredients.

[00216] (2) Carbopol® Polymers, Fixate™ PLUS Polymer, Glucamate™ Thickeners,

Amidex™ Surfactants, Chembetaine™ Surfactants, Chemoxide™ Surfactants, Chemonic™ Surfactants, Chemccinate™ Surfactants, Amidex™ BC-24 Surfactant, Chemoryl™ LB-30 Surfactant, Novethix™ L-10 Polymer, Ceralan™ Lanolin Product, Pemulen™ TR-1 Polymeric Emulsifier, Pemulen™ TR-2 Polymeric Emulsifier, Hydramol™ PGPD Ester, Schercodine™ M Amido-Amine, Schercodine™ P Amido-Aminc, Schcrcomid™ Dicthanolamidcs from The Lubrizol Corporation.

[00217] (3) Salcare® and Luvigel® from BASF Corporation.

[00218] (4) Aculyn™ 22, Aculyn™ 28, Aculyn™ 33, Aculyn™ 38, and Aculyn™ 44 from The Dow Chemical Company.

[00219] (5) Ammonyx® C and Stepan-Mild® GCC from Stepan Company.

[00220] (6) Stabileze™, Rapithix™ A-60, Rapithix™ A- 100, Ultrathix™ P-100, Lubrajel™ and FlexiThix™ from Ashland Specialty Ingredients (Bridgewater, NJ).

[00221] Also suitable as a thickener/rheology modifier are lightly- to moderately-crosslinked polyvinylpyrrolidones. Disclosures of these polymers are provided in the following publications, each of which is herein incorporated in its entirety by reference: U.S. patent 5,073,614; 5,312,619; 5,139,770; 5,716,634; 5,470,884; 5,759,524; 5,997,887; 6,024,942; as well as international application PCT/US 10/26973, PCT/US 10/26976, PCT/US 10/26940, PCT/US 11/32993, and PCT/US 11/34515.

[00222] Personal care compositions may comprise natural extracts and/or natural products. Extensive details on natural products that can be used in personal care compositions is provided in book chapter “Chemistry of Cosmetics, Comprehensive Natural Products II” in Chemistry and Biology, volume 3, 2010.

[00223] Also contemplated are additional personal care compositions that may comprise the polymers described herein. Disclosures on such compositions may be found in the publications listed below, each of which is herein incorporated in its entirety by reference: (1) Prototype Compositions - Personal Care Products (2009) from Xiameter, Dow Corning. (2) Sun care compositions under the category “Refreshing Sun”, “Younger Sun”, “Sun for Men”, and “Sunny Glow” from Dow Coming. (3) Cosmetic Nanotechnology, Polymers and Colloids in Cosmetics, 2007, ACS Symposium Series. (4) Review Paper: Lipid nanoparticles (SLN, NLC) in cosmetic and pharmaceutical dermal products, International Journal of Pharmaceutics, Volume 366, 2009. [00224] Non-limiting examples of properties that may be beneficially modified by the block copolymers and compositions disclosed herein arc solution viscosity, rheology, thickening, film formation, lubricity, gloss, adhesion, impact resistance, fluid snap, film brittleness, film toughness, coating hardness, water resistance, tack, surface gloss and shine, surface tension, wetting, foaming and foam stabilization, tensile strength, solvency, solubilization speed, compatibility, bioadhesion, particulate suspension, dispersive properties, delivery of hydrophobic compositions, formulation stabilization, suspension stability, dispersion stability, flexibility, chemical resistance, abrasion resistance, penetration, hydrolytic degradability, biodegradability, biocompatibility, and combinations thereof.

[00225] In a specific embodiment, the coating composition is a water-based coating composition, a solvent-based coating composition, a solvent-free coating composition, a dry coating composition, an aqueous coating composition, a non-aqueous coating composition, a polar coating composition, a non-polar coating composition, an oil-based coating composition, an emulsion coating composition, an enamel coating composition, an architectural coating composition, a bituminous coating composition, an anti-corrosive coating composition, a cement coating composition, a wood coating composition, a metal coating composition, a plastic coating composition, a glass coating composition, a rubber coating composition, a paper coating composition, a fabric coating composition, a ceramic coating composition, a stone coating composition, a curable coating composition, an oxidatively curable coating composition, a pigment composition, a tinting composition, a colorant composition, a paint composition, a decorative coating composition, a radiation reflective coating composition, a protective coating composition, a radiation protective coating composition, an auto-oxidizable coating composition, an aerosol coating composition, a water reducible coating composition, an antifouling coating composition, a polymeric coating composition, a flame retardant coating composition, an air drying coating composition, a waterproofing coating composition, a laminating coating composition, a transparent coating composition, a temperature resistant coating composition, a durable film coating composition, a sound insulation coating composition, a gloss coating composition, a semi-gloss coating composition, a low VOC coating composition, an anti-rust coating composition, a thermosettable coating composition, a luminous coating composition, a traffic coating composition, a self-priming coating composition, a lacquer coating composition, a varnish composition, a resin composition, an ink composition, a polish composition, a conductive coating composition, a solar energy absorbing coating composition, or a heat absorbing coating composition.

