WO2019096978A1 - Modificateurs de rhéologie multifonctionnels gonflables à l'acide - Google Patents

Modificateurs de rhéologie multifonctionnels gonflables à l'acide Download PDF

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Publication number
WO2019096978A1
WO2019096978A1 PCT/EP2018/081526 EP2018081526W WO2019096978A1 WO 2019096978 A1 WO2019096978 A1 WO 2019096978A1 EP 2018081526 W EP2018081526 W EP 2018081526W WO 2019096978 A1 WO2019096978 A1 WO 2019096978A1
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grams
acid
shell
core
reactor
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PCT/EP2018/081526
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English (en)
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Matthew Michael VANDERHOOF
Klin Aloysius RODRIGUES
Sajal PANTHA
Andrew James BAILEY
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Akzo Nobel Chemicals International B.V.
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Publication of WO2019096978A1 publication Critical patent/WO2019096978A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/546—Swellable particulate polymers

Definitions

  • the present application relates to rheology modifiers comprising acid- swellable core-shell polymers comprising a core and at least one crosslinked shell layer, wherein the mole percent of crosslinking agent in the at least one crosslinked shell layer is greater than the mole percent of crosslinking agent in the core.
  • the application relates to such acid-swellable core-shell polymer rheology modifiers suitable for use in aqueous systems, and which rheology modifiers provide other functions useful in a finished formulation.
  • the application relates to the formation of Theologically and phase stable surfactant aqueous compositions comprising such acid-swellable core-shell polymers.
  • Rheology modifiers also referred to as thickeners or viscosifiers
  • thickeners or viscosifiers are ubiquitous in various commercial formulations, such as personal care formulations, healthcare formulations agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations.
  • Rheological modifiers can be selected for a particular formulation to provide rheological properties for a particular purpose.
  • the rheological modifier can be selected for its ability to provide viscosity and flow characteristics, foamability, spreadability, clarity, sensory effects, and mildness.
  • the application relates to acid-swellable rheology modifiers suitable for use in aqueous compositions, the acid-swellable rheology modifiers comprising at least one core-shell polymer, the core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, wherein the at least one shell copolymer layer is an at least partially cross-linked copolymer containing a mole percent of crosslinking agent greater than the mole percent of crosslinking agent in the core polymer.
  • the application further relates to aqueous compositions comprising such acid-swellable rheology modifiers.
  • the core polymer and the at least one shell copolymer layer are each polymerized from a monomer composition comprising a) one or more cationic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; and d) optionally one or more associative monomers.
  • At least one of the shell copolymer layers will also include one or more crosslinking agents.
  • the core polymer optionally can include one or more crosslinking agents.
  • the core polymer and the at least one shell polymer are substantially free of anionic monomers.
  • the weight proportion of shell to core and the amount of crosslinking agent in each of the shell and the core are selected to provide preferred rheological properties for a particular end-use application.
  • the amount of shell polymer is less than 90 wt% of the total core-shell polymer. In some embodiments, the amount of the at least one shell copolymer layer is greater than 5 wt% of the total core-shell polymer.
  • a crosslinking agent is present in the core polymer.
  • an associative monomer is present in the core polymer, or in the at least one shell copolymer layer, or in both the core polymer and the at least one shell copolymer layer.
  • the core-shell polymers include CrC 6 alkyl (meth)acrylate monomers. In some embodiments, the core-shell polymers include both at least one CrC 6 alkyl acrylate monomer and at least one CrC 6 alkyl methacrylate monomer.
  • the application relates to acid-swellable rheology modifiers comprising core-shell polymers and further comprising a spray-drying adjuvant.
  • the application relates to acid-swellable rheology modifiers comprising core-shell polymers and further comprising a spray-drying adjuvant derived from a natural, renewable resource.
  • the natural renewable resource from which the spray-drying adjuvant is derived from a polysaccharide.
  • the natural renewable resource from which the spray-drying adjuvant is derived is based on cellulose.
  • the natural renewable resource from which the spray-drying adjuvant is derived is based on starch.
  • the application relates to acid-swellable rheology modifiers comprising core-shell polymers and further comprising a spray-drying adjuvant derived from a polyvinyl acetate derivative.
  • a method of making an acid-swellable rheology modifier composition comprises the steps of (i) providing an acid-swellable core-shell polymer as disclosed herein, (ii) blending the core-shell polymer with a spray-drying adjuvant, and (iii) drying the blend; whereby the acid-swellable rheology modifier is in the form of a dried powder.
  • the application relates to aqueous polymer emulsions comprising an acid-swellable core-shell polymer as described herein.
  • the application relates to formulations comprising acid-swellable rheology modifiers as disclosed herein.
  • the formulations comprising acid-swellable rheology modifiers as disclosed herein are selected from personal care formulations, health care formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations formulations for use in electronics industries, and formulations for use in construction industries.
  • the formulations are aqueous formulations further comprising one or more surfactants.
  • the surfactants can be selected from any of anionic, cationic, amphoteric and nonionic surfactants, and mixtures thereof.
  • the formulations are personal care formulations.
  • the personal care formulations are hair fixative formulations
  • the acid-swellable rheology modifiers provide the additional function of film-forming, such that the rheology modifier also functions as a hair fixative ingredient in the formulation.
  • the formulations are low pH formulations, which are compatible with the acid-based preservatives and cationic ingredients.
  • polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein.
  • the embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.
  • the term“(co)polymer” indicates polymer or copolymer.
  • the term“polymer” and the term“copolymer” are used herein interchangeably.
  • the terms“core-shell morphology”, “core-shell structure”,“core-shell polymer”,“staged core-shell polymer” and“two- staged polymer” or“multi-staged polymer” are used interchangeably and mean a polymer particle prepared by a sequential or staged polymerization process wherein each sequence or stage of monomer repeating units is added to the polymerization reactor and begins to undergo polymerization before the addition and polymerization of the subsequent sequence or stage of repeating units is commenced.
  • the polymerization of one stage will be substantially complete before the monomers of the next stage are added to the polymerization reactor; in some embodiments the polymerization of one stage may be only partially complete before the monomers of the next stage are added to the polymerization reactor.
  • these core-shell polymers disclosed herein have a structure in which a polymer(s) forming the core portion, sequence or stage and the polymer(s) forming the shell portion, sequence or stage are physically and/or chemically bonded and/or attracted to each other.
  • the structure and/or chemical composition (e.g., monomer composition and/or amount) of the disclosed copolymer particles changes from the inside to the outside of the particle and, as a result, these gradient zones can have different physical and chemical properties as well. These changes can be somewhat gradual, yielding a morphology having a gradient of polymeric structure or composition along any radius thereof. Alternatively, the change in polymeric structure or
  • the staged core-shell morphology can comprise multiple layers or zones of differing polymeric composition as long as at least one shell copolymer layer is an at least partially cross-linked polymer containing a mole percent of crosslinking agent greater than the mole percent of crosslinking agent in the core polymer.
  • the rate of change in the polymeric morphology of the particle is not particularly critical as long as the polymer exhibits the requisite properties described herein.
  • the terms“core” and“shell” refer to the polymeric content of the inside and the outside of the particle, respectively, and the use of said terms should not be construed as meaning that the disclosed polymer particles will necessarily exhibit a distinct interface between the polymers of the inside and the outside of the particle.
  • the staged core-shell polymer particle can be in a form in which the core portion is completely coated or encapsulated within the shell portion.
  • the core-shell polymer particle can be in a form in which the core portion is only partly coated or encapsulated.
  • the“core polymers” and the“shell polymers” of the disclosed staged core-shell polymers there can be a significant amount of interpenetration of the polymers residing in the core and shell of the polymer particles.
  • the“core polymers” can extend somewhat into the shell of the particle forming a domain in the shell particle, and vice versa.
  • core polymers and“shell polymers” and like terminology are employed herein to describe the polymeric material in the named portion of the polymeric particle in a general way without attempting to identify any particular polymers as strictly“shell” or strictly“core” polymers.
  • the term“(meth)acrylic” acid is meant to include both acrylic acid and methacrylic acid.
  • the term“alkyl (meth)acrylate” as used herein is meant to include alkyl acrylate and alkyl methacrylate.
  • aqueous as applied to formulations or media means that water is present in an amount sufficient to at least swell or dissolve the multi-purpose polymer in the composition into which it is formulated.
  • the acid-swellable core-shell polymers of the present invention provide desirable rheological properties to aqueous formulations having a pH in the range of about 1 - 7, or in the range of about 2 - 6.5, or in the range of about 2-6, or in the range of about 3- 6, said formulations being selected from personal care formulations, health care formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, industrial and institutional cleaning formulations, formulations for use in electronics industries, and formulations for use in construction industries.
  • the acid-swellable core-shell polymers of the present invention are compatible with cationic ingredients making them particularly useful as thickeners in products containing quaternary ammonium salts or amines.
  • the acid-swellable core-shell polymers of the present invention are useful in compositions containing one or more surfactants (e.g., anionic, cationic, amphoteric, non-ionic, and/or combinations of any two or more thereof).
  • surfactants e.g., anionic, cationic, amphoteric, non-ionic, and/or combinations of any two or more thereof.
  • the acid-swellable core-shell polymers can also provide hair setting efficacy.
  • the acid-swellable core-shell polymers are useful thickeners in products containing active acid components and are useful thickeners and emulsifiers for emulsions (creams, lotions).
  • the acid- swellable core-shell polymers are useful film formers, spreading aids and deposition aids for products containing surfactants, colorants, hair and skin conditioners, silicones, monoquaternium compounds, polyquaternium compounds, anti-dandruff agents, anti- aging, anti-wrinkle, anti-pigment anti-cellulite, anti-acne, vitamins, analgesics, anti- inflammatory compounds, self-tanning agents, hair growth promoting agents, UV protecting agents, skin lighteners, vegetable, plant and botanical extracts,
  • antiperspirants antioxidants, deodorants, hair fixative polymers, emollient oils, and combinations thereof.
  • the acid-swellable core-shell polymers as disclosed herein also impart desirable clarity properties, as measured in units of turbidity.
  • Aqueous compositions of the rheology modifiers disclosed herein can have a turbidity value of £ 1000 NTU in one aspect, £500 NTU in another aspect, £200 NTU in another aspect, £100 NTU in another aspect, and £50 NTU in a further aspect as measured in a thickened aqueous polymer composition comprising about 2% by weight polymer (active polymer solids) and the remainder water, and wherein the pH of the thickened composition is about 3-4.
  • rheological properties includes without limitation such properties as viscosity, increase or decrease in viscosity in response to shear stress, and flow characteristics; gel properties such as stiffness, resilience, flowability, and the like; foam properties such as foam stability, foam density, ability to hold a peak, and the like; suspension properties such as yield value; and aerosol properties such as ability to form aerosol droplets when dispensed from propellant- based or mechanical pump-type aerosol dispensers; the flow of a liquid through a pump dispenser; or any quality or property that can be measured with a viscometer or a rotational or extensional rheometer.
  • aqueous compositions of the rheology modifers disclosed herein will have yield values sufficient to support suspensions of aesthetic and cosmeceutical beads and particles, gaseous bubbles, exfoliants, and the like.
  • compositions refers to visual and tactile psychosensory product properties, such as color, clarity, smoothness, tack, lubricity, texture, conditioning and feel, and the like.
  • Acid-swellable rheology modifiers for use in aqueous compositions comprise core-shell polymers, the shell comprising one or more copolymer layers, wherein at least one shell copolymer layer is an at least partially cross-linked polymer containing a mole percent of crosslinking agent greater than the mole percent of crosslinking agent in the core polymer.
  • the core-shell polymers can include multiple shell copolymer layers, which can be the same as or different from the core layer and from each other with respect to both the type and proportions of monomers in the polymer backbone.
  • the multiple shell copolymer layers can have any mole percent of crosslinking agent, as long as the core (first stage) polymer has a mole percent of crosslinking agent less than at least one of the crosslinked shell (subsequent stage) copolymer layers.
  • the core-shell polymer comprises from about 1 % to about 95% by weight of the one or more shell layers, based on the total weight of the core-shell polymer. In one embodiment the core-shell polymer comprises about 5 wt% to about 60 wt% of the one or more shell layers, in one embodiment about 10 wt% to about 40 wt% of the one or more shell layers, and in one embodiment about 15 wt% to about 35 wt% of the one or more shell layers, in each case based on the total weight of the core- shell polymer, with the balance of the polymer being the core polymer.
  • the core is at least 10 wt% of the core-shell polymer; in one embodiment at least 20 wt%; in one embodiment at least 40 wt%; in one embodiment at least 50 wt%; in one embodiment at least 60 wt%; in one embodiment at least 70 wt%; in one embodiment at least 80 wt%; in one embodiment at least 85 wt%; in one embodiment at least 90 wt%; in one embodiment at least 95 wt%.
  • the core polymer comprises zero crosslinking agent, and the core is greater than 60 wt% of the core-shell polymer.
