TW201930533A - Acid-swellable multi-functional rheology modifiers - Google Patents

Abstract

Acid-swellable rheology modifier comprise a core-shell polymer, the core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, at least one shell copolymer layer being at least partially cross-linked and containing a mole percent of crosslinking agent greater than the mole percent of crosslinking agent in the core polymer, wherein said core polymer and said at least one shell copolymer layer are each polymerized from a monomer mixture 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. Aqueous compositions comprising the acid-swellable rheology modifier include personal care formulations, agricultural formulations, paint formulations, coating formulations, laundry and fabric care formulations, household cleaning formulations, and industrial and institutional cleaning formulations. In one embodiment the core-shell polymer is substantially free of anionic monomers.

Description

Acid swellable multifunctional rheology modifier

In one aspect, the present application is directed to a rheology modifier comprising an acid swellable core-shell polymer comprising a core and at least one crosslinked shell, wherein the at least one crosslink The percentage of moles of crosslinker in the shell is greater than the percentage of moles of crosslinker in the core. In another aspect, the present application relates to such acid swellable core-shell polymer rheology modifiers suitable for use in aqueous systems, and such rheology modifiers provide other functions that can be used in the final formulation. . Additionally, the present application relates to the formation of a rheologically stable and phase stable surfactant aqueous composition comprising such an acid swellable core-shell polymer.

Rheology modifiers, also known as thickeners or tackifiers, are ubiquitous in a variety of commercial formulations, such as personal care formulations, health care formulations, agricultural formulations, paint formulations, paint formulations, clothing and Fabric care formulations, household cleansing formulations, and industrial and institutional cleansing formulations. Rheology modifiers can be selected for a particular formulation to provide rheological properties for a particular purpose. For example, for personal care formulations, rheology modifiers can be selected for their ability to provide viscosity and flow characteristics, sudsing, applicability, clarity, sensory effects, and mildness.

The personal care formulation achieves a pH in the range of 2-6, whereby a milder preservative can be used in such formulations. Such lower pH formulations require the use of acid swellable rheology modifiers. However, there are very few acid swellable rheology modifiers available to the formulator. Accordingly, there is a need for an acid swellable rheology modifier that is easy to use, provides the desired rheological characteristics, and has good solubility. For some formulations, it is also desirable to have an acid swellable rheology modifier that provides good clarity. There is also a need for an acid swellable rheology modifier that provides these qualities and further provides hair fixing functionality. It is also desirable for such acid swellable rheology modifiers to provide such qualities in the pH range of about 2-6. Still further, it is desirable that at least a portion of the acid swellable rheology modifier is derived from natural renewable resources.

In one aspect, the application relates to an acid swellable rheology modifier suitable for use in an aqueous composition, the acid swellable rheology modifier comprising at least one core-shell polymer, the core-shell The polymer comprises 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 crosslinked copolymer having a molar percentage higher than a crosslinking agent in the core polymer A molar percentage of crosslinker.

The application is further directed 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 olefinic groups Saturated monomer; 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 also includes one or more crosslinkers. The core polymer may optionally include one or more crosslinking agents.

In one aspect, the core polymer and the at least one shell polymer are substantially free of anionic monomers.

In one aspect, the weight ratio of shell to core and the amount of crosslinker of the shell and core are selected to provide better rheological properties in a particular end use application.

In some embodiments, the amount of shell polymer is less than 90% by weight of the total core-shell polymer. In some embodiments, the at least one shell copolymer layer is present in an amount greater than 5 wt% of the total core-shell polymer.

In some embodiments, a crosslinking agent is present in the core polymer.

In some embodiments, an association monomer is present in the core polymer, or in the at least one shell copolymer layer, or in the core polymer and the at least one shell copolymer layer.

In some embodiments, the core - shell polymer comprising (meth) acrylic acid C ₁ -C ₆ alkyl ester monomers. In some embodiments, such core - shell polymer comprises at least one C ₁ -C ₆ alkyl ester of methacrylic acid monomer and at least one C ₁ -C ₆ alkyl esters of acrylic acid monomers.

In another aspect, the present application is directed to an acid swellable rheology modifier comprising a core-shell polymer and further comprising a spray dried adjuvant.

In another aspect, the present application is directed to an acid swellable rheology modifier comprising a core-shell polymer and further comprising a spray dried adjuvant derived from a natural renewable resource.

In one embodiment, the natural renewable resource as a source of spray-dried adjuvant is derived from a polysaccharide.