[00226] In a specific embodiment, the coating composition further comprises an ingredient selected from the group consisting of binders, alkyds, drying oils, corrosion inhibitors, UV- protective agents, radiation protective agents, surfactants, secondary emulsifiers, dispersants, spreading agents, suspending agents, coalescing agents, pigments, opacifiers, colorants, dyes, humectants, film-forming agents, solvents, anti-sagging agents, anti-settling agents, anti-floating agents, viscosity modifying agents, thinners, thickening agents, hydrophobic agents, hydrophilic agents, grinding aids, curing agents, crosslinking agents, and combinations thereof.

[00227] Any suitable rheology modifier may be incorporated into a coating composition. Exemplary polyurethane rheology modifiers include nonionic, solvent-free, hydrophobically modified ethylene oxide urethane (HEUR) rheology modifiers such as ACRYSOL™ RM-2020 NPR (sold by the Dow Chemical Company) and nonionic urethane rheology modifiers such as ACRYSOL™ RM-12W and ACRYSOL™ RM-8W (sold by the Dow Chemical Company).

[00228] The coating composition can include any suitable surfactant. In some embodiments, a phosphate surfactant can be included in a crosslinking acrylic latex resin of the coating composition. Exemplary phosphate surfactants include phosphate esters such as methyl phosphate, 2-ethylhexyl phosphate, decyl alcohol ethoxylated phosphate esters, lauryl alcohol ethoxylated phosphate esters, n-octyl phosphate, nonylphenol ethoxylated phosphate esters, octyl phenol ethoxylated phosphate esters, styrenated phenol ethoxylated phosphate esters, tridecyl alcohol ethoxylated phosphate esters, etc. An exemplary phosphate ester surfactant is DEXTROL™ OC- 50 (sold by Ashland Global Specialty Chemicals, Inc., Wilmington, DE). Other useful surfactants comprise TRITON™ CF-10 (sold by the Dow Chemical Company), E-SPERSE® RX 201, E- SPERSE® RX 202, and E-SPERSE® RX 203 (sold by Ethox Chemicals, Greenville, SC).

[00229] Any suitable dispersant, such as any one or more of anionic dispersants, cationic dispersants, amphoteric dispersants, or nonionic dispersants may be used in the coating composition. Exemplary dispersants include 2-amino-2-methyl-l-propanol (e.g., sold as AMP™ by Angus Chemical Company), DISPERBYK®-190 (sold by Byk of Altana Group), pyrophosphates such as tetrapotassium pyrophosphate and tetrasodium pyrophosphate, tripolyphosphates such as potassium tripolyphosphate and sodium tripolyphosphate, NUOSPERSE® FA 196 (sold by Elcmcntis Specialties), etc. Any suitable wetting agents such as any one or more of anionic wetting agents, cationic wetting agents, amphoteric wetting agents, or nonionic wetting agents may be used. Any suitable deflocculant, such as sodium potassium tripolyphosphate, can be used.

[00230] The coating composition may include any suitable humectant or other component suitable to improve the open time of the composition. Exemplary open time extenders include glycols such as ethylene glycol and propylene glycol. When used, the open time extenders can be used in any suitable amounts. For example, ethylene and propylene glycol may be used in amounts of at least 5 g/L, and particularly are used in amounts ranging from 40 to less than 50 g/L. Generally, the glycols may be used in amounts sufficient to improve the open time of the composition but such that the composition has a volatile organic compounds (VOC) content of less than 50 g/L as determined by ASTM D6886. The ASTM test is believed to operate within a margin of error of about ± 6 g/L; in practice, a composition that yields a result of less than about 56 g/L under this test will be deemed to be a composition that has a VOC content of less than 50 g/L. In some embodiments, the coating composition is essentially free of VOCs except for the ethylene or propylene glycol or other open time extenders.

[00231] The coating composition may, if desired, include one or more fillers or extenders. Exemplary fillers include, for example, sodium-potassium alumina silicates such as MINEX® 4 and MINEX® 10 (sold by Unimin Corporation, New Canaan, CT). When used, such fillers may be employed in any desired amount.

[00232] Useful antimicrobial additives include phosphates, zeolites, hydroxyapatites, organic acids, phenols, alcohols, quaternary ammonium compounds, additives containing metal ions such as ions of silver, zinc, and copper, etc. An exemplary antimicrobial additive is Zinc Omadine™ ZOE ™ dispersion (sold by Lonza Group AG).