  • the core polymer is polymerized from a monomer composition comprising a) one or more cationic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; d) optionally one or more associative monomers; and e) optionally one or more crosslinking agents.
  • the one or more shell copolymer layers are each polymerized from a monomer composition comprising a) one or more cationic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; c) optionally one or more nonionic ethylenically unsaturated monomers; d) optionally one or more associative monomers; and e) optionally one or more crosslinking agents, as long as at least one shell copolymer layer includes one or more crosslinking agents.
  • both the core polymer and the shell polymer are substantially free of non-associative anionic monomers, as described below.
  • the one or more crosslinking agents will be present in the monomer composition of at least one of the shell layers, and optionally present in the core monomer composition, as long as there is more crosslinking agent in the at least one shell layer than in the core polymer.
  • the term "cationic ethylenically unsaturated monomer” means an ethylenically unsaturated monomer which is capable of developing a positive charge when the polymer in which the monomer is polymerized is in an aqueous solution.
  • the cationic ethylenically unsaturated monomer has at least one primary, secondary, or tertiary amine functionality, or is an acyclic ethylenically unsaturated formamide or acetamide.
  • the term “amine salt” means that the nitrogen atom of the amine functionality is covalently bonded to from one to three organic groups and is associated with an anion.
  • the cationic ethylenically unsaturated monomer is selected from one or more of N,N-dimethylaminoethyl methacrylate, tert-butylaminoethylmethacrylate, N,N-dimethylaminopropyl
  • methacrylamide 3-(dimethylamino)propyl methacrylate, 2-(dimethylamino)propane-2-yl methacrylate, 3-(dimethylamino)-2,2-dimethylpropyl methacrylate, 2-(dimethylamino)-2- methylpropyl methacrylate and 4-(dimethylamino)butyl methacrylate and mixtures of any of the foregoing.
  • the most preferred cationic ethylenically unsaturated monomers are N,N-dimethylaminoethyl methacrylate, tert-butylaminoethylmethacrylate and N,N- dimethylaminopropyl methacrylamide, and mixtures of any of the foregoing.
  • the cationic ethylenically unsaturated monomer can be present as at least about 10 mol% or more of the total monomer used to produce the core polymer or shell copolymer layer of the acid swellable core-shell polymer in which it is present, or at least about 15 mol% or more, or at least about 20 mol% or more, or at least 30 mol%, or at least 40 mol%, or at least 50mol%.
  • the maximum proportion of the cationic ethylenically unsaturated monomer in the core polymer or shell copolymer layer of the acid-swellable core-shell polymer in which it is present can be about 80 mol% or less, preferably about 70 mol% or less, and most preferably about 60 mol% or less, in each case the mol% being based on the total moles of monomers present in that stage not including the crosslinking agent.
  • hydrophobic ethylenically unsaturated monomer means a monomer that is hydrophobic and enables the formation of an emulsion system when reacted with the cationic ethylenically unsaturated monomer.
  • a hydrophobic ethylenically unsaturated monomer can be sparingly soluble in water but has a water solubility of less than 6 grams per 100 mis of water at 25°C, or less than 3 grams per 100 mis of water at 25°C, preferably less than 2 grams per 100 mis of water at 25°C, and most preferably less than 1.6 gram per 100 mis of water at 25°C.
  • hydrophobic monomers may contain linear or branched alk(en)yl, cycloalkyl, aryl, or alk(en)aryl moieties.
  • Suitable hydrophobic ethylenically unsaturated monomers include CrC 32 alkyl esters of acrylic acid and methacrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl
  • esters of acrylic acid and methacrylic acid including benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl ethoxylate (meth)acrylate, phenyl ethoxylate (meth)acrylate, 6-hydroxy hexyl (meth)acrylate, and 10-hydroxydecyl (meth)acrylate ; and C 4 -C 32 alkyl amides of acrylic and methacrylic acid, including tertiary butyl (meth)acrylamide, t-octyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, n-octyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, and behenyl (meth)acrylamide.
  • hydrophobic monomers include styrene, omethyl styrene, vinyl toluene, t-butyl styrene, iso-propyl styrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (meth)acrylonitrile, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1 -allyl naphthalene, 2-allyl naphthalene, 1 -vinyl
  • naphthalene 2-vinyl naphthalene
  • All of the foregoing monomers may be used in any combination thereof.
  • Preferred are ethyl (meth)acrylate, methyl (meth)acrylate, 2- ethylhexyl acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl
  • ethyl acrylate, methyl acrylate, methyl methacrylate, vinyl acetate, butyl acrylate and combinations thereof are preferred.
  • ethyl acrylate is preferred.
  • the hydrophobic ethylenically unsaturated monomers set forth under the second monomer component b) are utilized in an amount ranging from about 90 mol% to about 20 mol%, from about 80 mol% to about 30 mol% in another aspect, and from about 75 mol% to about 35 mol% in still another aspect, and from about 60 mol% to about 40 mol%, , or in still another aspect is greater than 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 30 mol%, or at least 40 mol%, or at least 50 mol% based upon the total moles of the monomers in the core polymer or shell copolymer layer in which the hydrophobic ethylenically unsaturated monomer is used, in each case the mol% being based on the total moles of monomers present in that stage not including the crosslinking agent.
  • the hydrophobic ethylenically unsaturated monomer is present at 20-30 mol%,
  • nonionic ethylenically unsaturated monomer means an ethylenically unsaturated monomer which does not introduce a charge into the core- shell polymers, and which is neither a hydrophobic ethylenically unsaturated monomer, nor an associative monomer, nor a crosslinker, each as defined herein.
  • nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, N-Ci-C 3 alkyl(meth)acrylamides and N,N-Cr
  • C 3 dialkyl(meth)acrylamides such as N-methylmethacrylamide, N-ethylacrylamide, N- propylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, and N,N - dimethylmethacrylamide; vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butanoate, , ethoxylated alkyl, alkaryl or aryl monomers such as methoxypolyethylene glycol (meth)acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth)acrylate, Ci to C 4 hydroxyalkyl esters of (meth)acrylic acid, and others.
  • n 1 to 100, preferably 3 - 50, and most preferably 5 - 20, ethoxylated CrC 4 alkyl, C r C alkaryl or aryl monomers.
  • unsaturated monomer component c) is methoxypolyethylene glycol (meth)acrylate.
  • the optional Ci to C 4 hydroxyalkyl esters of (meth)acrylic acid can include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (butane diol mono(meth)acrylate).
  • the hydroxyalkyl ester of component c) is selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2- hydroxybutyl (meth)acrylate.
  • the optional nonionic ethylenically unsaturated monomers of component c), when present, can be present as about 5 mol% to about 30 mol%, or from about 10 mol% to about 25 mol% in the core polymer or shell copolymer layer in which the optional nonionic ethylenically unsaturated monomer is used, in each case the mol% being based on the total moles of monomers present in that stage not including the
  • associative monomer is intended to mean an ethylenically unsaturated monomer containing a hydrophobe and a spacer moiety which allows the hydrophobe to be sufficiently far away from the backbone of the polymer to form hydrophobic associations in aqueous solutions, and wherein the hydrophobe
  • the spacer moieties are usually ethoxylate groups but any other group that extends the hydrophobe away from the backbone of the polymer may be used.
  • the hydrophobes with a spacer moiety include, but are not limited to, alcohol ethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated silicones and the like.
  • the preferred hydrophobes with spacer moieties include alcohol ethoxylates and/or alkylphenoxy ethoxylates.
  • alcohol ethoxylates containing alcohols with carbon chain lengths of 6 to 40 and 6 to 100 moles of ethoxylation are more preferred.
  • alcohol ethoxylates containing alcohols with carbon chain lengths of 12 to 22 and 15 to 30 moles of ethoxylation are particularly preferred.
  • the hydrophobes may be linear or branched alk(en)yl, cycloalkyl, aryl, alk(en)aryl or an alkoxylated derivative.
  • the most preferred hydrophobes are linear or branched alcohols and amines containing 12 to 32 carbons.
  • the associative monomer may contain an ethylenically unsaturated monomer covalently linked to the hydrophobe.
  • the ethylenically unsaturated monomer part of the associate monomer preferably is a (meth)acrylate, itaconate and/or maleate which contains ester linking groups.
  • the associative monomer may also contain amide, urea, urethane, ether, alkyl, aryl and other suitable linking groups.
  • the hydrophobe may be an alkylamine or dialkylamine ethoxylate.
  • the (meth)acrylate group is most preferred.
  • preferred associative monomers are Ci 2- 3 2 (EO)IO_3O meth(acrylates) or CI 2-3 2(EO)IO-3O itaconates or or CI 2-3 2(EO)IO-3O maleates.
  • the associative monomer has the structure of formula (I)
  • Ri is -H, -CH 3 , -COOH, or -CH 2 COOH;
  • A is -CH 2 C(0)0-, -C(0)0-, -0-, -CH 2 0-, -CH 2 C(0)N-, -C(0)N-, -CH 0-C(0>
  • R 4 is C 6 -C 36 linear or branched, saturated or unsaturated alk(en)yl or alk(en)aryl, preferably C 8 -C 32 linear or branched alk(en)yl, more preferably C 10 -C 22 linear alk(en)yl or C 10 -C 32 branched alk(en)yl; and
  • R 5 is -CH 2 - or -(C)(CH 3 ) 2 -.
  • Suitable associative monomers include methacrylate and itaconate esters of a hydrophilic ethoxylate chain and a hydrophobic alkyl chain.
  • the associative monomer is an alkyl ethoxylate methacrylate ester having the structure of formula l(A):
  • the associative monomer is an itaconate-based associative monomer such as cetyl ethoxylate itaconate, behenyl ethoxylate itaconate, or stearyl ethoxylate itaconate having the structure of formula I (B, C, D respectively):
  • the optional associative monomers set forth under the monomer component d), when present, are utilized in an amount ranging from about 0.001 mol% to about 20 mol%, from about 0.005 mol% to about 10 mol% in another aspect, and from about 0.01 mol% to about 5 mol% in still another aspect in the core polymer or0 shell copolymer layer in which the associative monomer is used, in each case the mol% being based on the total moles of monomers present in that stage not including the crosslinking agent.
  • both the core polymer and the one or more shell polymers are identical to each other.
  • an anionic monomer as used herein is a non-associative ethylenically unsaturated monomer which is capable of developing a negative charge when the polymer is in an aqueous solution.
  • the core polymer contains no anionic monomers.
  • the one or more shell polymers contain no anionic monomer.
  • the core polymer and the one or more shell polymers contain no anionic monomer.
  • anionic monomers include (meth)acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acid, and vinyl phosphonic acid and salts thereof, and mixtures thereof.
  • the term“substantially free” means that any anionic monomer that may be present is in such a low amount that it will not impede the swelling and rheology modification function of the core-shell polymer when the polymer is activated in the formluation in which it is to be used by lowering the pH using an acidic material, as described further herein.
  • the core polymer and the at least one shell polymer layer each comprise less than 10 mol% anionic monomer, in one embodiment less than 5 mol% anionic monomer, in one embodiment less than 3 mol% anionic monomer, in one embodiment less than 2 mol% anionic monomer, in one embodiment less than 1 mol% anionic monomer.
  • At least one shell copolymer layer of the core-shell polymer includes a crosslinking agent such that the layer containing the crosslinking agent is a partially or substantially-crosslinked network.
  • the core also can contain crosslinking agent, whereby the core will be a partially or substantially-crosslinked network, as long as the mole percent of crosslinking agent in the core (first stage) polymer is less than the mole percent of crosslinking agent in the at least one of the shell copolymer layers
  • the crosslinking agent can be selected from one or more of a crosslinking monomer having two or more carbon-carbon double bonds, or a polyfunctional crosslinking compound that reacts with pendant functional groups on the polymer.
  • Exemplary crosslinking monomers include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,6-butylene glycol
  • pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether; polyallyl ethers of trimethylolpropane such as
  • trimethylolpropane diallyl ether and trimethylolpropane triallyl ether are examples of suitable polyunsaturated compounds.
  • suitable polyunsaturated compounds include divinyl glycol, divinyl benzene, and N,N’- methylenebisacrylamide.
  • suitable polyunsaturated monomers can be synthesized via an esterification reaction of a polyol made from ethylene oxide or propylene oxide or combinations thereof with unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, or an addition reaction with unsaturated isocyanate such as 3-isopropenyl-oa-dimethylbenzene isocyanate.
  • unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride
  • unsaturated isocyanate such as 3-isopropenyl-oa-dimethylbenzene isocyanate.