In one embodiment, the natural renewable resource as a source of spray-dried adjuvant is based on cellulose.

In one embodiment, the natural renewable resource as a source of spray-dried adjuvant is based on starch.

In another aspect, the present application is directed to an acid swellable rheology modifier comprising a core-shell polymer and further comprising a spray dried adjuvant derived from a polyvinyl acetate derivative.

In one embodiment, 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) the core-shell The polymer is co-mixed with a spray-dried adjuvant; and (iii) the blend is dried; wherein the acid-expandable rheology modifier is in the form of a dry powder.

In another aspect, the application is directed to an aqueous polymer emulsion comprising an acid swellable core-shell polymer as described herein.

In another aspect, the application is directed to a formulation comprising an acid swellable rheology modifier as disclosed herein.

In one embodiment, a formulation comprising an acid swellable rheology modifier as disclosed herein is selected from the group consisting of a personal care formulation, a healthcare formulation, an agricultural formulation, a paint formulation, a paint formulation, Clothing and fabric care formulations, household cleaning formulations, as well as industrial and institutional cleansing formulations, formulations for use in the electronic components industry, and formulations used in the construction industry.

In one embodiment, the formulations further comprise an aqueous formulation of one or more surfactants. The surfactants can be selected from any of anionic, cationic, amphoteric and nonionic surfactants, and mixtures thereof.

In one embodiment, the formulations are personal care formulations.

In one embodiment, the personal care formulations are hair fixative formulations, and the acid swellable rheology modifiers additionally provide a film forming function such that the rheology modifier is also used as hair in the formulation. Fixed ingredients.

In one embodiment, the formulations are low pH formulations compatible with the acid preservative and the cationic component.

An illustrative embodiment in accordance with the present application will be described. Various modifications, changes and variations of the exemplary embodiments may be apparent to those skilled in the art. It is to be understood that all such improvements, modifications, and variations of the teachings of the present application are deemed to be within the scope and spirit of the present application, and the teachings are.

The polymers and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process descriptions described herein. The embodiments disclosed herein exemplarily may be practiced without any elements not specifically disclosed herein.

In the context of the present invention, the term "(co)polymer" means a polymer or copolymer. The term "polymer" and the term "copolymer" are used interchangeably herein.

As used throughout this document and throughout this specification, the terms "core-shell morphology", "core-shell structure", "core-shell polymer", "segmented core-shell polymer" and "two-stage polymer" or "Multi-stage polymer" is used interchangeably and means polymer particles prepared by a sequential or staged polymerization procedure in which monomeric repeat units of each sequence or stage are added to a polymerization reactor and begin The polymerization is carried out, followed by the addition of the repeating unit of the subsequent sequence or stage and the polymerization. In some embodiments, one stage of polymerization will be substantially completed before the next stage of monomer addition to the polymerization reactor; in some embodiments, one stage of polymerization can be added to the polymerization in the next stage of polymerization. The reactor was only partially completed before. As best understood, in the structures of such core-shell polymers disclosed herein, the polymer forming the core portion, sequence or stage and the polymer system forming the shell portion, sequence or stage are physically and/or Bonded and/or attracted to each other chemically. The structure and/or chemical composition (e.g., monomer composition and/or amount) of the disclosed copolymer particles vary from the interior to the exterior of the particle and, therefore, such gradient regions can also have different physical and chemical properties. These changes can be progressive to some extent, resulting in a morphology having a polymer structure or composition gradient along any radius thereof. Alternatively, when moving from the center toward the outside along the radius of the particle, the change in polymer structure or composition can be relatively preferably determined to produce a relatively different core portion having a polymer composition and a relatively different polymer composition. The shape of the shell part. The segmented core-shell morphology may comprise a plurality of layers or zones having different polymer compositions, as long as at least one shell copolymer layer is at least partially crosslinked polymer having a molar percentage higher than that of the core polymer The molar percentage of the cross-linking agent. The rate of change of the polymer morphology of the particles is not particularly critical as long as the polymer exhibits the requisite characteristics described herein. Therefore, as used herein, the terms "core" and "shell" refer to the polymeric material inside and outside the particle, respectively, and the use of such terms should not be construed to mean that the disclosed polymer particles must be A different interface is exhibited between the inside and outside of the particle.