[00233] One or more types of pigment may be included in a coating composition via any suitable technique, such as by adding raw pigment or a pigment vehicle during manufacture of the composition or by instilling a pigment at the point of sale. Exemplary pigments include azo pigments, anazurite, aluminum silicate, aluminum potassium silicate, aluminum paste, anthraquinone pigments, antimony oxide, barium metaborate, barium sulfate, cadmium sulfide, cadmium selenide, calcium carbonate, calcium metaborate, calcium mctasilicatc, carbon black, chromium oxides, clay, copper oxides, copper oxychloride, dioxazine pigments, feldspar, hansa yellows azo pigments (some of which are listed above), benzimidazolones, iron oxides such as yellow and red iron oxides, isoindoline pigments, kaolinite, lithopone, magnesium silicates, metallic flakes, mica, napthol pigments such as napthol reds, nitioso pigments, nepheline syenite, perinone pigments, perylene pigments, polycyclic pigments, pyrropyrrol pigments, pthalocyanines such as copper pthalocyanine blue and copper pthalocyanine green, quinacridones such as quinacridone violets, quinophthalone pigments, silicates, sulfides, talc, titanium dioxide, ultramarine, zinc chromate, zinc oxide, and zinc phosphate. In addition, pearlescents, optical brighteners, ultraviolet stabilizers, and the like may be added to a coating composition.

[00234] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the home care compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the home care compositions.

[00235] Non-limiting examples of home care compositions include laundry detergents, fabric conditioning compositions, dishwashing liquids, wood and furniture polishes, floor polishes, bath and tile cleaners, toilet bowl cleaners, hard surface cleaners, window cleaners, antifogging agents, drain cleaners, dishwashing agents, carpet cleaners, pre-wash detergents, rust cleaners, and other types of detergents.

[00236] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the nutrition compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the nutrition compositions and if the ingredients are generally regarded as safe or approved by a regulatory authority for consumption.

[00237] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the pharmaceutical compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the pharmaceutical compositions and if the ingredients arc generally regarded as safe or approved by a regulatory authority for usage in pharmaceutical compositions.

[00238] In general, therapeutic agents which may be administered via pharmaceutical compositions according the claimed and/or disclosed inventive concepts include, without limitation, antiinfectives, such as antibiotics and antiviral agents; analgesics and analgesic combinations; anorexics; antihelmintics; antiarthritics; antiasthmatic agents; anticonvulsants; antidepressants; antidiuretic agents; antidiarrheals; antihistamines; antiinflammatory agents; antimigraine preparations; antinauseants; antineoplastics; antiparkinsonism drugs; antipruritics; antipsychotics; antipyretics, antispasmodics; anticholinergics; sympathomimetics; xanthine derivatives; cardiovascular preparations including calcium channel blockers and beta-blockers such as pindolol and antiarrhythmics; antihypertensives; diuretics; vasodilators, including general coronary, peripheral and cerebral; central nervous system stimulants; cough and cold preparations, including decongestants; hormones, such as estradiol and other steroids, including corticosteroids; hypnotics; immunosuppressives; muscle relaxants; parasympatholytics; psychostimulants; sedatives; tranquilizers; naturally derived or genetically engineered proteins, polysaccharides, glycoproteins, or lipoproteins; oligonucleotides, antibodies, antigens, cholinergics, chemotherapeutics, hemostatics, clot dissolving agents, radioactive agents and cystostatics.

[00239] In a specific embodiment, the agricultural composition further comprises an ingredient selected from the group consisting of an agrochemically active ingredient, other alkyds, binders, surfactants, emulsifiers, dispersants, spreading agents, suspending agents, coalescing agents, pigments, opacifiers, colorants, dyes, humectants, film-forming agents, solvents, viscosity modifying agents, thinners, thickening agents, hydrophobic agents, hydrophilic agents, and combinations thereof.

[00240] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the agricultural compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the agricultural compositions. [00241] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive conccpt(s) can also be used in the adhesive compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the adhesive compositions.

[00242] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the battery compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the battery compositions.

[00243] In specific embodiments, the battery composition is selected from the group consisting of a lithium primary battery, a rechargeable lithium metal battery, a rechargeable lithium-ion battery, a thin film lithium-ion battery, a lithium-ion polymer battery, a lithium iron phosphate battery, a lithium sulfur battery, a solid-state lithium battery, a lithium air battery, and a nanowire battery.

[00244] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the oilfield compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the oilfield compositions.

[00245] One or more ingredients described herein which can be included in the personal care compositions according to the disclosed and/or claimed inventive concept(s) can also be used in the metal working fluid compositions according to the disclosed and/or claimed inventive concept(s) if the ingredients impart one or more desired performance attributes to the metal working fluid compositions.