  • Exemplary polyfunctional crosslinking compounds include polyhaloalkanols such as 1 ,3-dichloroisopropanol and 1 ,3-dibromoisopropanol; sulfonium zwitterions such as the tetrahydrothiophene adduct of novolac resins; haloepoxyalkanes such as
  • epichlorohydrin epibromohydrin, 2-methyl epichlorohydrin, and epiiodohydrin;
  • polyglycidyl ethers such as 1 ,4-butanediol diglycidyl ether, glycerine-1 ,3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, bisphenol A-epichlorohydrin epoxy resins and mixtures of the foregoing. Mixtures of two or more of the foregoing polyfunctional compounds can also be used.
  • the crosslinking agent can be used in an amount ranging from about 0.001 mol% to about 20 mol% in one aspect, from about 0.01 mol% to about 10 mol% in another aspect, and from about 0.03 mol% to about 7.5 mol% in a further aspect, in each case based upon the total moles of monomers in the stage in which the crosslinking agent is used, not counting the amount of crosslinking agent.
  • the amount of crosslinking agent in each layer will be selected depending on the desired properties the core-shell polymer.
  • the molar percentage of crosslinking agent in a given stage when present, is about 0.001 mol% to about 20 mol%, preferably about 0.01 mol% to about 15 mol%, and more preferably about 0.05 mol% to about 10 mol%, and most preferably from about 0.5 mol% to about 7 mol%, in each case based on the total moles of monomers present in that stage not including the crosslinking agent.
  • the crosslinking agent of at least one shell (subsequent stage) polymer can be present during the synthesis of that stage in an amount ranging from about 0.05 mol% to about 20 mol%, preferably from about 0.05 mol% to 10 mol%, and most preferably from about 0.1 mol% to about 10 mol%, in each case based on the total moles of monomers in that shell stage not including the crosslinking agent.
  • Chain transfer agents can be used in any stage of the core-shell polymerization process.
  • the chain transfer agent can be any chain transfer agent which reduces the molecular weight of the disclosed staged polymers.
  • Suitable chain transfer agents include, but are not limited to, thio and disulfide containing compounds, such as CrCi 8 alkyl mercaptans, Ci-Ci 8 alkyl mercaptoalcohols, mercaptocarboxylic acids, mercaptocarboxylic esters, thioesters, Ci-Ci 8 alkyl disulfides, aryldisulfides,
  • polyfunctional thiols such as trimethylolpropane-tris-(3-mercaptopropionate), pentaerythritol-tetra-(3-mercaptopropionate), pentaerythritol-tetra-(thioglycolate), and pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioglycolate), and the like; phosphites and hypophosphites; haloalkyl compounds, such as carbon tetrachloride, bromotrichloromethane, and the like; and catalytic chain transfer agents such as, for example, cobalt complexes (e.g., cobalt (II) chelates).
  • cobalt complexes e.g., cobalt (II) chelates.
  • the chain transfer agent is selected from n-dodecyl mercaptan, methyl mercaptopropionate, and 3-mercaptopropionic acid, 2-mercaptoethanol, combinations thereof and the like, octyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, isooctyl 3-mercaptopropionate, butyl 3-mercaptopropionate, butyl thioglycolate, isooctyl thioglycolate, and dodecyl thioglycolate.
  • the chain transfer agent can be present in an amount ranging from about 0.005 mol% to about 1 mol%, or from about 0.01 mol% to about 1 mol%, in each based on the total moles of monomer in the stage in which the chain transfer agent is used, not including the crosslinking agent.
  • the core-shell polymers disclosed herein comprise at least two polymers synthesized sequentially via free radical emulsion polymerization techniques known to the art.
  • the core polymer is synthesized in a first emulsion polymerization step from a monomer composition comprising a) one or more, cationic ethylenically unsaturated monomers; b) one or more hydrophobic ethylenically unsaturated monomers; and optionally c) one or more nonionic ethylenically unsaturated monomers, and/or d) one or more associative monomers, and/or e) one or more crosslinking agent, all as disclosed above.
  • a chain transfer agent also can be used.
  • the core monomer composition is pre-emulsified in a water and surfactant mixture in a first vessel before being added to the reactor where emulsion polymerization takes place.
  • water and surfactant are added to the reactor before the core monomer composition and then the emulsion
  • the emulsion polymerization reaction mixture also includes one or more free radical initiators.
  • the one or more free radical initiators are present in an amount in the range of about 0.01 weight percent to about 3 weight percent based on total monomer weight.
  • the polymerization can be performed in an aqueous or aqueous alcohol medium at neutral to moderately alkaline pH.
  • Suitable surfactants for facilitating emulsion polymerizations include nonionic, anionic, amphoteric, cationic surfactants, and mixtures thereof. Most commonly, nonionic surfactants are utilized.
  • the physical properties of the neutralized polymer e.g., viscosity, spreadability, clarity, texture, and the like
  • Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art, and include, without limitation, linear or branched alcohol ethoxylates, C 8 to Ci 2 alkylphenol alkoxylates, such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like.
  • nonionic surfactants include C 8 to C 22 fatty acid esters of polyoxyethylene glycol, mono and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C 8 to C 22 fatty acid glycol esters, block copolymers of ethylene oxide and propylene oxide having an HLB value of greater than about 12, ethoxylated octylphenols, and combinations thereof.
  • linear alcohol alkoxylates include polyethylene glycol ethers of cetearyl alcohol (a mixture of cetyl and stearyl alcohols) sold under the trade names PLURAFAC® C-17, PLURAFAC® A-38 and PLURAFAC® A-39 by BASF Corp.
  • polyoxyethylene polyoxypropylene block copolymers include copolymers sold under the trade names PLURONIC® F127, and PLURONIC® L35 by BASF Corp.
  • nonionic surfactants include, but are not limited to, Ethoxylated linear fatty alcohols such as DISPONIL® A 5060 (Cognis), Ethal LA-23 and Ethal LA-50 (Ethox Chemicals), branched alkyl ethoxylates such as GENAPOL® X 1005 (Clariant Corp.), secondary Ci 2 to Oi 4 alcohol ethoxylates such as TERGITOL® S15-30 and S15-40 (Dow Chemical Co.), ethoxylated octylphenol-based surfactants such as TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887, and 897 (Rhodia, Inc.), ICONOL® OP 3070 and 4070 (BASF Corp.), SYNPERONIC® OP 30 and 40 (Uniqema), block copolymers of ethylene oxide and propylene oxide such as PLURONIC® L35 and
  • Suitable polymeric stabilizers for the emulsion polymerization process of this invention are water-soluble polymers, including, for example, synthetic polymers, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers and the like; water- soluble natural polymers, such as gelatin, pectins, alginates, casein, starch, and the like; and modified natural polymers, such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl modified hydroxyethylcellulose, and the like.
  • synthetic polymers such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, carboxylate-functional addition polymers, polyalkyl vinyl ethers and the like
  • water- soluble natural polymers such as gelatin, pect
  • Polymeric stabilizers can be utilized in amounts up to about 10 weight percent based on the total emulsion weight, or up to about 7.5 weight percent, or up to about 5 weight percent, or up to about 2.5 weight percent, or up to about 2 weight percent based on the total emulsion weight.
  • a polymeric stabilizer is included in an amount in the range of about 0.001 weight percent to about 10 weight percent, or from about 0.01 weight percent to about 7.5 weight percent, or from about 0.1 weight percent to about 5 weight percent, or from about 0.5 weight percent to about 2.5 weight percent, or even from about 1 weight percent to about 2 weight percent, based on the total emulsion weight.
  • emulsifying surfactant such as a nonionic surfactant
  • the emulsion is deoxygenated by any convenient method, such as by sparging with nitrogen, and then a
  • Typical initiating systems may include a thermal initiating system or redox initiators such as sodium persulfate and sodium bisulfite, or any other suitable addition polymerization catalyst, as is well known in the emulsion polymerization art.
  • the initiating system is split in to 2 parts and added both during the first stage and the second stage.
  • the initiating system is split in to proportions of the weight percent of each stage.
  • the total time of addition is 120 minutes. If the system has 20% of the monomer in stage 1 (core) then 20% of the initiating system is added over 24 minutes (20% of 120 minutes). The initiator feeds are stopped and the mixture is cooked for 30 minutes.
  • second stage of monomers is added as a bulk addition individually or as a mixture with agitation. Initiator feeds are then resumed as described above, where the total initiator is typically fed over 120 minutes. The reaction product is stirred until the
  • the monomer emulsion can be heated to a temperature in the range of about 20° C. to about 95° C. prior to addition of the initiator, if desired. Unreacted monomer can be eliminated by addition of more initiator as well as other methods well known in the emulsion polymerization art.
  • the resulting polymer emulsion product can then be discharged from the reactor and packaged for storage or use.
  • the pH or other physical and chemical characteristics of the emulsion can be adjusted prior to discharge from the reactor.
  • the product emulsion has total solids (TS) content in the range of about 10 weight percent to about 50 weight percent.
  • the total polymer content of the product emulsion is in the range of about 15 weight percent to about 40 weight percent, generally not more than about 40 weight percent.
  • the emulsion polymerization reactions are carried out at a reaction temperature in the range of about 20 to about 99°C, however, higher or lower temperatures can be used.
  • the emulsion polymerization reactions can be performed in an aqueous or aqueous alcohol medium.
  • the surfactant can be added to the monomer composition to form a pre-emulsion, or the surfactant can be added directly to the polymerization reactor during the emulsion polymerization, or both.
  • the emulsion polymerization is carried out in the presence of surfactant ranging in the amount of about 0.1 % to about 10% by weight in one aspect, from about 0.5 % to about 8% in another aspect, and from about 1.0 % to about 5 % by weight in a further aspect, based on a total emulsion weight basis.
  • free radical initiators that generate a free radical during the polymerization process are utilized.
  • the initiating system is any free radical initiating system.
  • the free radical initiators are present in an amount ranging from about 0.01% to about 3% by weight based on total monomer weight.
  • the initiating system is soluble in water to at least 0.1 weight percent at 25°C.
  • Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as tert-butyl hydroperoxide and erythorbic acid, and metal ion based initiating systems.
  • Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t- butyl hydroperoxide.
  • the inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate, are preferred.
  • the initiators comprise metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides.
  • Organic peracids such as peracetic acid can be used.
  • Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • reducing agents such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like.
  • a preferred system is the redox system of sodium persulfate and sodium bisulfite.
  • Azo initiators especially water soluble azo initiators, may also be used.
  • Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2- (2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-Azobis(2- methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis ⁇ 2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane ⁇ dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1 - imino-1-pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Az
  • emulsion polymerization additives and processing aids which are well known in the emulsion polymerization art, such as auxiliary emulsifiers, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides, antifoam agents, and pH adjusting agents can be included in the emulsion polymerization additives and processing aids.
  • auxiliary emulsifiers such as auxiliary emulsifiers, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides, antifoam agents, and pH adjusting agents.
  • multi-staged or multi-layered polymers can be formed through the sequential emulsion polymerization of monomer charges in the presence of polymer particles of a previously formed emulsion polymer.
  • the core-shell polymers as disclosed herein, it is possible to adjust any of (i) the relative mole ratios of the individual monomers, (ii) the mass percent of each of the core and shell stages in the core-shell polymer, (iii) the choice of monomers, crosslinking agent, or associative monomers in any of the layers, (iv) the addition rate of monomer mixtures, surfactant solutions, and initiator solutions, and (v) the mole percentage of crosslinking agent in any of the layers, as long as the mole percent of crosslinking agent in the core (first stage) is less than the mole percent of crosslinking agent in at least one of the shell (subsequent stage) layers.
  • the rheology modifier compositions can be in the form of dried rheology modifiers. In one embodiment the rheology modifier composition can be dried by spray drying.
  • the present disclosure further relates to a method of making rheology modifier compositions, comprising blending the core-shell polymer with a spray drying adjuvant, and drying the resultant mixture.
  • spray-drying can be facilitated by the presence of a spray-drying adjuvant.
  • the spray drying adjuvant can be a polysaccharide, such as a starch or cellulose.
  • the polysaccharide is present in the emulsion polymer composition by virtue of its use as a chain transfer agent or emulsion stabilizer during the polymerization process.
  • spray drying adjuvant is blended into the emulsion polymerization product prior to spray drying.
  • the core-shell polymers that are emulsion polymerized as described above and then blended with a spray drying adjuvant polymer can be dried, preferably by spray drying, to provide dried rheology modifier compositions in the form of stable powders.
  • the spray drying adjuvant may be a polysaccharide, suitable examples of which include starch and cellulose, and derivatives thereof.
  • Other suitable spray drying adjuvants include derivatives of polyvinyl acetate such as polyvinyl alcohol, copolymers of polyvinyl alcohol/polyvinyl acetate, and other copolymers of polyvinyl alcohol.
  • dried rheology modifier composition means a composition comprising at least one core-shell polymer and at least one polysaccharide, the composition being in a dry form comprising less than 25 wt% water, in one embodiment less than 20 wt% water, in one embodiment less than 10 wt% water, in one
  • the polysaccharide component allows the resulting composition to be dried to produce a dried rheology modifier composition with less than 25 weight percent water. Without being bound by theory, it is believed that higher glass transition temperatures of the polysaccharide polymer make it easier to dry the rheology modifier composition. In one embodiment the polysaccharide polymer has a glass transition temperature of at least 50°C, in one embodiment at least 75°C, and in one embodiment at least 90°C.