In some embodiments, the segmented core-shell polymer particles can be in the form of a core portion that completely coats the shell portion or encapsulates within the shell portion. In other embodiments, the core-shell polymer particles may be in the form of a core portion that is only partially coated or encapsulated. It should also be understood that in describing the "nuclear polymer" and "shell polymer" of the segmented core-shell polymer disclosed, a large amount of polymer interpenetration may be present in the core and shell of the polymer particles. Thus, a "nuclear polymer" can extend to some extent into the shell of the particle, forming a region in the shell particle, and vice versa.

The terms "nuclear polymer" and "shell polymer" and like terms are used herein to describe a polymeric material in the named portion of a polymer particle in a conventional manner without attempting to identify any particular polymer as "shell." Or absolutely "nuclear" polymer.

As used herein, the term "(meth)acrylic acid" is intended to include both acrylic acid and methacrylic acid. Similarly, as used herein, the term "alkyl (meth)acrylate" is intended to include alkyl acrylates and alkyl methacrylates.

The term "aqueous" as used in the formulation or medium means that the water is present in an amount sufficient to at least swell or dissolve the polymer in the composition formulated in the multi-purpose polymer.

The acid swellable core-shell polymer of the present invention has a pH in the range of from about 1 to about 7, or in the range of from about 2 to about 6.5, or from about 2 to about 6, or from about 3 to about 6 Aqueous formulations having desirable rheological properties selected from the group consisting of personal care formulations, health care formulations, agricultural formulations, paint formulations, paint formulations, clothing and fabric care formulations, households Clean formulations, industrial and institutional cleansing formulations, formulations used in the electronic components industry, and formulations used in the construction industry. The acid swellable core-shell polymer of the present invention is compatible with the cationic component, making it particularly useful as a thickening agent in products containing quaternary ammonium salts or amines. In addition, the acid swellable core-shell polymer of the present invention can be used to contain one or more surfactants (eg, anionic, cationic, amphoteric, nonionic surfactants, and/or any two or more thereof) The composition of the combination). In some embodiments, the acid swellable core-shell polymer can also provide hair styling efficacy when used in a personal care formulation as a hair styling formulation. In some embodiments, the acid swellable core-shell polymer is a useful thickener in products containing the active acid component and is a useful thickener and emulsifier for emulsions (creams, lotions). Agent. In some embodiments, for containing a surfactant, a colorant, a hair and skin conditioner, a polyoxygen, a mono-quaternary ammonium compound, a polytetra-ammonium compound, an anti-dandruff agent, an anti-aging compound, an anti-wrinkle compound, an anti-drug Pigment compound, anti-cellulite compound, anti-acne compound, vitamin, analgesic, anti-inflammatory compound, self-tanning agent, hair growth promoter, UV protectant, skin whitening agent, vegetable, plant and plant extract, In addition to thickening, acid-swellable core-shell polymers are also useful film formers and coating aids for products such as sweats, antioxidants, deodorants, hair-fixing polymers, emollient oils and combinations thereof. And deposition aids.

In some preferred embodiments, the acid swellable core-shell polymer disclosed herein imparts the desired clarity characteristics in addition to the desired rheological properties as described above, in units of turbidity. Measure. The aqueous composition having a rheology modifier disclosed herein is in one state as measured in a thickened aqueous polymer composition comprising about 2% by weight polymer (active polymer solids) and the balance being water. The sample may have a turbidity value of N1000 NTU, in another aspect a turbidity value ≦500 NTU, in another aspect ≦200 NTU, in another aspect ≦100 NTU, and in another aspect The medium is 50 NTU, and wherein the thickened composition has a pH of about 3-4.

As used herein, the term "rheological properties" and grammatical variations include, but are not limited to, properties such as viscosity, ie, viscosity increases or decreases in response to shear stress, and flow characteristics; gelling properties such as stiffness, Elasticity, fluidity, and the like; foaming characteristics such as foam stability, foam density, ability to maintain peaks, and the like; suspension characteristics, such as yield values; and aerosol characteristics, such as when self-propelled or mechanically pumped The ability of the aerosol dispenser to form aerosol droplets when dispensed; the flow of liquid through the pump dispenser; or any quality or characteristic that can be measured with a viscometer or a rotary or tensile rheometer. In some preferred embodiments, the aqueous compositions having rheology modifiers disclosed herein will have yield values sufficient to support aesthetic and cosmetic pharmaceutical beads and particles, air bubbles, exfoliating agents, and the like.