[00246] In specific embodiments, the metal working fluid composition further comprises at least one secondary emulsifier. Choices of secondary emulsifiers depend on the amount of water, the amount and type of the oil component used. Emulsifiers are selected from any of the conventional anionic, cationic, nonionic, or amphoteric surfactants. In specific embodiments, the emulsifier component is selected from amphoteric compounds. Examples include alkyl-3 -iminodipropionate; alkyl-3 -amino-propionate; fatty imidazolines and betaines, more specifically 1 coco-5- hydroxyethyl-5-carboxymethyl imidazoline; dodecyl-3-alanine; N-dodecyl-N, N-dimethyl amino acetic acid; 2-trimcthyl amino lauric acid inner salts; and the like.

[00247] In specific embodiments, the emulsifier component is selected from nonionic surfactants such as ethylene oxide adducts of alcohols, polyols, phenols, carboxylic acids, and carboxylic acid esters such as ethylene oxide adducts of oleyl alcohol, nonyl phenol, glycerol, sorbitol, mannitol, pentaerythritol, sorbitan monolaurate, glycerol monooleate, pentaerythritol monostearate, oleic acid, stearic acid, and the like.

[00248] In specific embodiments, the emulsifier component is selected from cationic compounds include cetyl pyridinium bromide, hexadecyl morpholinium chloride, dilauryl triethylene tetramine diacetate, didodecylamine lactate, 1 -amino-2-heptadecenyl imidazoline acetate, cetyl amine acetate, oleylamine acetate, ethoxylated tallow, coco, stearyl, oleyl or soya amine, and the like. Useful anionic compounds include alkali metal salts of petroleum sulfonic acids, alkali metal salts of fatty acids, amine and ammonium soaps of fatty acids, alkali metal dialkyl sulfosuccinates, sulfated oils, sulfonated oils, alkali metal alkyl sulfates, and the like.

[00249] Non-limiting examples of saponifiers/buffers include alkanolamines, aminomethyl propanol (AMP-95), diglycolamine (DGA), mono ethanolamine (MEA), mono isopropanolamine (MIPA), butyl ethanolamine (NBEA), dicylclohexyl amine (DCHA), diethanolamine (DEA), butyl diethanolamine (NBDEA), triethanolamine (TEA), metal alkali hydroxides, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, triethanolamine and ethylenediaminetetraacetic acid.

[00250] Non-limiting examples of corrosion inhibitors include organic amines, metallic salts of organic sulfonates, petroleum oxidates, organic diamines, organic amine condensates of fatty alcohols, and substituted imidazolines.

[00251] Non-limiting examples of anti -wear additives (lubricity improvers) include organic acids, caprylic acid, pelargonic acid, isononanoic acid, capric acid, lauric acid, stearic acid, oleic acid, benzoic acid, p-tert-butylbenzoic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, and dodecandioic acid. [00252] In specific embodiments, the metal working fluid composition further includes at least an extreme prcssurc/coupling agent selected from zinc dithiophosphatc (ZDP), zinc dialkyl dithio phosphate (ZDDP), tricresyl phosphate (TCP), halocarbons (chlorinated paraffins), glycerol mono oleate, stearic acid, nonionic surfactant include ethers such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether; esters such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene fatty acid ester; and conventional coupling agents such as volatile alcohols such as sec-butanol, butyl oxitol or cyclohexanol.

Methods of Synthesis

[00253] RAFT polymerization is one of the most robust and versatile methods for providing living characteristics to radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes.

[00254] When preparing, for example, a block copolymer in the presence of the control agent, the end of the growing block is provided with a specific functionality that controls the growth of the block by means of reversible free radical deactivation. The functionality at the end of the block is of such a nature that it can reactivate the growth of the block in a second and/or third stage of the polymerization process with other ethylenically unsaturated monomers providing a covalent bond between, for example, a first and second block [A] and [B] and with any further optional blocks.

[00255] Further details on the chemistry of synthesis of block copolymers by RAFT processes may be found in the following publications, each of which is herein incorporated in its entirety by reference: Polymer, 2008, volume 49, 1079-1131; Chemical Society Reviews, 2014, volume 43, 496-505; Macromolecules, 1998, volume 31, 5559-5562; and Polymer, 2013, volume 54, 2011- 2019.