  • the weight percent of the polysaccharide polymer or other spray drying adjuvant is at least about 20 wt % of the dried rheology modifier composition, preferably at least about 25 wt% of the dried rheology modifier composition, and most preferably at least about 30 wt% of the dried rheology modifier composition.
  • the maximum weight percent of the polysaccharide polymer or other spray drying adjuvant is no more than about 90 wt % of the dried rheology modifier composition, in another embodiment preferably no more than about 85 wt % of the dried rheology modifier composition, and in yet another embodiment most preferably no more than about 80 wt % of the dried rheology modifier composition.
  • the dried rheology modifier composition comprises a mixture of the products of at least two different core-shell copolymer compositions.
  • the dried rheology modifier composition comprises more than one polysaccharide polymer or other spray drying adjuvant.
  • a second composition is added, the second composition comprising a second core-shell polymer and optionally a second polysaccharide polymer or other spray drying adjuvant, wherein each of the second core-shell polymer and the optional second polysaccharide polymer or other spray drying adjuvant of the second composition can be the same as or different from the at least one core-shell polymer and at least one polysaccharide polymer, respectively, of the initial polymer blend
  • the particle size of the solid product may be adjusted using methods known in the art such as milling. Spray-Drying Adjuvant Polymers
  • the rheology modifiers as disclosed herein can be blended with a spray drying adjuvant polymer before being spray dried.
  • Suitable spray drying adjuvant polymers include polysaccharide polymers, which includes without limitation starch and starch derivatives, cellulose and cellulose derivatives, and gums; and polyvinyl acetate derivatives.
  • Polysaccharides useful as spray drying adjuvant polymers can be derived from plant, animal and microbial sources.
  • examples of such polysaccharides include starch, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin, carrageenan, inulin and gellan, and derivatives of each of the foregoing.
  • the polysaccharides may need to depolymerized or derivatized to be water soluble.
  • a starch may need to be depolymerized to a molecular weight of 10 million or less to be water soluble.
  • a cellulose may have to be derivatized, for example to a carboxymethyl cellulose, to be water soluble.
  • the weight average molecular weight of the polysaccharide based spray drying adjuvant polymers can be about 20,000,000 or less, or 10,000,000 or less, or about 1 ,000,000 or less, or about 100,000 or less, or about 10,000 or less.
  • Starches include those derived from maize and conventional hybrids of maize, such as waxy maize and high amylose (greater than 40% amylose) maize, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth, including conventional hybrids or genetically engineered materials.
  • the starches can be of the native variety or a hybrid variety produced by traditional breeding programs or by artificial gene manipulation. These hybrids include but are not limited to waxy versions (starches with little or no amylose) and high amylose cultivars. Waxy starches are typically defined as having about 5% or less amylose and sometime containing about 2% or less amylose.
  • the waxy starches have about 95% or greater amylopectin.
  • High amylose starches are defined as having about 40% or greater amylose (with the exception of pea starch which has a high amylose content of about 27% or greater amylose).
  • the high amylose starches have an amylose content of about 60% or greater amylose.
  • starches which have altered chain length and branch points are included in this application.
  • the preferred polysaccharides are starches and starch derivatives, including, but not limited, to thermal and/or mechanically treated starch, oxidatively, hydrolytically or enzymatically degraded starches, and chemically modified starches.
  • These preferred polysaccharides include maltodextrins, dextrin, pyrodextrins, oxidized starches, cyclodextrins and substituted cyclodextrins and higher molecular weight starches or derivatives thereof.
  • the preferred starches are waxy maltodextrins, waxy dextrins, waxy pyrodextrins, waxy oxidized starches, and higher molecular weight waxy starches or derivatives thereof.
  • the most preferred starches are waxy maltodextrins.
  • Chemical modification includes hydrolysis by the action of acids, enzymes, oxidizers or heat, esterification or etherification.
  • the chemically modified starches, after undergoing chemical modification may be cationic, anionic, non-ionic or amphoteric or hydrophobically modified.
  • the polysaccharide is a maltodextrin.
  • Maltodextrins are polymers having d-glucose units linked primarily by a-1 ,4 bonds and a dextrose equivalent (‘DE’) of about 20 or less.
  • Dextrose equivalent is a measure of the extent of starch hydrolysis. It is determined by measuring the amount of reducing sugars in a sample relative to dextrose (glucose). The DE of dextrose is 100, representing 100% hydrolysis. The DE value gives the extent of hydrolysis (e.g., 10 DE is more hydrolyzed than 5 DE maltodextrin).
  • Maltodextrins are available as a white powder or concentrated solution and are prepared by the partial hydrolysis of starch with acid and/or enzymes.
  • Suitable polysaccharides can further include corn syrups.
  • Corn syrups are defined as degraded starch products having a DE of 27 to 95.
  • specialty corn syrups include high fructose corn syrup and high maltose corn syrup.
  • monosaccharides and oligosaccharides such as galactose, mannose, sucrose, maltose, fructose, ribose, trehalose, lactose, etc., can be used as spray drying adjuvants in the disclosed compositions and methods, and for purposes hereof are considered to fall within the scope of spray drying adjuvant polymers.
  • the polysaccharide has a DE of about 65 or less, 45 or less, 20 or less, in another embodiment a DE of about 15 or less and in still another embodiment a DE of about 5 or less. In an embodiment, the polysaccharide has a DE with a range having a lower limit of at least about 1.
  • the polysaccharides are pregelatinized starch and its derivatives.
  • the pregelatinized starches suitable herein are those starches that have been treated with heat, moisture, or chemicals to disrupt the natural granular structure and render the starch soluble in water at below the gelatinization temperature of the native starch.
  • pregelatinized starches are also referred to as cold water soluble starches (CWS) and the terms are used interchangeably.
  • CWS cold water soluble starches
  • the starches suitable for use herein can further be modified to contain anionic, cationic, non-ionic and reactive groups. Derivatives of these types are described in“Modified Starches: Properties and Uses” O.B. Wurzburg, CRC Press Boca Raton, Florida, 1986 chapters 3-9.
  • the modified starches can be prepared in the granular form and then made cold water soluble or can be cooked before being reacted in solution to produce the polymers.
  • the polysaccharides are celluloses and/or their derivatives such as carboxymethyl cellulose (CMC), hydroxethyl cellulose (HEC), carboxymethyl hydroxethyl cellulose (CMHEC), hydroxypropyl cellulose, sulfoethyl cellulose and its derivatives, ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl celluloses HM-EHEC some of which are available from AkzoNobel.
  • CMC carboxymethyl cellulose
  • HEC hydroxethyl cellulose
  • CHEC carboxymethyl hydroxethyl cellulose
  • CHEC carboxymethyl hydroxethyl cellulose
  • MEHEC methyl ethyl hydroxyethyl cellulose
  • Polysaccharides also include cellulosic derivatives, including plant heteropolysaccharides commonly known as hemicelluloses which are by-products of the paper and pulp industry. Hemicelluloses include xylans, glucuronoxylans, arabinoxylans, glucomannans, and xyloglucans. Xylans are the most common heteropolysaccharide and are preferred. Polysaccharides such as
  • the preferred cellulosic materials are carboxymethyl cellulose (CMC), hydroxethyl cellulose (HEC), carboxymethyl hydroxethyl cellulose (CMHEC), hydroxypropyl cellulose, ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxy ethyl celluloses (HM-EHEC).
  • CMC carboxymethyl cellulose
  • HEC hydroxethyl cellulose
  • CHEC carboxymethyl hydroxethyl cellulose
  • CHEC carboxymethyl hydroxethyl cellulose
  • EHEC hydroxypropyl cellulose
  • EHEC ethyl hydroxyethyl cellulose
  • MEHEC methyl ethyl hydroxyethyl cellulose
  • HM-EHEC hydrophobically modified ethyl hydroxy ethyl celluloses
  • Suitable polysaccharides include guar, unwashed guar gum, washed guar gum, cationic guar, carboxymethyl guar (CM guar), hydroxyethyl guar (HE guar),
  • hydroxypropyl guar HP guar
  • carboxymethylhydroxypropyl guar CMHP guar
  • hydrophobically modified guar HM guar
  • hydrophobically modified carboxymethyl guar HMCM guar
  • hydrophobically modified hydroxyethyl guar HMHE guar
  • hydrophobically modified hydroxypropyl guar HMHP guar
  • cationic hydrophobically modified hydroxypropyl guar cationic HMHP guar
  • hydrophobically modified carboxymethylhydroxypropyl guar HMCMHP guar
  • hydrophobically modified cationic guar HM cationic guar
  • guar hydroxypropyl triammonium chloride hydroxypropyl guar hydroxypropyl triammonium chloride.
  • Suitable polyvinyl acetate and derivatives thereof include polyvinyl alcohol, copolymers of polyvinyl alcohol/polyvinyl acetate and copolymers of vinyl acetate and graft copolymers of polyvinyl alcohol/polyvinyl acetate, and polyvinyl pyrollidones.
  • the derivatives of polyvinyl acetate can be anionic such as copolymers with anionic ethylenically unsaturated monomers or non-ionic such as copolymers with non-ionic ethylenically unsaturated monomers.
  • the polyvinyl acetate derivatives may be completely or partially saponified and/or modified polyvinyl alcohols with a degree of hydrolysis of preferably approximately 70 to 100 mol%, in particular approximately 80 to 98 mol%, and a Hoppler viscosity in 4% aqueous solution of preferably 1 to 50 mPas, in particular of approximately 3 to 40 mPas (measured at 20°C. according to DIN 53015).
  • the weight average molecular weight of the polyvinyl acetate based polymers can be about 1 ,000,000 or less or 500,000 or less, or about 100,000 or less if it is reacted to form the dried emulsion rheology modifier.
  • the weight average molecular weight of the polyvinyl acetate based polymers can be about 100,000 or less, or about 50,000 or less, or about 10,000 or less.
  • the protective water soluble polymers are selected from polyvinyl pyrrolidone and derivatives.
  • the preferred polyvinyl pyrrolidones are homopolymers but copolymers may be used.
  • the polymer may have any molecular weight as long as the rheology modifer remains effective.
  • polyvinylpyrrolidone it may be specifically PVP K- 15 (10,000 in average molecular weight), K-30 (40,000 in average molecular weight), or K-90 (360,000 in average molecular weight) manufactured by Ashland.
  • Weight average molecular weight of spray drying adjuvant polymers that are starches can be determined by the following procedure:
  • Starch samples were prepared at 2.00 mg/ml in 0.03M NaCI in dimethylsulfoxide (DMSO). The starch sample solutions were heated at 100°C for 60 minutes and were clear after heating. The solutions were filtered using a 0.45 micron filter. The molecular weight was measured using gel permeation chromatography with multi-angle light scattering (“GPC/MALS”) detection as follows:
  • Dried rheology modifier compositions disclosed herein may comprise an anti-caking agent.
  • anticaking agents include but are not limited to kaolin,
  • anticaking agents are preferably in the range of from 100 nm to 10 pm. More than one anticaking agent may be used.
  • the core-shell polymers are first prepared as described above.
  • the spray drying adjuvant polymer such as a starch can be present during the polymerization process.
  • the spray drying adjuvant polymer can added to the prepared core-shell emulsion composition.
  • the core-shell polymer composition can be diluted before the spray drying adjuvant polymer is added.
  • an aqueous composition of the spray drying adjuvant polymer is added to the core-shell polymer composition with a suitable amount of mixing.
  • the core-shell polymer composition can be added to an aqueous composition of the spray drying adjuvant polymer.
  • a dry spray drying adjuvant polymer is added to the core-shell polymer composition with concurrent dilution in water.
  • the weight percent of core-shell in the core-shell composition may be in the range of 5-50% and preferably in the range 10-30%.
  • the solids of the aqueous composition of the spray drying adjuvant polymer may be in the range of 5-50% and preferably in the range 10-30%.
  • the solids of the aqueous blend of the core-shell polymer and the spray drying adjuvant polymer may be in the range of 5-50% and preferably in the range 10-30% and most preferably in the range 15-25%.
  • This blend may be dried as is or may be further diluted if necessary before drying.
  • the preferred drying method is spray drying. However, other methods such as drum drying, tray drying, fluidized bed drying etc. may be used.
  • the spray drying adjuvant polymers as described herein will be suitable for use in any of these alternative drying methods.
  • rheology modifier includes the core-shell polymer either in the form of a liquid emulsion or dried to a solid, with or without blended spray drying adjuvant polymer, unless otherwise stated.
  • Product formulations comprising the rheology modifier compositions as disclosed herein may be selected from personal care products, home care products, healthcare products, institutional and industrial care products, adhesives, coatings, agricultural, formulations for use in electronics industries, and formulations for use in construction industries, and other applications.