When applied to a composition, the term "aesthetic properties" and its grammatical variations refer to visual and tactile psychosensory product characteristics such as color, clarity, smoothness, viscosity, lubricity, texture, conditioning and feel, and Similar characteristics.

Here, as well as elsewhere in the specification and claims, individual values (including carbon atom values) or limits may be combined to form additional undisclosed and/or unrepresented ranges.

The headings provided herein are intended to illustrate and not limit the application in any way.

Core-shell polymer The acid swellable rheology modifier for use in an aqueous composition comprises a core-shell polymer comprising one or more copolymer layers, wherein at least one of the shell copolymer layers is at least partially crosslinked A polymer comprising a crosslinking agent having a molar percentage greater than the molar percentage of the crosslinking agent in the core polymer. The core-shell polymers may comprise a plurality of shell copolymer layers which may be the same or different in terms of the type and proportion of monomers in the polymer backbone from the core layer and between each other. The plurality of shell copolymer layers may have any molar percentage of crosslinker as long as the core (first stage) polymer has a lower molar percentage of crosslinker than the crosslinked shell (subsequent stage) of the copolymer layer At least one of them can be.

In one aspect, the core-shell polymer comprises from about 1% to about 95% by weight, based on the total weight of the core-shell polymer, of the one or more shell layers. In one embodiment, the core-shell polymer comprises from about 5 wt% to about 60 wt% of the one or more shell layers, and in one embodiment from about 10 wt% to about 40 wt% of the one or more a shell layer, and in one embodiment, from 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, and the polymerization The remainder of the material is a core polymer.

In one embodiment, the core comprises 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 In embodiments, it is at least 90 wt%; in one embodiment at least 95 wt%.

In one embodiment, the core polymer does not comprise a crosslinking agent and the core comprises more than 60% by weight of the core-shell polymer.

Monomer component 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 crosslinkers, as long as at least one shell copolymer layer comprises One or more crosslinking agents. In one embodiment, the core polymer and 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 the at least one shell layer, and optionally in the core monomer composition, as long as the crosslinker in the at least one shell layer is more than the core polymer The cross-linking agent can be used.

Cationic Monomer As used herein, the term "cationic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer capable of generating a positive charge when the polymer polymerized from the monomer is in an aqueous solution. In one embodiment, the cationic ethylenically unsaturated monomer has at least one primary, secondary or tertiary amine functional group, or is a non-cyclic ethylenically unsaturated formamide or acetamide. As used herein, the term "amine salt" means that the nitrogen atom of the amine functional group is covalently bonded to one to three organic groups and is associated with an anion.

Such cationic ethylenically unsaturated monomers having primary, secondary or tertiary amine functional groups include, but are not limited to, N,N-dialkylaminoalkyl (meth)acrylate, (meth)acrylic acid N-alkylaminoalkyl ester, N,N-dialkylaminoalkyl (meth) acrylamide and N-alkylaminoalkyl (meth) acrylamide, wherein the alkyl group is independently C _{1 - 22} straight chain, branched chain or cyclic moiety; aromatic amine-containing monomer such as vinyl pyridine; alkenylamine-containing monomer, wherein alkenyl unsaturated C _{1 - 22} linear, branched chain Or a cyclic moiety such as an allylamine or a vinylamine; and an acyclic ethylenically unsaturated formamide or acetamide such as vinylformamide, vinylacetamide and the like. Mixtures of any of the foregoing may be used. Preferably, the cationic ethylenically unsaturated monomer is selected from one or more of the following: N,N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, N, N - dimethylaminopropyl methacrylamide, 3-(dimethylamino)propyl methacrylate, 2-(dimethylamino)propan-2-yl methacrylate, methyl 3-(Dimethylamino)-2,2-dimethylpropyl acrylate, 2-(dimethylamino)-2-methylpropyl methacrylate and 4-(dimethyl) methacrylate Amino) butyl ester, and mixtures of any of the foregoing. Optimum cationic ethylenically unsaturated single system N,N-dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate and N,N-dimethylaminopropyl Methyl acrylamide, and mixtures of any of the foregoing.

The cationic ethylenically unsaturated monomer may comprise at least about 10 mol% or more of the total monomer of the core polymer or shell copolymer layer used to make the acid swellable core-shell polymer of the monomer. 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 50 mol%. The maximum proportion of the monomer in the core polymer or shell copolymer layer of the acid swellable core-shell polymer in which the cationic ethylenically unsaturated monomer is present may be about 80 mol% or less, preferably It is about 70 mol% or less, and most preferably about 60 mol% or less, in each case, the mol% is the total amount of the monomers present in the stage excluding the crosslinking agent. Ear meter.