[00256] In a fourth aspect, the disclosed and/or claimed inventive concept(s) provides a method for preparing a block copolymer, the method comprising: (a) initiating ring-opening polymerization of at least one cyclic diester monomer by including in the polymerization medium a reversible addition-fragmentation chain transfer agent and a catalyst resulting in a moiety having repeating units derived from said cyclic dicstcr monomer, (b) dissolving the moiety in at least one acrylate and/or acrylamide monomer(s), (c) polymerizing the acrylate and/or acrylamide monomer(s) in bulk at a temperature ranging from about 40° C to about 90° C until a conversion from about 5% to about 80% of the acrylate and/or acrylamide monomer(s) is achieved, (d) adding water at a temperature ranging from about 40° C to about 90° C to the polymerization medium to obtain an aqueous dispersion, and optionally (e) continuing polymerization of the acrylate and/or acrylamide monomer(s) until a conversion of at least about 95% of the acrylate and/or acrylamide monomer(s) is achieved.

[00257] In a specific embodiment, the reversible addition-fragmentation chain transfer agent has a hydroxyl functionality.

[00258] In a specific embodiment, the reversible addition— fragmentation chain transfer agent may be one or more compounds selected from the group consisting of dithioesters, thioether- thiones, trithiocarbonates, dithiocarbamates, xanthates and mixtures thereof.

[00259] The block copolymers according to the disclosed and/or claimed inventive concept(s) may be prepared according to the examples set out below. These examples are presented herein for purposes of illustration of the disclosed and/or claimed inventive concept(s) and are not intended to be limiting, for example, the preparations of the polymers. In the examples, the following abbreviations are used:

PLLA: poly(L-lactide)

BHETTC: Benzyl 2-hydroxyethyl tri thiocarbonate

TTC: trithiocarbonate

DMAP: 4-(dimethylamino)pyridine

DMAC: /v/.\'%li methyl acrylamide

PDMAC: polyDMAC

ACVA: 4,4'-Azobis(4-cyanopentanoic acid)

NAM: .V-acryloyl morpholine

PNAM: polyf/V-acryloyl morpholine)

DMF: N, A ’-Dimethylformamide NMR: Nuclear magnetic resonance

CTA: Chain transfer agent

DP: Degree of polymerization

GPC: Gel permeation chromatography

UV: Ultraviolet

TEM: Transmission electron microscopy

DLS: Dynamic light scattering

M_n: Number-average molecular weight

M_w: Weight-average molecular weight

EXAMPLES

[00260] All reagents were used as received, unless stated otherwise. ACVA (98%), DMAC (99%), anhydrous magnesium sulfate and lithium bromide were purchased from Sigma-Aldrich (Dorset, UK). Ammonia solution (28%), NAM (> 97%), and DMAP were purchased from Alfa Aesar (Heysham, UK). DMF was purchased from VWR (Leicestershire, UK). Methanol, ammonium chloride, potassium hydroxide, Oxoid™ phosphate-buffered saline tablets hydrochloric acid (38%) and L-lactide (> 98%) were purchased from Fisher Scientific (Loughborough, UK). The latter monomer was recrystallized from toluene before use. Deuterated dichloromethane (99.8%) was purchased from Goss Scientific Instruments Ltd (Cheshire, UK). Anhydrous dichloromethane was obtained from an in-house Grubbs purification solvent system. BHETTC was prepared using the protocol described in the paper titled ‘Facile one pot synthesis of a range of reversible addition-fragmentation chain transfer (RAFT) agents’ in Chem. Commun. , 2008, 4183-4185, by Skey J. and O’Reilly R. K., which is herein incorporated in its entirety by reference. Deionized water was dispensed from an Elgastat Option 3A water purification system with a resistivity of 15 Mil cm.

[00261] Example 1: Synthesis of trithiocarbonate-capped poly(L-lactide) SCHEME 1

[00262] Synthesis of the PLLA14-TTC precursor was performed according to Samaraj eewa, S.; Shrestha, R.; Li, Y.; Wooley, K. L., Degradability of Poly(Lactic Acid)-Containing Nanoparticles: Enzymatic Access through a Cross-Linked Shell Barrier, J. Am. Chem. Soc. 2012, 134, 1235-1242, which is herein incorporated in its entirety by reference. The reaction is shown in Scheme 1. All glassware was dried in a 200° C oven overnight prior to use. To a flame-dried Schlenk flask charged with a magnetic stirrer bar, L-lactide (5.91 g, 41.0 mmol; target DP = 20), DMAP (0.75 g, 6.12 mmol), BHETTC RAFT agent (0.50 g, 0.45 mL, 2.05 mmol) and dry CH2Q2 (30 mL) were added under a flow of nitrogen gas. The reaction mixture was stirred at 35° C under a nitrogen atmosphere for 18 h. The resulting solution was precipitated into methanol that had been pre-chilled in a -20° C freezer overnight and filtered. The solid product was then washed with excess methanol and dried under vacuum. ' H NMR spectroscopy was used to estimate the mean degree of polymerization (DP) of the PLLA-TTC precursor by end-group analysis (the integrated PLLA backbone signal was compared to the aromatic signal assigned to the BHETTC initiator). The final L-lactide conversion was 70%, which corresponded to a mean DP of 14.