  • the present application further relates to the use of the rheology modifier compositions as disclosed herein as components of such product formulations along with product formulation active ingredients.
  • home care products includes, without being limited thereto, products employed in a domestic household for surface cleaning or maintaining sanitary conditions, such as in the kitchen and bathroom (e.g., hard surface cleaners, furniture polishes, hand and automatic dish washing formulations, toilet bowl cleaners and disinfectants), and laundry products for fabric care and cleaning (e.g., detergents, fabric conditioners, pre-treatment stain removers), and the like.
  • sanitary conditions such as in the kitchen and bathroom (e.g., hard surface cleaners, furniture polishes, hand and automatic dish washing formulations, toilet bowl cleaners and disinfectants), and laundry products for fabric care and cleaning (e.g., detergents, fabric conditioners, pre-treatment stain removers), and the like.
  • health care products includes, without being limited thereto, pharmaceuticals (controlled release pharmaceuticals), pharmacosmetics, oral care (mouth and teeth) products, such as oral suspensions, mouthwashes, toothpastes, dentifrices, and the like, and over-the-counter products and appliances (topical and transdermal), such as patches, plasters and the like, externally applied to the body, including the skin, scalp, nails and mucous membranes of humans and animals, for ameliorating a health-related or medical condition, for generally maintaining hygiene or well-being, and the like.
  • pharmaceuticals controlled release pharmaceuticals
  • oral care products such as oral suspensions, mouthwashes, toothpastes, dentifrices, and the like
  • over-the-counter products and appliances topical and transdermal
  • l&l includes, without being limited thereto, products employed for surface cleaning or maintaining sanitary conditions in institutional and industrial environments, textile treatments (e.g., textile conditioners, carpet and upholstery cleaners), automobile care (e.g., hand and automatic car wash detergents, tire shines, leather conditioners, liquid car polishes, plastic polishes and conditioners), paints and coatings, and the like.
  • textile treatments e.g., textile conditioners, carpet and upholstery cleaners
  • automobile care e.g., hand and automatic car wash detergents, tire shines, leather conditioners, liquid car polishes, plastic polishes and conditioners
  • paints and coatings e.g., paints and coatings, and the like.
  • the disclosed rheology modifier compositions are useful in agrochemical formulations. They can provide stabilization, thickening, dispersion, or suspension properties to the agrochemical formulations due to their rheological properties.
  • One particularly useful agrochemical formulation is a suspension concentrate (SC).
  • Another particularly useful agrochemical formulation is a solid formulation including wettable powder (WP), water dispersible granule (WDG), and water soluble granule (WSG).
  • WP wettable powder
  • WDG water dispersible granule
  • WSG water soluble granule
  • the disclosed rheology modifier compositions can stabilize or suspend agrochemicals in diluted aqueous systems.
  • the disclosed rheology modifier compositions can be used in formulations used in fracturing operations.
  • Such compositions may be used to stimulate oil wells wherein impeded flow paths lead to an insufficient hydrocarbon production, a technique known as (hydraulic) fracturing and the specialized fluids used in said technique are referred to as fracturing fluids.
  • the compositions are typically injected via the wellbore into the formation at sufficient pressures to create fractures in the formation rocks, thus creating channels through which the hydrocarbons may more readily flow into the wellbore.
  • the fracturing fluids should impart a minimal pressure drop in the pipe within the wellbore during placement and have an adequate viscosity to carry proppant (sand) material that prevents the fracture from closing. Moreover, the fracturing fluids should have a minimal leak-off rate to avoid fluid migration into the formation rocks so that, notably, the fracture can be created and propagated and should degrade so as not to leave residual material that may prevent accurate hydrocarbons to flow into the wellbore.
  • formulations in which the disclosed rheology modifiers can be used include adhesives, asphalt emulsions, paints and coatings, superabsorbents and other industrial applications.
  • the rheology modifiers compositions may be added to these formulations at least about 0.1% modifier by weight of the formulation, more preferably at least about 0.5% modifier by weight of the formulation and most preferably at least about 1.0% modifier by weight of the formulation.
  • the rheology modifiers compositions may be added to these formulations at most about 20% modifier by weight of the formulation, more preferably at most about 15% modifier by weight of the formulation and most preferably at most about 10% modifier by weight of the formulation.
  • the rheology modifiers can be used in aqueous protective coating compositions. These rheology modifiers increase and maintain the viscosity at required levels under specific processing conditions and end-use situations. In particular, the rheology modifiers are useful in all kinds of coatings such as decorative and protective coatings.
  • the rheology modifiers can be used as rheology modifiers for water-based protective coating compositions. Water-based protective coating compositions are commonly known as latex paints or dispersion paints and have been known for a considerable number of years.
  • the polymers as disclosed herein can be used in paper coating applications.
  • a paper coating formulation imparts certain qualities to the paper, including weight, surface gloss, smoothness or reduced ink absorbency.
  • a uniform coating on paper contributes to an enhanced printing surface and properties such as coverage, smoothness, and gloss may be improved.
  • Paper and board grades are sometimes coated to improve the printability, visual properties, or functionality of the sheet.
  • the properties and printability of coated papers are affected by the base sheets (fiber types, sheet formation, internal sizing, and base weight), coating materials (pigment types, binder types, rheology modifiers, water-retention aids, lubricants, defoamers, etc.), coating formulations (ratios of coating components, solids and pH’s), coating process (coating application types and speed), coat weights, drying conditions (dryer types, drying temperature, drying time, and final moisture level), etc.
  • base sheets fiber types, sheet formation, internal sizing, and base weight
  • coating materials pigment types, binder types, rheology modifiers, water-retention aids, lubricants, defoamers, etc.
  • coating formulations ratios of coating components, solids and pH’s
  • coating process coating application types and speed
  • coat weights drying conditions (dryer types, drying temperature, drying time, and final moisture level), etc.
  • Paper coating formulas typically contain three main categories of ingredients:
  • pigments improve printing and optical properties of the sheet
  • binders adhere the pigment particles to each other and to the sheet
  • additives either assist in the coating process or enhance sheet properties.
  • rheology modifiers are used to achieve desired rheological properties as well as improved runnability during the coating process.
  • the rheology modifier compositions disclosed herein especially those that contain acid swellable polymers, uncoil when neutralized in the coating formulation, which increases the viscosity.
  • This viscosity increase helps control pick up rates on applicator rolls, affects flow properties during metering processes and changes immobilization and leveling properties after the metering step in the coating process.
  • the ratio of the hydrophilic to hydrophobic monomers in the polymer affects water retention properties and the degree of interaction with the binder.
  • the molecular weight of the polymer and its branching affect both the low shear and high shear viscosity profile.
  • the rheology modifier compositions which contain a hydrophobically modified acid swellable polymer are also useful in paper coating applications. Such products are highly effective in lightweight coatings (LWC). These products are used in high solids carbonate coatings, which require water retention with minimal high shear viscosity development.
  • LWC lightweight coatings
  • personal care products includes without limitation cosmetics, toiletries, cosmeceuticals, beauty aids, insect repellents, personal hygiene and cleansing products applied to the body, including the skin, hair, scalp, and nails of humans and animals.
  • the personal care applications include, but are not limited to, formulations for hair styling gels, skin creams, sun tan lotions, sunscreens,
  • moisturizers for example, moisturizers, tooth pastes, medical and first aid ointments, cosmetic ointments, suppositories, cleansers, lipstick, mascara, hair dye, cream rinse, shampoos, body soap and deodorants, hair care and styling formulations, shaving preparations, depilatories and hand sanitizers, including alcohol based hand sanitizers.
  • Suitable personal care applications also include formulations for use on the skin, eyelashes or eyebrows, including, without limitation, cosmetic compositions such as mascara, facial foundations, eyeliners, lipsticks, and color products; skin care compositions such as moisturizing lotions and creams, skin treatment products, skin protection products in the form of an emulsion, liquid, stick, or a gel; sun care compositions such as sunscreens, sunscreen emulsions, lotions, creams, sunscreen emulsion sprays, liquid/alcohol sunscreen sprays, sunscreen aqueous gels, broad spectrum sunscreens with UVA and UVB actives, sunscreens with organic and inorganic actives, sunscreens with combinations of organic and inorganic actives, suntan products, self-tanning products, and after sun products etc.
  • cosmetic compositions such as mascara, facial foundations, eyeliners, lipsticks, and color products
  • skin care compositions such as moisturizing lotions and creams, skin treatment products, skin protection products in the form of an emulsion, liquid, stick, or a gel
  • compositions are personal care emulsions, more particularly suitable are sun care compositions such as sunscreen emulsions and sunscreen emulsion sprays.
  • the personal care composition may be in any form, including without limitation in sprays, emulsions, lotions, gels, liquids, sticks, waxes, pastes, powders, and creams.
  • the personal care compositions may also include other optional components commonly used in the industry, and these will vary greatly depending upon the type of composition and the functionality and properties desired. Without limitation, these components include thickeners, suspending agents, emulsifiers, UV filters, sunscreen actives, humectants, moisturizers, emollients, oils, waxes, solvents, chelating agents, vitamins, antioxidants, botanical extracts, silicones, neutralizing agents, preservatives, fragrances, dyes, pigments, conditioners, polymers, antiperspirant active ingredients, antiacne agents, anti-dandruff actives, surfactants, exfoliants, depilatory active ingredients, film formers, propellants, tanning accelerator, hair fixatives and colors.
  • these components include thickeners, suspending agents, emulsifiers, UV filters, sunscreen actives, humectants, moisturizers, emollients, oils, waxes, solvents, chelating agents, vitamins, antioxidants, botanical extract
  • sunscreen compositions may contain at least one component selected from the group comprising organic UV filters, inorganic UV actives, UVA and/or UVB suncreen actives, octinoxate, octisalate, oxybenzone, homosalate, octocrylene, avobenzene, titanium dioxide, starch, conditioning agents, emulsifiers, other rheology modifiers and thickeners, neutralizers, emollients, solvents, film formers, moisturizers, antioxidants, vitamins, chelating agents, preservatives, fragrances, and zinc oxide.
  • Skin care and cosmetic compositions may contain at least one component selected from the group consisting of vitamins, anti-aging agents, moisturizers, emollients, emulsifiers, surfactants, preservatives, pigments, dyes, colors and insect repellents.
  • the personal care, home care, health care, agricultural, and l&l care compositions comprising the staged core-shell polymers can be formulated at pH ranges from about 0.5 to about 12.
  • the desired pH for the compositions will depend upon the specific end product applications. Generally, certain personal care applications have a desired pH range of about 3 to about 7.5 in one aspect, and from about 3.5 to about 6 in another aspect.
  • the staged core-shell/surfactant compositions when formulated at low pH values give a clear formulation while maintaining desirable rheology properties (e.g., viscosity and yield values).
  • the staged core-shell polymer/surfactant compositions when formulated at pH values of about 6 and below give a clear formulation while maintaining desirable rheology properties of the compositions in which they are included.
  • the staged core-shell/surfactant compositions when formulated at pH values of about 5.0 and below give a clear formulation while maintaining desirable rheology properties of the compositions in which they are included.
  • the staged core-shell/surfactant compositions when formulated at pH values of from about 3.5 to about 4.5 give a clear formulation while maintaining desirable rheology properties of the compositions in which they are included.
  • home care applications have a desired pH range of about 1 to about 12 in one aspect, and from about 3 to about 10 in another aspect, depending on the desired end-use application.
  • the pH of the compositions as disclosed herein can be adjusted with any combination of acidic and/or basic pH adjusting agents known to the art.
  • the polymers of this invention are typically supplied in the alkaline pH range.
  • the polymers have to be activated in the formulation by lowering the pH using an acidic material.
  • Various acidic materials can be utilized as a neutralizing agent/pH adjusting agent.
  • Such acidic materials include organic acids and inorganic acids, for example, acetic acid, citric acid, tartaric acid, alpha-hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof.
  • Other acidic materials can be used alone or in combination with the above mentioned inorganic and organic acids.
  • Such materials include materials which when combined in a composition containing the staged core-shell polymer are capable of reducing the pH of the composition.
  • the acidic pH adjusting agents can serve more than one function.
  • acidic preservative compounds and acid based cosmeceutical compounds e.g., alpha- and beta-hydroxy acids
  • acid based cosmeceutical compounds not only serve their primary preservative and cosmeceutical functions, respectively, they can also be utilized to reduce or maintain the pH of a desired formulation.
  • Buffering agents can be used in the disclosed compositions. Suitable buffering agents include, but are not limited to, alkali or alkali earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates, and the like, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate, and sodium carbonate.
  • the pH adjusting agent and/or buffering agent is utilized in any amount necessary to obtain and/or maintain a desired pH value in the composition.
  • the core-shell polymers disclosed herein can be formulated with or without at least one surfactant.