Hydrophobic Monomer As used herein, the term "hydrophobic ethylenically unsaturated monomer" means a monomer that is hydrophobic and capable of forming an emulsion system when reacted with a cationic ethylenically unsaturated monomer. For the purposes of this application, the hydrophobic ethylenically unsaturated monomer can be sparingly soluble in water and has a water solubility of less than 6 g/100 ml water at 25 ° C or less than 3 g / 100 ml at 25 ° C. The water, preferably below 2 g/100 ml water at 25 ° C, and preferably below 1.6 g/100 ml water at 25 ° C. These hydrophobic monomers may contain a linear or branched alk(en)yl, cycloalkyl, aryl or alk(en)aryl moiety. Suitable hydrophobic ethylenically unsaturated monomers include C ₁ -C ₃₂ alkyl acrylates and methacrylates, including methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. Ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, (A) Isoamyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-(meth) acrylate Butyloctyl ester, 2-hexyldecyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, (meth)acrylic acid 2 - lauryl cetyl ester, behenyl (meth) acrylate, lauryl (meth) acrylate and methacrylate (meth) acrylate; other esters of acrylic acid and methacrylic acid, including (methyl Benzyl acrylate, phenyl (meth) acrylate, ethoxylated benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and (meth)acrylic acid 10-hydroxyl Esters; and acrylic and methacrylic acid C ₄ -C ₃₂ alkyl Amides, including tert-butyl (meth) acrylamide, t-octyl (meth) acrylamide, 2-ethylhexyl ( Methyl) acrylamide, n-octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide and behenyl (meth) acrylamide. Other suitable hydrophobic monomers include styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, isopropyl styrene and p-chlorostyrene; vinyl acetate, vinyl butyrate, glycol Vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl phthalate, vinyl phthalate, vinyl neodecanoate, vinyl laurate, vinyl caprolactam, (methyl) Acrylonitrile, isobutylene, isoprene, vinyl chloride, vinylidene chloride, 1-allyl naphthalene, 2-allyl naphthalene, 1-vinylnaphthalene, 2-vinylnaphthalene, all of the foregoing monomers may be Use in any combination. Preferred is ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Third butyl ester, vinyl acetate, tert-butyl acrylamide, and combinations thereof. In one embodiment, ethyl acrylate, methyl acrylate, methyl methacrylate, vinyl acetate, butyl acrylate, and combinations thereof are preferred. In one embodiment, ethyl acrylate is preferred.

In one aspect, the hydrophobic olefin stated under the second monomer component b) is based on the total moles of monomers in the core polymer or shell copolymer layer of the hydrophobic ethylenically unsaturated monomer. The amount of the unsaturated monomer is from about 90 mol% to about 20 mol%, in another aspect from about 80 mol% to about 30 mol%, and in yet another aspect, about 75 mol% to About 35 mol%, and about 60 mol% to about 40 mol%, or in still another aspect, more 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%, in each case, mol% is based on the total moles of monomer present in the stage excluding the crosslinker. In one embodiment, the hydrophobic ethylenically unsaturated mono system is present in an amount of from 20 to 30 mole percent based on the total moles of monomer present in the stage excluding the crosslinking agent.

Optional Nonionic Ethylenically Unsaturated Monomer As used herein, the term "nonionic ethylenically unsaturated monomer" means an ethylenically unsaturated monomer that does not introduce a charge into the core-shell polymer, and It is neither a hydrophobic ethylenically unsaturated monomer nor an associative monomer nor a crosslinker (each as defined herein). Such nonionic ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, NC ₁ -C ₃ alkyl (meth) acrylamide, and N, NC ₁ - C ₃ Alkyl (meth) acrylamide, such as N-methyl methacrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-isopropyl acrylamide, N, N- Dimethyl acrylamide and N,N-dimethyl methacrylamide; vinyl morpholine, vinyl pyrrolidone, vinyl propionate, vinyl butyrate, ethoxylated alkyl, alkane or aryl monomers such as methoxypolyethylene glycol (meth) acrylate, allyl glycidyl ether, allyl alcohol, glycerol (meth) acrylate, (meth) acrylic acid C ₁ to C ₄ -hydroxyalkyl ester and the like. Nonionic ethylenically unsaturated monomers include (poly)C ₁ -C ₄ alkoxylated (meth) acrylates such as poly(ethylene glycol) _n (meth) acrylate and poly(propylene glycol) _n ( a methyl acrylate wherein n = 1 to 100, preferably 3 to 50, and most preferably 5 to 20; ethoxylated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkaryl or Aryl monomer. In one aspect, the optional nonionic ethylenically unsaturated monomer component c) is methoxypolyethylene glycol (meth) acrylate.