[00263] Example 2 and 3: Synthesis of trithiocarbonate-capped poly(L-lactide)

[00264] For the analogous syntheses of PLLA34-TTC and PLLA48-TTC, essentially the same protocol was followed as in Example 1, except that the mass of BHETTC was reduced to 0.20 g and 0.14 g respectively and the mass of the DMAP was reduced to 0.30 g and 0.21 g respectively. [00265] Example 4-20: RAFT polymerization of DMAC in bulk using PLLA14-TTC

[00266] Example 4: A 14 mL vial was charged with PLLA14-TTC prepared as per Example 1 (0.10 g, 0.044 mmol), DMAC (1.31 g, 13.3 mmol, target DP = 300), ACVA (1.2 mg, 4.4 pmol, [TTC]/[ACVA] molar ratio = 10.0) and a magnetic stirrer bar and sealed with a rubber septum. The contents of this vial were deoxygenated with a stream of dry nitrogen gas for 30 min while the vial was immersed in an ice bath to prevent evaporation. The vial was then allowed to warm to room temperature for 10 min before immersion in an oil bath set at 70° C. The reaction mixture was stirred magnetically and monitored by visual inspection. When the reaction mixture became much more viscous after 32 min, deoxygenated deionized water (3.30 mL, preheated to 70° C, targeting 30% w/w solids) was added using a degassed syringe/needle. At this point, the reaction vial was removed from the oil bath and subjected to vortex mixing for 2 min to ensure a homogeneous solution, then returned to the oil bath. At this time point, the reaction mixture was sampled for ¹ H NMR spectroscopy analysis, which indicated an instantaneous DMAC conversion of 13% (PDMAC DP ~ 39). The DMAC polymerization was allowed to proceed for 16 h prior to quenching by exposing the reaction mixture to air while cooling to 20° C. A final DMAC conversion of more than 99% was indicated by 'H NMR studies. The reaction is shown in Scheme 2. [00267] Examples 5-21: Synthesis of block copolymers with different PDMAC and PLLA DPs

[00268] The procedure in Example 4 was followed. The parameters of the reaction and the DPs of the resulting block copolymers are shown in Table 1.

Table 1. Summary of reagent quantities used for the initial bulk polymerization of DMAC using a PLLAu- TTC or PLLA34-TTC precursor, with subsequent dilution with addition of deoxygenated deionized water at 70° C. Instantaneous conversions at the time of dilution were determined via 'H NMR spectroscopy. For Examples 16, 17, and 18, this synthesis was conducted at 90° C.

[00269] Example 22: RAFT polymerization of NAM in the bulk using PLLAu-TTC

[00270] A 14 mL vial was charged with PLLAu-TTC (0.10 g, 0.044 mmol), NAM (2.50 g, 17.7 mmol, target DP = 400), ACVA (1.2 mg, 4.4 pmol [TTC]/[ACVA] molar ratio = 10.0) and a magnetic stirrer bar and sealed with a rubber septum. The contents of this vial were deoxygenated with a stream of dry nitrogen gas for 30 min while the vial was immersed in an ice bath to prevent evaporation. The vial was then allowed to warm to room temperature for 10 min before immersion in an oil bath set at 70° C. The reaction mixture was stirred magnetically and monitored by visual inspection. When the reaction mixture became much more viscous after 10 min, deoxygenated deionized water (6.06 mL, preheated to 70° C, targeting 30% w/w solids) was added using a degassed syringe/needle. At this point, the reaction vial was removed from the oil bath and subjected to vortex mixing for 2 min to ensure a homogeneous solution, then returned to the oil bath. At this time point, the reaction mixture was sampled for *H NMR spectroscopy analysis, which indicated an instantaneous NAM conversion of 22% (PNAM DP ~ 88). The NAM polymerization was allowed to proceed for 16 h prior to quenching by exposing the reaction mixture to air while cooling to 20° C. A final NAM conversion of more than 99% was indicated by 'H NMR studies. For analogous syntheses in which a PNAM DP of 100 was targeted, the reagent quantities and volume of added water were adjusted accordingly. Water was added a 15 min at an intermediate NAM conversion of 38% (PNAM DP ~ 38).