  • Such compositions can comprise any combination of optional additives, adjuvants, and benefit agents suitable for a desired personal care, home care, health care, and institutional and industrial care product known in the art.
  • the choice and amount of each optional component employed will vary with the purpose and character of the end product, and can be readily determined by one skilled in the formulation art and from the literature.
  • additive, adjuvant, and benefit agents and components set forth herein can serve more than one function in a composition, such as, for example, surfactants, emulsifiers, solubilizers, conditioners, emollients, humectants, lubricants, pH adjusting agents, and acid based preservatives.
  • Optional additives and adjuvants include, but are not limited to insoluble materials, pharmaceutical and cosmeceutical actives, chelators, conditioners, diluents, solvents, fragrances, humectants, lubricants, solubilizers, emollients, opacifiers, colorants, anti- dandruff agents, preservatives, spreading aids, emulsifiers, sunscreens, fixative polymers, botanicals, viscosity modifiers, and the like, as well as the numerous other optional components for enhancing and maintaining the properties of a desired personal care, home care, health care, agricultural, and l&l care composition.
  • additives such as active and functional ingredients
  • emollients such as hair care and styling formulations, for example styling gels
  • humectants such as thickening agents
  • electrolytes and salts surfactants such as UV light inhibitors
  • fixative polymers preservatives pigments dyes, colorants, alpha hydroxy acids
  • aesthetic enhancers such as starch perfumes and fragrances
  • film formers water proofing agents
  • conditioning agents can be used in combination with the disclosed polymers, for example, cationic guar gum, cationic hydroxyethyl cellulose, cationic synthetic polymers and cationic fatty amine derivatives. These blended materials help to provide more substantivity and effective conditioning properties in hair.
  • the electrolytes and salts are particularly useful in boosting the viscosity of the shampoo and improving its suspending properties.
  • polyoxythylenated vinyl acetate/croton ic acid copolymers vinyl acetate crotonic acid (90/10) copolymers, vinyl acetate/crotonic acid/vinyl neodecanoate terpolymers, N- octylacrylamide/methylacrylate/hydroxypropyl methacrylate/acrylic acid/tert- butylaminoethyl methacrylate copolymers, and methyl vinyl ether/maleic anhydride (50/50) copolymers monoesterified with butanol or ethanol, acrylic acid/ethyl acrylate/N-tert-butyl-acrylamide terpolymers, and poly (methacrylic
  • acrylates/octylacrylamide copolymer VA/crotonates/vinyl Neodeanoate copolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide), corn starch modified, sodium polystyrene sulfonate, polyquaterniums such as polyquaternium-4, polyquaternium-7, polyquaternium-10, polyquaternium-1 1 , polyquarternium-16, polyquaternium-28, polyquaternium-29, polyquaternium-46, polyether-1 , polyurethanes, VA acrylates/lauryl methacrylate copolymer, adipic acid/dimethylaminohydroxypropyl diethylene
  • PVP/dimethylaminoethylmethacrylate copolymer PVP/DMAPA acrylates copolymer
  • PVP/vinylcaprolactam/DMAPA acrylates copolymer
  • acrylates/octylacrylamide copolymer VA/crotonates/vinyl Neodecanoate copolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide), polyurethane, corn starch modified, sodium polystyrene sulfonate, polyquaternium-4, polyquarternium-10, and
  • Suitable cationic polymers that may be used in formulations comprising the disclosed rheology modifier compositions are those best known with their CTFA category name Polyquaternium.
  • Some examples of this class of polymer are Polyquaternium 6, Polyquaternium 7, Polyquaternium 10, Polyquaternium 11 , Polyquaternium 16, Polyquaternium 22 and Polyquaternium 28, Polyquaternium 4, Polyquaternium 37, Quaternium-8, Quaternium-14, Quaternium-15, Quaternium-18, Quaternium-22, Quaternium-24, Quaternium-26, Quaternium-27, Quaternium-30, Quaternium-33, Quaternium-53, Quaternium-60, Quaternium-61 , Quaternium-72, Quaternium-78, Quaternium-80, Quaternium-81 , Quaternium-82, Quaternium-83 and Quaternium-84.
  • Naturally derived cellulose type polymers known as Polymer JR® type from Amerchol, Polyquaternium 10 or cationic guar gum known with trade name Jaguar® from Rhone- Poulenc, and Guar hydroxypropyl trimonium chloride, chitosan and chitin can also be included in the personal care formulations as cationic natural polymers in formulations comprising the disclosed rheology modifier compositions.
  • the rheology modifiers may be used in personal care compositions that may also include a cosmetically acceptable ingredient.
  • the ingredient can be an emollient, fragrance, exfoliant, medicament, whitening agent, acne treatment agent, a
  • preservative vitamins, proteins, a cleanser or conditioning agent.
  • cleansers suitable for use in compositions herein include, but are not limited to, are sodium lauryl sulfate (SLS), sodium laureth sulfate (SLES), ammonium lauryl ether sulfate (ALES), alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amines, sulfonated amines and amides, betaines, block polymers, carboxylated alcohol or alkylphenol ethoxylates, diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than glycol, glycerol, etc.), fluorocarbon-based surfactants, glycerol esters, glycol esters
  • the formulation further comprises a sulfate free surfactant.
  • sulfate free surfactants include, but are not limited to, ethoxylated alkylphenols, ethoxylated amines and/or amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (other than glycol, glycerol, etc.), fluorocarbon-based surfactants, glycerol esters, glycol esters, heterocyclics, imidazolines and imidazoline derivatives, isethionates, lanolin-based derivatives, lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters,
  • the sulfate free surfactants are sulfonates or ethoxylates.
  • the formulation contains sulfated surfactants.
  • sulfated surfactants are sodium lauryl sulfate (SLS), sodium laureth sulfate (SLES), alkanolamides, alkylaryl sulfonic acids, sulfates of oils and fatty acids, sulfates of ethoxylated alkyl phenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfosuccinamates, sulfosuccinates and derivatives thereof.
  • SLS sodium lauryl sulfate
  • SLES sodium laureth sulfate
  • alkanolamides alkylaryl sulfonic acids
  • sulfates of oils and fatty acids sulfates of ethoxylated
  • the personal care formulation comprising the disclosed rheology modifier is a hair fixative or styling formulation, such as a hair gel, mousse, spray, pomade, wax, or styling lotion.
  • a hair fixative or styling formulation such as a hair gel, mousse, spray, pomade, wax, or styling lotion.
  • compositions may optionally include other ingredients.
  • these ingredients include, but are not limited to, conditioning agents such as silicone oils, either volatile or non-volatile, natural and synthetic oils.
  • conditioning agents such as silicone oils, either volatile or non-volatile, natural and synthetic oils.
  • Suitable silicone oils that can be added to the compositions include dimethicone, dimethiconol, polydimethylsiloxane, silicone oils with various DC fluid ranges from Dow Corning.
  • Suitable natural oils such as olive oil, almond oil, avocado oil, wheatgerm oil, ricinus oil and the synthetic oils, such as mineral oil, isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate and oleyl erucate can also be used.
  • synthetic oils such as mineral oil, isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate and oleyl erucate can also be used.
  • non-ionic conditioning agents are polyols such as glycerin, glycol and derivatives, polyethyleneglycols, which may be known by the trade names Carbowax® PEG from Union Carbide and Polyox® WSR range from Amerchol, polyglycerin, polyethyleneglycol mono- or di- fatty acid esters.
  • Preservatives can be used in personal care formulations to provide long term shelf stability. These can be selected from among methylparaben, propylparaben, butylparaben, DMDM hydantoin, imidazolidinyl urea, gluteraldehyde, phenoxyethanol, benzalkonium chloride, methane ammonium chloride, benzethonium chloride, benzyl alcohol, chlorobenzyl alcohol, methylchloroisothiazolinone, methylisothiazolinone, sodium benzoate, chloracetamide, triclosan, iodopropynyl butylcarbamate, sodium pyrithione, and zinc pyrithione.
  • the rheology modifier compositions as disclosed herein can also be used in liquid detergent compositions that include one or more surfactants, such as those selected from anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants.
  • the preferred surfactants are suitable for use in isotropic liquid detergent compositions and are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants.
  • Liquid detergent compositions comprising the disclosed rheology modifier compositions may also be used in liquid detergent compositions and may further optionally comprise at least one additive.
  • Suitable additives may include, for example, builders,
  • dispersants polymers, ion exchangers, alkalis, anticorrosion materials, antiredeposition materials, antistatic agents, optical brighteners, perfumes, fragrances, dyes, fillers, oils, chelating agents, enzymes, fabric whiteners, brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, soil removal agents, soil release agents, fabric softening agents, and opacifiers.
  • such additives and their amounts are known to those skilled in the art.
  • stable aqueous compositions comprise a staged core-shell rheology modifier as disclosed herein and a surfactant(s).
  • Suitable surfactants include anionic, cationic, amphoteric, and nonionic surfactants, as well as mixtures thereof.
  • Such compositions are useful, for example, in personal care cleansing compositions that contain various components such as substantially insoluble materials requiring suspension or stabilization (e.g., a silicone, an oily material, a pearlescent material, aesthetic and cosmeceutical beads and particles, gaseous bubbles, exfoliants, and the like).
  • the anionic surfactant can be any of the anionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable anionic surfactants include but are not limited to alkyl sulfates, alkyl ether sulfates, alkyl sulphonates, alkaryl sulfonates, a-olefin-sulphonates, alkylamide sulphonates, alkarylpolyether sulphates, alkylamidoether sulphates, alkyl monoglyceryl ether sulfates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl ether sulphosuccinates, alkyl amidosulfosuccinates; alkyl sulphoacetates, alkyl phosphate
  • the cation moiety of the forgoing salts is selected from sodium, potassium, magnesium, ammonium, mono-, di- and triethanolamine salts, and mono-, di-, and tri-isopropylamine salts.
  • the alkyl and acyl groups of the foregoing surfactants contain from about 6 to about 24 carbon atoms in one aspect, from 8 to 22 carbon atoms in another aspect and from about 12 to 18 carbon atoms in a further aspect and may be unsaturated.
  • the aryl groups in the surfactants are selected from phenyl or benzyl.
  • the ether containing surfactants set forth above can contain from 1 to 10 ethylene oxide and/or propylene oxide units per surfactant molecule in one aspect, and from 1 to 3 ethylene oxide units per surfactant molecule in another aspect.
  • anionic surfactants include sodium, potassium, lithium, magnesium, and ammonium salts of laureth sulfate, trideceth sulfate, myreth sulfate, Ci2-Ci 3 pareth sulfate, C12-C14 pareth sulfate, and Ci 2 -Ci 5 pareth sulfate, ethoxylated with 1 , 2, and 3 moles of ethylene oxide; sodium, potassium, lithium, magnesium, ammonium, and triethanolamine lauryl sulfate, coco sulfate, tridecyl sulfate, myrstyl sulfate, cetyl sulfate, cetearyl sulfate, stearyl sulfate, oleyl sulfate, and tallow sulfate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, sodium cocoyl iseth
  • the cationic surfactants can be any of the cationic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable classes of cationic surfactants include but are not limited to alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds, and quaternized esters. In addition, alkyl amine oxides can function as a cationic surfactant at a low pH.
  • Alkylamine surfactants can be salts of primary, secondary and tertiary fatty C12-C22 alkylamines, substituted or unsubstituted, and substances sometimes referred to as “amidoamines”.
  • alkylamines and salts thereof include dimethyl cocamine, dimethyl palmitamine, dioctylamine, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N- tallowpropane diamine, ethoxylated stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, dimethyl lauramine, stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride, and
  • amodimethicone (INCI name for a silicone polymer and blocked with amino functional groups, such as aminoethylamino propylsiloxane).
  • amidoamines and salts thereof include stearamido propyl dimethyl amine, stearamidopropyl dimethylamine citrate, palmitamidopropyl
  • alkyl imidazoline surfactants include alkyl hydroxyethyl imidazoline, such as stearyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.
  • Non-limiting examples of ethyoxylated amines include PEG-cocopolyamine, PEG-15 tallow amine, quaternium-52, and the like.
  • R 5 R 6 R 7 R 8 N + ) E wherein R 5 , R 6 , R 7 , and R 8 are independently selected from an aliphatic group having from 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having 1 to about 22 carbon atoms in the alkyl chain; and E is a salt-forming anion such as those selected from halogen, (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate.
  • halogen e.g., chloride, bromide
  • the aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, ester linkages, and other groups such as amino groups.
  • the longer chain aliphatic groups e.g., those of about 12 carbons, or higher, can be saturated or unsaturated.
  • the aryl groups are selected from phenyl and benzyl.
  • Exemplary quaternary ammonium surfactants include, but are not limited to cetyl trimethylammonium chloride, cetylpyridinium chloride, dicetyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, behenyl trimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride, and di(coconutalkyl)dimethyl ammonium chloride, ditallowedimethyl ammonium chloride, dehydrogenated tallow)dimethyl ammonium chloride, dehydrogenated tallow)dimethyl ammonium acetate,
  • amine oxides can protonate and behave similarly to N-alkyl amines.