The C ₁ to C ₄ hydroxyalkyl (meth) acrylate may include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and (butanediol mono ( Methyl) acrylate). In one aspect, the hydroxyalkyl ester of component c) is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate.

The optional nonionic ethylenically unsaturated monomer of component c), when present, may be present in the range of from about 5 mol% to about 30 mol%, or from about 10 mol% to about 25 mol%, using the optional nonionic In the core polymer or shell copolymer layer of the ethylenically unsaturated monomer, in each case, mol% is based on the total molar amount of the monomer present in the stage excluding the crosslinking agent.

Associative Monomer As used herein, the term associative monomer is intended to mean an ethylenically unsaturated monomer containing a hydrophobe and leaving the hydrophobe far enough away from the polymer backbone to form a hydrophobically associated spacer moiety in the aqueous solution. And wherein the hydrophobe comprises at least six carbon atoms. The spacer moieties are typically ethoxylate groups, but any other group that allows the hydrophobe to extend away from the polymer backbone can also be used. Hydrophobes with spacer moieties include, but are not limited to, alcohol ethoxylates, alkylphenoxy ethoxylates, propoxylated/butoxylated ethoxylates, ethoxylated polyfluorenes Oxygen and the like. In one embodiment, preferred hydrophobes with spacer moieties include alcohol ethoxylates and/or alkylphenoxy ethoxylates. In another embodiment, an alcohol having a carbon chain length of from 6 to 40 and from 6 to 100 moles of an ethoxylated alcohol ethoxylate are more preferred. In still another embodiment, an alcohol having a carbon chain length of 12 to 22 and 15 to 30 mol of an ethoxylated alcohol ethoxylate are particularly preferred. The hydrophobe may be a linear or branched alk(en)yl group, a cycloalkyl group, an aryl group, an alk(en)aryl group or an alkoxylated derivative. In one embodiment, the optimal hydrophobe is a linear or branched alcohol and amine having from 12 to 32 carbons. The associative monomer may contain an ethylenically unsaturated monomer covalently attached to the hydrophobe. In one embodiment, the ethylenically unsaturated monomer portion of the associative monomer is preferably a (meth) acrylate, itaconate, and/or maleate containing an ester linking group. However, the associative monomers may also contain guanamines, ureas, urethanes, ethers, alkyl groups, aryl groups, and other suitable linking groups. The hydrophobe may be an alkylamine or a dialkylamine ethoxylate. In one embodiment, the (meth) acrylate group is optimal. In another embodiment, a preferred association system C _{12 - 32} (EO) _{10 - 30} methyl (acrylate), or C _{12 - 32} (EO) _{10 - 30} itaconate, or C _{12 - 32} (EO) _{10 - 30} maleate.

In one embodiment, the associative monomer has the structure of formula (I)

among them
R ₁ Department of -H, -CH _3, -COOH or -CH ₂ COOH;
A system _{-CH 2 C (O) O -} , - C (O) O -, - O -, - CH 2 O -, - CH 2 C (O) N -, - C (O) N -, - CH ₂ -, -OC(O)-, -NHC(O)O-, -NHC(O)NH-, -C ₆ H ₄ (R ₅ )-NH-C(O)-O-, -C ₆ H ₄ (R ₅ )-NH-C(O)-NH-, -C(O)O-CH ₂ -CH(CH ₂ OH)-O-, -C(O)O-CH ₂ -CH(CH ₂ OH)-NH-, -C(O)O-CH ₂ -CH-CH ₂ (OH)-O-, -C(O)O-CH ₂ -CH-CH ₂ (OH)-NH-, -CH _2- O-CH ₂ -CH(CH ₂ OH)-O-, -CH ₂ -O-CH ₂ -CH-CH ₂ (OH)-O-, -CH ₂ -O-CH ₂ -CH (CH ₂ OH)-NH- or -CH ₂ -O-CH ₂ -CH-CH ₂ (OH)-NH-;
(R ₃ -O) _n- based polyoxyalkylene group, which is a homopolymer, random copolymer or block copolymer formed of a C ₂ to C ₄ oxygen alkyl unit, wherein each R _{3 is} independently -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ - or a mixture thereof, and n is an integer in the range of from about 5 to about 250, preferably, n is from 5 to 100, more preferably The ground is 10-50 and the best is 15-30;
R ₄ is a C ₆ -C ₃₆ straight or branched chain, a saturated or unsaturated alk(en)yl or alk(en)aryl group, preferably a C ₈ -C ₃₂ straight or branched alk(en)yl group. , better still C ₁₀ -C ₂₂ straight chain alk (en) yl, or C ₁₀ -C ₃₂ branched alk (en) yl; and
R ₅ based -CH ₂ - or _{- (C) (CH 3)} 2 -.