[00271] Hydrolytic degradation of block copolymer nanoparticles in aqueous solution

Acidic, basic and phosphate-buffered saline (PBS) buffer solutions were prepared as follows. Potassium dihydrogen phosphate (10.00 g, 0.073 mol) was dissolved in deionized water (80 mL). Then the solution pH was adjusted with 0.1 M HC1 and made up to 100 mL with deionized water to provide a final solution pH of 2.7. Ammonium chloride (6.80 g, 0.127 mol) was dissolved in 28% aqueous ammonia solution (100 mL) to afford a final solution pH of 10.8. A single Oxoid PBS tablet was dissolved in deionized water (100 mL) and 0.1 M HC1 was used to adjust the solution pH to pH 7.4. A 30% w/w aqueous dispersion of PLLA14-PDMAC40 nanoparticles was diluted to 1.0% w/w using each of the above aqueous solutions in turn. The resulting three aqueous copolymer dispersions were stirred at 37° C for two weeks and sampled periodically for DMF GPC analyses (refractive index detector). For accelerated degradation experiments, potassium hydroxide (0.50 g, 8.91 mmol) was dissolved in deionized water (10 mL). The solution pH was measured to be 14. This alkaline solution was then used to dilute a 30% w/w aqueous dispersion of PLLA14-PDMAC40 nanoparticlcs to 1.0% w/w and this dilute dispersion was then stirred at 60° C. Characterization Techniques

‘II NMR Spectroscopy

[00272] All spectra were recorded in CD2Q2 using a 400 MHz Bruker Avance-400 spectrometer operating at 298 K. Sixteen scans were averaged per spectrum. Aqueous copolymer dispersions were dried with anhydrous magnesium sulfate before passing through a 0.20 pm filter. DMAC conversions were calculated by comparing the integrated vinyl proton signals at 6.63, 6.23 and 5.66 ppm to the aromatic signals assigned to the benzyl end-group at 7.07-7.39 ppm.

GPC

[00273] All chromatograms were recorded at 60° C with an Agilent 1260 Infinity GPC system comprising two Agilent PL-gel 5 pm Mixed-C columns and a guard column connected in series, a differential refractive index detector and a UV detector (X = 305 nm) and a flow rate of 1.0 ml min'

Agilent GPC/SEC software was used to determine the number-average molecular weight (M_n), weight-average molecular weight (Af_w) and dispersity (Af_w/M_n) for each (co)polymer. Unless otherwise stated, HPLC-grade DMF containing 10 mM LiBr was used as the eluent. The system was calibrated with a series of twelve near-monodisperse poly(methyl methacrylate) standards with M_p values ranging from 800 g mol'¹ to 2,200,000 g mol'¹. Samples were prepared for GPC analysis by diluting to 1.0% w/w using the GPC eluent.

DLS

[00274] All experiments were conducted at 20° C using a Malvern Instruments Zetasizer Nano ZS instrument equipped with a 4 mW He-Ne laser (X = 633 nm), where scattered light was detected at 173° with an avalanche photodiode detector. Samples were prepared for DLS analysis by diluting to 0.1% w/w with deionized water prior to analysis. Samples of PLLA34-PDMAC150 particles diluted to 0.1% w/w were stirred for 24 h to ensure complete dispersion. All samples were equilibrated in the DLS spectrometer for five minutes prior to analysis to allow for thermal equilibration. The mean z-average particle diameter (£>-) and polydispersity index (PDI) were averaged over two consecutive runs consisting of ten measurements each. TEM

[00275] An FEI Tecnai Spirit 2 microscope equipped with an Orius SC1000B camera operating at 80 kV was used for imaging. A plasma glow discharge was used to treat copper/palladium grids (Agar Scientific, UK) that had been coated in-house with a thin film of amorphous carbon for 30 seconds to generate a hydrophilic surface. Subsequently, a 10 pL droplet of freshly diluted 0.1% w/w aqueous copolymer dispersion was placed on a hydrophilic grid for 1 min, then blotted to remove excess sample. A 10 pL droplet of aqueous uranyl formate solution (0.75% w/v) was used to negatively stain the samples for a further 25 seconds before the grid was carefully blotted to remove excess stain. Each grid was carefully dried with the aid of a vacuum hose.

[00276] TEM analysis of the series of PLLA14-PDMAC70-300 nanoparticles confirmed that the final copolymer morphology depended on the target PDMAC DP. Targeting the highest PDMAC DP of 300 led to the formation of diamond-like platelets. In contrast, short rod-like nanoparticles were obtained when targeting the lowest PDMAC DP of 70.

[00277] TEM analysis of dilute aqueous dispersions of the PLLA34-PDMAC150 nanoparticles confirmed that a rod-like morphology was formed when targeting a PDMAC DP of 150.

Aqueous Electrophoresis

[00278] To prepare copolymer dispersions for analysis, 1 mM KC1 was used to dilute aqueous copolymer dispersions to 0.1% w/w. A Malvern Instruments Zetasizer Nano ZS instrument was used for electrophoretic characterization and mobilities were determined at 20° C. Solution pH adjustments were performed using either 0.1 M NaOH or 0.1 M HC1 as required. Zeta potentials were calculated from the Henry equation using the Smoluchowski approximation.