  • Examples include, but are not limited to, dimethyl-dodecylamine oxide, oleyldi(2- hydroxyethyl)amine oxide, dimethyltetradecylamine oxide, di(2-hydroxyethyl)- tetradecylamine oxide, dimethylhexadecylamine oxide, behenamine oxide, cocamine oxide, decyltetradecylamine oxide, dihydroxyethyl C12-15 alkoxypropylamine oxide, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, dihydroxyethyl tallowamine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallowamine oxide, hydroxyethyl hydroxypropyl C 12 -C 15 alkoxypropylamine oxide, lauramine oxide, myristamine oxide, cetylamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3
  • Amphoteric or zwitterionic surfactants are molecules that contain acidic and basic moieties and have the capacity of behaving either as an acid or a base.
  • Suitable surfactants can be any of the amphoteric surfactants known or previously used in the art of aqueous surfactant compositions.
  • Exemplary amphoteric surfactant classes include but are not limited to amino acids (e.g., N-alkyl amino acids and N-acyl amino acids), betaines, sultaines, and alkyl amphocarboxylates.
  • Suitable amino acid based surfactants include surfactants represented by the formula:
  • R 10 represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or an acyl group containing a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms
  • Y is hydrogen or methyl
  • Z is selected from hydrogen,— CH 3 ,— CH(CH 3 ) 2 ,— CH 2 CH(CH 3 ) 2 ,— CH(CH 3 )CH 2 CH 3 ,— CH 2 C 6 H 5:
  • R 10 represents a radical selected from a linear or branched Ci 0 to C 22 alkyl group, a linear or branched Ci 0 to C 22 alkenyl group, an acyl group represented by R 11 C(0)— , wherein R 11 is selected from a linear or branched C 9 to C 22 alkyl group, a linear or branched C 9 to C 22 alkenyl group.
  • M + is selected from sodium, potassium, ammonium, and triethanolamine (TEA).
  • the amino acid surfactants can be derived from the alkylation and acylation of oamino acids such as, for example, alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, and valine.
  • oamino acids such as, for example, alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, and valine.
  • N-acyl amino acid surfactants are, but not limited to the mono- and di-carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated glutamic acid, for example, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, and potassium myristoyl glutamate; the carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated alanine, for example, sodium cocoyl alaninate, and TEA lauroyl alaninate; the carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated glycine, for example, sodium coco
  • betaines and sultaines useful in the disclosed compositions are selected from alkyl betaines, alkylamino betaines, and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the formulas:
  • R 12 is a C7-C22 alkyl or alkenyl group
  • each R 13 independently is a C1-C4 alkyl group
  • R 14 is a C1-C5 alkylene group or a hydroxy substituted C1-C5 alkylene group
  • n is an integer from 2 to 6
  • A is a carboxylate or sulfonate group
  • M is a salt forming cation.
  • R 12 is a Cn-Ci 8 alkyl group or a Cn-Ci 8 alkenyl group.
  • R 13 is methyl.
  • R 14 is methylene, ethylene or hydroxy propylene.
  • n is 3.
  • M is selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine cations.
  • betaines include, but are not limited to, lauryl betaine, coco betaine, oleyl betaine, cocohexadecyl dimethylbetaine, lauryl amidopropyl betaine, cocoamidopropyl betaine, and cocamidopropyl hydroxysultaine.
  • alkylamphocarboxylates such as the alkylamphoacetates and
  • alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula: wherein R 12 is a C7-C22 alkyl or alkenyl group, R 15 is— CH 2 C(0)0 M + ,— CH 2 CH 2 C(0)0 M + , or— CH 2 CH(0H)CH 2 S0 3 M + , R 16 is a hydrogen or— CH 2 C(0)0 M + , and M is a cation selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine.
  • alkylamphocarboxylates include, but are not limited to, sodium
  • cocoamphoacetate sodium lauroamphoacetate, sodium capryloamphoacetate, disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium
  • caprylamphodiacetate disodium capryloamphodiacetate, disodium
  • cocoamphodipropionate disodium lauroamphodipropionate, disodium
  • caprylamphodipropionate and disodium capryloamphodipropionate.
  • the nonionic surfactant can be any of the nonionic surfactants known or previously used in the art of aqueous surfactant compositions.
  • Suitable nonionic surfactants include, but are not limited to, aliphatic (C 6 -Ci 8 ) primary or secondary linear or branched chain acids, alcohols or phenols; alkyl ethoxylates; alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy moieties); block alkylene oxide condensates of alkyl phenols; alkylene oxide condensates of alkanols; and ethylene oxide/propylene oxide block copolymers.
  • nonionic surfactants include mono- or dialkyl alkanolamides; alkyl polyglucosides (APGs); sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; polyoxyethylene sorbitol esters;
  • nonionic surfactants include coco mono- or diethanolamide, coco glucoside, decyl diglucoside, lauryl diglucoside, coco diglucoside, polysorbate 20, 40, 60, and 80, ethoxylated linear alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG-100 stearate, laureth 7, and oleth 20.
  • non-ionic surfactants include, but are not limited to,
  • alkoxylated methyl glucosides such as, for example, methyl gluceth-1 0, methyl gluceth- 20, PPG-10 methyl glucose ether, and PPG-20 methyl glucose ether, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucam® E10, Glucam®
  • hydrophobically modified alkoxylated methyl glucosides such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate, and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate® DOE-120, GlucamateTM LT, and GlucamateTM SSE-20, respectively, are also suitable.
  • Other exemplary hydrophobically modified alkoxylated methyl glucosides are disclosed in U.S. Pat. Nos. 6,573,375 and 6,727,357, the disclosures of which are hereby incorporated by reference in their entirety.
  • surfactants which can be utilized in the disclosed compositions are set forth in more detail in WO 99/21530, U.S. Pat. No. 3,929,678, U.S. Pat. No. 4,565,647, U.S.
  • the amounts of the surfactant utilized in a composition comprising the disclosed staged core-shell polymer can vary widely depending on a desired application, the amounts which are often utilized generally range from about 1% to about 80% by weight in one aspect, from about 3% to about 65% weight in another aspect, from about 5% to about 30% by weight in a still another aspect, from about 6% to about 20% by weight in a further aspect, and from about 8% to about 16% by weight, based upon the total weight of the personal care, home care, health care, and institutional and industrial care composition in which it is included.
  • the personal care, home care, health care, agricultural and l&l care compositions disclosed herein comprise a staged core-shell polymer in combination with at least one anionic surfactant.
  • the compositions comprise a staged core-shell polymer with at least one anionic surfactant and at least one amphoteric surfactant.
  • the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl sulphonates, alkaryl sulfonates, alkarylpolyether sulphates, and mixtures thereof wherein the alkyl group contains 10 to 18 carbon atoms, the aryl group is a phenyl, and the ether group contains 1 to 10 moles of ethylene oxide.
  • Representative anionic surfactants include, but are not limited to, sodium and ammonium lauryl ether sulfate (ethoxylated with 1 , 2, and 3 moles of ethylene oxide), sodium, ammonium, and triethanolamine lauryl sulfate.
  • amphoteric surfactant is selected from an alkyl betaine, an alkylamino betaine, an alkylamido betaines, and mixtures thereof.
  • Representative betaines include but are not limited to lauryl betaine, coco betaine, cocohexadecyl dimethylbetaine, cocoamidopropyl betaine, cocoamidopropylhyrdoxy sultaine, and mixtures thereof.
  • TMPTA trimethylolpropane triacrylate (from Alfa Aesar)
  • the core polymers and the shell polymers are made of ethyl acrylate, N,N-dimethylaminoethyl methacrylate, and cetyl 20 EO itaconate in a mole ratio of 71.6/27.8/0.6.
  • crosslinker is used in the shell, the mole% is reported as based on the total moles of ethyl acrylate and N,N- dimethylaminoethyl methacrylate and cetyl 20 EO itaconate without including the moles of crosslinker.
  • Example 1 20/80 core/shell (wt%); 0.15 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.82 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of Polystep® TD 507 nonionic surfactant (Stepan Company) and 8.30 grams of 5% sodium hydroxide were added to the reactor.
  • Example 2 20/80 core/shell (wt%); 0.05 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.91 grams of 41 % sodium bisulfite and 37.36 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 24 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes.
  • Example 3 80/20 core/shell (wt%); 0.15 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.82 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 96 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 25.2 grams ethyl acrylate (0.252 moles), 2.56 grams of cetyl 20 EO itaconate associative monomer (0.002 moles) and 0.1214 grams of TMPTA (0.0005 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 15.4 grams DMAEMA (0.098 moles) and 2.3 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 24 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7887 grams of sodium persulfate and 23.98 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 20.5% solids at a pH of 8.23.
  • Example 4 80/20 core/shell (wt%); 1.15 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.82 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • Example 5 70/30 core/shell (wt%); 0.15 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.81 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.57 grams of
  • a monomer mixture of 88.3 grams of ethyl acrylate (0.882 moles) and 8.97 grams of cetyl 20 EO itaconate associative monomer (0.007 moles) was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 53.8 grams of DMAEMA (0.342 moles) and 8.16 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed. Next, initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 1.3224 grams of sodium persulfate and 41.36 grams of water.
  • Initiator B was prepared using 3.91 grams of 41 % sodium bisulfite and 37.32 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 84 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 37.9 grams ethyl acrylate (0.378 moles), 3.85 grams of cetyl 20 EO itaconate associative monomer (0.003 moles) and 0.1916 grams of TMPTA (0.0006 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 6 70/30 core/shell (wt%); 1.15 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.84 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • a monomer mixture of 88.3 grams of ethyl acrylate (0.882 moles) and 8.97 grams of cetyl 20 EO itaconate associative monomer (0.007 moles) was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 53.8 grams of DMAEMA (0.342 moles) and 8.16 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed. Next, initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 1.3210 grams of sodium persulfate and 41.32 grams of water.
  • Initiator B was prepared using 3.92 grams of 41 % sodium bisulfite and 37.40 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 84 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes.
  • Example 7 85/15 core/shell (wt%); 2.8 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.81 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 102 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 18.9 grams ethyl acrylate (0.189 moles), 1.92 grams of cetyl 20 EO itaconate associative monomer (0.002 moles) and 2.1818 grams of TMPTA (0.007 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 11.5 grams DMAEMA (0.073 moles) and 1.78 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 18 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7914 grams of sodium persulfate and 23.96 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 20.6% solids at a pH of 8.13.
  • Example 8 90/10 core/shell (wt%); 2.8 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.92 grams of 41 % sodium bisulfite and 37.34 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4487 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7919 grams of sodium persulfate and 23.98 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 20.5% solids at a pH of 8.17.
  • Example 9 95/5 core/shell (wt%); 2.8 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 617.62 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 9.92 grams of Polystep® TD 507 and 7.78 grams of 5% sodium hydroxide were added to the reactor.
  • Example 10 95/5 core/shell (wt%); 5.6 mol% crosslinker in shell
  • a 1 liter reactor vessel was charged with 617.64 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 9.93 grams of Polystep® TD 507 and 7.79 grams of 5% sodium hydroxide were added to the reactor. A monomer mixture of 112.4 grams of ethyl acrylate (1.123 moles) and 11.41 grams of cetyl 20 EO itaconate associative monomer (0.009 moles) was added to the reactor at 20 ml/min using sub surface feed.
  • Initiator B was prepared using 3.68 grams of 41 % sodium bisulfite and 35.02 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 1 14 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes.
  • Example 12 Comparative example - no core-shell, no cross-linker
  • a 1 liter reactor vessel was charged with 658.82 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Example 13 Evaluation of viscosity, clarity, and suspension 1.75 wt. % active polymer in body wash formulation.
  • surfactant based formulation 200 grams was prepared by adding 16.83 grams of polymer emulsion (3.5 grams active polymer) of the Examples as indicated to 59.77 grams of Deionized water in a 250 ml beaker. A small 1 1 ⁇ 2 inch jiffy mixer blade was inserted into the beaker and attached to an overhead mixer. The batch was allowed to mix with a vortex extending to the middle of the beaker. This was followed by adding 100 grams of Sodium Laureth Sulfate (25.2% active Standapol ES-2 from BASF). This was allowed to mix for 15 minutes. Then, 14.8 grams of Cocamidopropyl Betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for another 15 minutes.
  • Example 14 Evaluation of viscosity and clarity, 1.0 wt. % active polymer in body wash formulation.