Suitable associative monomers include methacrylates and itaconates having a hydrophilic ethoxylate chain and a hydrophobic alkyl chain.

In one embodiment, the association system has an alkyl ethoxylated methacrylate having the structure of Formula I(A):

A-cetyl/stearyl ethoxylated (20) methacrylate

In one embodiment, the association system is based on an itaconate-associating monomer, such as cetyl ethoxylated itaconate having the structure of Formula I (B, C, D, respectively), Hawthorn ethoxylated itaconate or stearyl ethoxylated itaconate:

In one aspect, the optional associative monomer described under monomer component d), when present, is present in the core polymer or shell copolymer layer of the association monomer in an amount of about 0.001 mol% In the range of about 20 mol%, in another range from about 0.005 mol% to about 10 mol%, and in still another aspect in the range of from about 0.01 mol% to about 5 mol%, in each case Next, mol% is based on the total molar amount of the monomer present in the stage excluding the crosslinking agent.

Substantially free of anionic monomers. In one aspect, the core polymer and the one or more shell polymers are substantially free of anionic monomers, wherein as used herein, anionic single systems are polymerized. A non-associative ethylenically unsaturated monomer capable of producing a negative charge when in an aqueous solution. In one embodiment, the core polymer is free of anionic monomers. In one embodiment, the one or more shell polymers are free of anionic monomers. In one embodiment, the core polymer and the one or more shell polymers are free of anionic monomers. Representative anionic monomers include (meth)acrylic acid, itaconic acid, methyl maleic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, 2-propenylamine 2-methylpropanesulfonic acid, vinylsulfonic acid, sodium methallylsulfonate, sulfonated styrene, allyloxybenzenesulfonic acid, and vinylphosphonic acid and salts thereof, and mixtures thereof. As used herein, the term "substantially free" means that any anionic monomer may be present in lower amounts such that when the pH is lowered by the use of an acidic material, the polymer in the formulation in which the anionic monomer is intended to be used is used. Upon activation, the anionic monomer does not interfere with the expansion and rheology modification functions of the core-shell polymer, as further described herein. In one embodiment, the core polymer and the at least one shell polymer layer each comprise less than 10 mol% anionic monomer, and in one embodiment less than 5 mol% anionic monomer, in one embodiment Less than 3 mol% of anionic monomers are included, in one embodiment less than 2 mol% of anionic monomers, and in one embodiment less than 1 mol% of anionic monomers.

Crosslinking Agent In one aspect, at least one of the shell copolymer layers of the core-shell polymer comprises a crosslinking agent such that the layer containing the crosslinking agent is in a partially or substantially crosslinked network structure. The core may also contain a crosslinking agent, whereby the core will be in a partially or substantially crosslinked network structure as long as the molar percentage of the crosslinking agent in the core (first stage) polymer is lower than the core-shell polymer. The percentage of moles of the crosslinking agent in the at least one shell copolymer layer (subsequent stage) of the crosslinking agent may be included.

The crosslinking agent may be selected from one or more of a crosslinking monomer having two or more carbon-carbon double bonds or a polyfunctional crosslinking compound reactive 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-butanediol di(meth)acrylate, 1,6-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,2'-bis(4-(acryloxy-propoxyphenyl)propane, 2,2' - bis(4-(propylene decyloxydiethoxy-phenyl)propane and zinc acrylate (ie, 2(C ₃ H ₃ O ₂ )Zn ⁺⁺ ); a tri(meth) acrylate compound, such as Trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethyl(ethoxylate)propane tri(meth)acrylate and tetramethylolethane Tris(meth)acrylate; tetra(meth)acrylate compound such as bis(trimethylolpropane)tetra(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, and pentaerythritol IV ( Methyl) acrylate; hexa(meth) acrylate compound such as dipentaerythritol hexa(methyl) Allyl compound; allyl compound, such as allyl (meth) acrylate, diallyl phthalate, diallyl itaconate, diallyl fumarate and cis-butene Diallyl acrylate; polyallyl ether of sucrose having 2 to 8 alkyl groups per molecule, polyallyl ether of pentaerythritol, such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl Polyether ether of trimethylolpropane, such as trimethylolpropane diallyl ether and trimethylolpropane triallyl ether. Other suitable polyunsaturated compounds include divinylethylene Alcohol, divinylbenzene and N,N'-methylenebis acrylamide.