Differential Scanning Calorimetry

[00279] Measurements were performed using a TA DSC25 Discovery series instrument operating from 0 to 150° C at a heating/cooling rate of 10° C min ¹ using aluminum T_zero pans and standard lids. Instrument calibration was performed using an indium standard. All DSC analyses involved three heating/cooling cycles. X-Ray Diffraction

[00280] Prior to XRD analysis, all aqueous dispersions were freeze-dried overnight. Powder X-RD analysis was performed using Cu-Kcr radiation (40 kV, 40 mA) on a Bruker D8 ADVANCE X-ray powder diffractometer equipped with a motorized divergence slit for Bragg-Brentano geometry and a high- resolution energy-dispersive Lynxeye XE detector. The crystallinity of the PLLA component of each diblock copolymer was calculated using Igor 8.04 multipeak fit software. The crystallinity for the PLLA14-TTC precursor was calculated using diffrac.eva v6.1 software.

Claims

What we claim is:

1. A block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

2. The block copolymer according to claim 1 wherein said cyclic diester monomer is selected from the group consisting of lactides, glycolides, and combinations thereof.

3. The block copolymer according to claim 2 wherein said lactide is selected from the group consisting of L-lactide, D-lactide, and combinations thereof.

4. The block copolymer according to claim 1 wherein said second monomer is a functionalized or unfunctionalized Ci-Cis alkyl acrylate or Ci-Cis alkyl (meth)acrylate.

5. The block copolymer according to claim 1 wherein said second monomer is selected from the group consisting of acrylamide, (meth)acrylamide, A-Ci-Cis alkyl acrylamide, A-Ci- Cis alkyl (meth)acrylamide, A,A'-diCi-Ci8 alkyl acrylamide, A.A'-diCi-Cis alkyl (meth)acrylamide, and combinations thereof.

6. The block copolymer according to claim 5 wherein said second monomer is selected from the group consisting of acrylamide, (meth)acrylamide, A-m ethyl acrylamide, A-methyl (meth)acrylamide, AA'-dimethyl acrylamide, AA'-dimethyl (meth)acrylamide, N- acryloyl morpholine, and combinations thereof.

7. The block copolymer according to claim 1 having a structure selected from the group consisting of

wherein each m ranges from about 5 to about 100 and each n ranges from about 10 to 5,000.

8. A composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

9. The composition according to claim 8 which is in the form of an aqueous dispersion.

10. The composition according to claim 9 which is in the form of a Pickering emulsion.

11. The composition according to claim 8 wherein said block copolymer is in the form of colloidal particles.

12. The composition according to claim 11 wherein said colloidal particles are nanoparticles.

13. The composition according to claim 12 wherein said nanoparticles have semicrystalline cores.

14. An emulsifier composition comprising a block copolymer comprising repeating units obtained by polymerizing at least one cyclic diester monomer and at least one second monomer selected from the group consisting of acrylates, acrylamides, and combinations thereof.

15. The composition according to claim 8 that is a coating composition, a personal care composition, a nutrition composition, a pharmaceutical composition, a home care composition, an agricultural composition, an adhesive composition, a battery composition, an oilfield composition, or a metal working fluid composition.

16. The composition according to claim 15 further comprising at least one additive selected from the group consisting of solubilizers, binders, lubricants, surfactants, oils, waxes, solvents, secondary emulsifiers, preservatives, antioxidants, antiradical protecting agents, vitamins, perfumes, dyes, pigments, humectants, fillers, thickeners, film formers, stabilizers, buffers, spreading agents, electrolytes, acids, bases, structuring agents, abrasives, and combinations thereof.

17. A method for preparing a block copolymer, said method comprising: (a) initiating ringopening polymerization of at least one cyclic diester monomer by including in the polymerization medium a reversible addition-fragmentation chain transfer agent and a catalyst resulting in a moiety having repeating units derived from said cyclic diester monomer, (b) dissolving said moiety in at least one acrylate and/or acrylamide monomer(s), (c) polymerizing said acrylate and/or acrylamide monomer(s) in bulk at a temperature ranging from about 40° C to about 90° C until a conversion from about 5% to about 80% of said acrylate and/or acrylamide monomer(s) is achieved, (d) adding water at a temperature ranging from about 40° C to about 90° C to said polymerization medium to obtain an aqueous dispersion, and optionally (e) continuing polymerization of said acrylate and/or acrylamide monomer(s) until a conversion of at least about 95% of said acrylate and/or acrylamide monomer(s) is achieved.

18. The method for preparing a block copolymer according to claim 17 wherein said reversible addition-fragmentation chain transfer agent is selected from the group consisting of dithioesters, xanthates, dithiocarbamates, trithiocarbonates, and combinations thereof.