  • Typical surfactant based formulation was prepared by adding 9.71 grams of polymer (2.0 grams active polymer) to 68.89 grams of Deionized water in a 250 ml beaker. A small 1 1 ⁇ 2 inch jiffy mixer blade was inserted into the beaker and attached to an overhead mixer. The batch was allowed to mix with a vortex extending to the middle of the beaker. This was followed by adding 100 grams of Sodium Laureth Sulfate (25.2% active Standapol ES-2 from BASF). This was allowed to mix for 15 minutes. Then, 14.8 grams of Cocamidopropyl Betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for another 15 minutes.
  • Example 15 Evaluation of viscosity and clarity, 1.4 wt. % active polymer in body wash formulation.
  • Example 16 Evaluation of viscosity, clarity, and suspension, 3.0 wt. % active polymer in body wash formulation.
  • 200 grams of typical body wash formulation was prepared by adding 48.16 grams of polymer (6 grams active polymer) to 28.44 grams of Deionized water in a 250 ml beaker. A small 1 1 ⁇ 2 inch jiffy mixer blade was inserted into the beaker and attached to an overhead mixer. The batch was allowed to mix with a vortex extending to the middle of the beaker. This was followed by adding 100 grams of Sodium Laureth Sulfate (25.2% active Standapol ES-2 from BASF). This was allowed to mix for 15 minutes. Then,
  • Example 17 Evaluation of viscosity, clarity and suspension, 1.5 wt. % active polymer in body wash formulation.
  • Example 18 Evaluation of viscosity, clarity, and suspension, 2 wt. % active polymer in body wash formulation
  • the solid pesticides (Tebuconazole, Azoxystrobin, Diuron) is first wet-milled in a bead milling machine (Eiger Torrance MiniMoto 250) to a particle size of ⁇ 5 micrometers.
  • compositions of the milled samples are shown in the weight % indicated in Table 8.
  • the milled samples are used as the bases of the suspension concentrates.
  • Two suspension concentrates are prepared by adding a polymer of the invention to the milled samples MS-1 and MS-2 with stirring and adjusting the sample to a pH of about 4.5. Additional water is added to the milled sample.
  • the amounts of each component are listed in Table 9. Table 9
  • Example 22 50 wt. % starch and 90/10 core/shell (wt. %); 2.8 mole % crosslinker in shell
  • a 1 liter reactor vessel was charged with 579.60 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. When the temperature reached 35°C, 83.24 grams of Star DRI 10, (DE 10 maltodextrin from Tate & Lyle) and 140.00 grams of water were added to the reactor vessel using a funnel. When the temperature reached 65.6°C, the sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 3.72 grams of Polystep® TD 507 and 0.79 grams of
  • a monomer mixture of 39.8 grams of ethyl acrylate (0.397 moles) and 3.42 grams of cetyl 20 EO itaconate associative monomer (0.003 moles) was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 24.2 grams of DMAEMA (0.154 moles) and 3.67 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed. Next, initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 0.4661 grams of sodium persulfate and 42.01 grams of water. Initiator B was prepared using 1.36 grams of 41 % sodium bisulfite and 42.00 grams of water.
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 4.4 grams ethyl acrylate (0.044 moles), 0.40 grams of cetyl 20 EO itaconate associative monomer (0.0003 moles) and 0.5098 grams of TMPTA (0.002 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 2.7 grams DMAEMA (0.049 moles) and 0.41 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 12 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.2927 grams of sodium persulfate and 14.02 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 15.2% solids at a pH of 8.25.
  • Example 23 90/10 core/shell (wt%); 2.8 mol% EGDMA (ethylene glycol
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub-surface sparged with nitrogen. The sub-surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.92 grams of 41% sodium bisulfite and 37.34 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.00874487 grams of Ethylene glycol dimethacrylate from Sartomer 206 (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 24- 90/10 core/shell (wt. %); 2.8 mol. % of Komerate-T093 (TMP(EO)9TA ) as crosslinker in shell
  • a 1 -liter reactor vessel was charged with 658.85 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • Initiator B was prepared using 3.95 grams of 41% sodium bisulfite and 37.33 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.29 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 3.5124 grams of Komerate-T093 (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 25 10/90 core/shell (wt%); 0.15 mol% of crosslinker in the shell
  • a 1 liter reactor vessel was charged with 658.86 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 12 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 1 13.6 grams ethyl acrylate (1.136 moles), 1 1.57 grams of cetyl 20 EO itaconate associative monomer (0.009 moles) and 0.704 grams of TMPTA (0.002 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 69.1 grams DMAEMA (0.44 moles) and 10.51 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 108 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7925 grams of sodium persulfate and 23.99 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.3% solids at a pH of 8.33.
  • a 1 liter reactor vessel was charged with 658.85 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.57 grams of
  • a monomer mixture of 113.7 grams of ethyl acrylate (1.134 moles), 1 1.51 grams of cetyl 20 EO itaconate associative monomer (0.009 moles) and 0.2612 (0.0009 moles) grams of TMPTA was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 69.2 grams of DMAEMA (0.44 moles) and 10.51 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed. Next, initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 1.3208 grams of sodium persulfate and 41.29 grams of water.
  • Initiator B was prepared using 3.91 grams of 41 % sodium bisulfite and 37.36 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.26 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4490 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 27 90/10 core/shell (wt.%); 2.8 mol.% crosslinker in the shell and C22 with 25 moles EO itaconate associative monomer
  • a 1 liter reactor vessel was charged with 658.86 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.60 grams of
  • Initiator B was prepared using 3.90 grams of 41% sodium bisulfite and 37.31 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 12 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.65 grams of C22 with 25 moles EO itaconate associative monomer (0.001 moles) and 1.4479 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 28 90/10 core/shell (wt.%); 2.8 mol% crosslinker in the shell and C22 with 20 moles EO itaconate associative monomer
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.92 grams of 41% sodium bisulfite and 37.34 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 12 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.4828 grams of C22 with 20 moles EO itaconate associative monomer (0.001 moles) and 1.4487 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • a 1 liter reactor vessel was charged with 658.84 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4466 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 7.7 grams DMAEMA (0.049 moles) and 1.19 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 12 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7928 grams of sodium persulfate and 24.03 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.3% solids at a pH of 8.24.
  • Example 30 90/10 core/shell (wt. %); 2.8 mol. % crosslinker; no associative in the shell
  • a 1 -liter reactor vessel was charged with 658.86 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.57 grams of
  • Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.33 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), and 1.4477 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 7.7 grams DMAEMA (0.049 moles) and 1.16 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 12 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7915 grams of sodium persulfate and 23.95 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.4% solids at a pH of 8.34.
  • Example 31 90/10 core/shell (wt. %); 2.8 mol. % crosslinker; lower DMAEMA in the shell
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.31 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 13.2 grams ethyl acrylate (0.131 moles), 1.46 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4521 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 32 90/10 core/shell (wt. %); 2.8 mol. % crosslinker; higher DMAEMA in the shell
  • a 1 liter reactor vessel was charged with 658.85 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • Initiator B was prepared using 3.94 grams of 41% sodium bisulfite and 37.35 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.1 grams ethyl acrylate (0.121 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4512 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 33 90/10 core/shell (wt. %); 2.8 mol. % crosslinker; lower DMAEMA in the core
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • a monomer mixture of 118.2113.6 grams of ethyl acrylate (1.181 134 moles) and 1 1.5253 grams of cetyl 20 EO itaconate associative monomer (0.009 moles) was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 61.969.1 grams of DMAEMA (0.39444 moles) and 9.3610.49 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed. Next, initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 1.3204 grams of sodium persulfate and 41.33 grams of water.
  • Initiator B was prepared using 3.92 grams of 41 % sodium bisulfite and 37.34 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 12.6 grams ethyl acrylate (0.126 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4487 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 34 90/10 core/shell (wt. %); 2.8 mol. % crosslinker; higher DMAEMA in the core
  • a 1 liter reactor vessel was charged with 658.83 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.59 grams of
  • Initiator B was prepared using 3.92 grams of 41% sodium bisulfite and 37.34 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes Next, a monomer mixture of 12.61 grams ethyl acrylate (0.121 moles), 1.27 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4509 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • Example 35 90/10 core/shell (wt. %); 2.8 mol. % crosslinker in the shell; no associative and low DMAEMA
  • a 1 liter reactor vessel was charged with 658.82 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.57 grams of
  • reaction temperature was increased to 60°C.
  • a solution of 0.7914 grams of sodium persulfate and 23.92 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.5% solids at a pH of 8.29.
  • Example 36 90/10 core/shell (wt. %); 2.8 mol. % crosslinker in the shell; no associative monomer higher DMAEMA
  • a 1 liter reactor vessel was charged with 658.85 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • a monomer mixture of 108.7 grams of ethyl acrylate (1.084 moles) was added to the reactor at 20 ml/min using sub surface feed. While maintaining the temperature at 55.6°C, a mixture of 76.7 grams of DMAEMA (0.488 moles) and 1 1.21 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • initiator solutions A and B were added concurrently over 120 minutes. Initiator A was prepared using 1.3216 grams of sodium persulfate and 41.35 grams of water. Initiator B was prepared using 3.91 grams of 41 % sodium bisulfite and 37.31 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed.
  • reaction temperature was increased to 60°C.
  • a solution of 0.791 1 grams of sodium persulfate and 24.19 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.2% solids at a pH of 8.26.
  • a 1 liter reactor vessel was charged with 658.85 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.57 grams of
  • Initiator B was prepared using 3.90 grams of 41 % sodium bisulfite and 37.33 grams of water. The temperature of the reactor was maintained below 60°C during the initiator solution feed. 12 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 113.6 grams ethyl acrylate (1.134 moles), 11.53 grams of cetyl 20 EO itaconate associative monomer (0.009 moles) and 0.6187 grams of TMPTA (0.002 moles) was added to the reactor at 20 ml/min using subsurface feed.
  • the final product was an opaque white emulsion with 21.4% solids at a pH of 8.33.
  • a 1 liter reactor vessel was charged with 658.86 grams of water and heated to 65.6°C and sub surface sparged with nitrogen. The sub surface nitrogen sparging was continued for one hour and then moved to the surface. Then, 10.58 grams of
  • the temperature of the reactor was maintained below 60°C during the initiator solution feed. 108 minutes into the initiator solution feeds, both initiator solution A and B feeds were stopped and the reaction mixture was held at 55.6°C for 30 minutes. Next, a monomer mixture of 10.7 grams ethyl acrylate (0.107 moles), 1.28 grams of cetyl 20 EO itaconate associative monomer (0.001 moles) and 1.4519 grams of TMPTA (0.005 moles) was added to the reactor at 20 ml/min using subsurface feed. Then, a mixture of 10.7 grams DMAEMA (0.068 moles) and 1.63 grams of propylene glycol was added to the reactor at 20 ml/min using subsurface feed.
  • the initiator solution A and B feed were resumed and continued for the next 12 minutes.
  • the temperature was maintained below 60°C during the initiator solution feeds.
  • reaction temperature was increased to 60°C.
  • a solution of 0.7912 grams of sodium persulfate and 24.14 grams of water was then added into the reactor over 60 minutes.
  • temperature was increased to 76.7°C and held at 76.7°C for 60 minutes.
  • the reactor was then cooled down to room temperature and reaction product was filtered through 210 micron filter.
  • the final product was an opaque white emulsion with 21.4% solids at a pH of 8.34.
  • Example 39 Evaluation of viscosity and clarity, 2 wt. % active polymer

Abstract

L'invention concerne un modificateur de rhéologie gonflable à l'acide comprenant un polymère à noyau-enveloppe, le polymère à noyau-enveloppe comprenant un polymère de noyau et une enveloppe comprenant au moins une couche de copolymère d'enveloppe, au moins une couche de copolymère d'enveloppe étant au moins partiellement réticulée et contenant un pourcentage molaire d'agent de réticulation supérieur au pourcentage molaire d'agent de réticulation dans le polymère de noyau. Ledit polymère de noyau et ladite au moins une couche de copolymère d'enveloppe sont chacun polymérisés à partir d'un mélange de monomères comprenant a) un ou plusieurs monomères cationiques à insaturation éthylénique ; b) un ou plusieurs monomères hydrophobes à insaturation éthylénique ; c) facultativement un ou plusieurs monomères non ioniques à insaturation éthylénique ; et d) facultativement un ou plusieurs monomères associatifs. L'invention concerne également des compositions aqueuses comprenant le modificateur de rhéologie gonflable à l'acide comprenant des formulations de soins personnels, des formulations pour l'agriculture, des formulations de peinture, des formulations de revêtement, des formulations de blanchisserie et d'entretien de tissu, des formulations de nettoyage ménager et des formulations de nettoyage industriel et institutionnel. Dans un mode de réalisation, le polymère à noyau-enveloppe est sensiblement exempt de monomères anioniques.
PCT/EP2018/081526 2017-11-17 2018-11-16 Modificateurs de rhéologie multifonctionnels gonflables à l'acide WO2019096978A1 (fr)

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WO2022128680A1 (fr) * 2020-12-14 2022-06-23 Syngenta Crop Protection Ag Procédé de préparation de microcapsules

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