In another aspect, suitable polyunsaturated monomers can be prepared via ethylene oxide or propylene oxide or a combination thereof with an unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride. The esterification reaction or synthesis reaction with an unsaturated isocyanate such as 3-isopropenyl-α-α-xylene isocyanate.

Exemplary polyfunctional crosslinking compounds include polyhaloalkanols such as 1,3-dichloroisopropanol and 1,3-dibromoisopropanol; hydrazine zwitterions such as tetrahydrothiophene adducts of novolak resins; a halocycloalkane such as epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin and epiiodohydrin; a polyglycidyl ether such as 1,4-butanediol diglycidyl ether, glycerol-1, 3-diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A- Epichlorohydrin epoxy resin and a mixture of the foregoing. Mixtures of two or more of the foregoing polyfunctional compounds may also be used.

The amount of crosslinking agent can range 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 in another aspect. In the range of from about 0.03 mol% to about 7.5 mol%, in each case, the total moles of monomers in the stage of using the crosslinker, wherein the amount of crosslinker is not included.

The amount of crosslinker in each layer will depend on the desired core-shell polymer characteristics.

In some embodiments in which at least one associative monomer is present during at least one core-shell synthesis stage and/or at least one crosslinker is present during the core (first) synthesis stage, a given stage is present when a crosslinking agent is present The molar percentage of the medium crosslinker is from about 0.001 mol% to about 20 mol%, preferably from about 0.01 mol% to about 15 mol%, and more preferably from about 0.05 mol% to about 10 mol%, and more preferably from 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 monomer present in the stage excluding the crosslinker.

No association monomer exists in any stage of core-shell particle synthesis, no crosslinker is present during the nuclear (first) stage synthesis, and the core (first stage) has a mass of more than 60% of the core-shell particle mass. In another embodiment, the crosslinking agent in the at least one shell (subsequent stage) polymer may be present in the range of from about 0.05 mol% to about 20 mol%, preferably about 0.05 mol%, during the synthesis of the stage. It is in the range of 10 mol%, and most preferably in the range of about 0.1 mol% to about 10 mol%, in each case in terms of the total moles of monomers in the shell stage excluding the crosslinker.

Chain Transfer Agents 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 that reduces the molecular weight of the disclosed segmented polymer. Suitable chain transfer agents include, but are not limited to, compounds containing a thio group and a disulfide group, such as a C ₁ -C ₁₈ alkyl mercaptan, a C ₁ -C ₁₈ alkyl mercapto alcohol, a mercapto carboxylic acid, a mercapto carboxylic acid ester, Thioester, C ₁ -C ₁₈ alkyl disulfide, aryl disulfide, polyfunctional thiol such as trimethylolpropane-gin-(3-mercaptopropionate), pentaerythritol-tetra-(3-mercapto) Propionate), pentaerythritol-tetra-(thioglycolate) and pentaerythritol-tetra-(thiolactate), dipentaerythritol-hexa-(thioethylalcoate) and the like; phosphite and Hypophosphite; a halogenated alkyl compound such as carbon tetrachloride, trichlorobromomethane and the like; and a catalytic chain transfer agent such as a cobalt complex (e.g., a cobalt (II) chelate).

In one aspect, the chain transfer agent is selected from the group consisting of n-dodecyl mercaptan, methyl mercaptopropionate, 3-mercaptopropionic acid, 2-mercaptopropionic acid, combinations and analogs thereof, octyl mercaptan, and third-tenth Dialkyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, isooctyl 3-mercaptopropionate, butyl 3-mercaptopropionate, butyl thioglycolate, isooctyl thioglycolate Ester and dodecyl thioglycolate.

When a chain transfer agent is utilized, it may be present in an amount ranging from about 0.005 mol% to about 1 mol%, or in a range from about 0.01 mol% to about 1 mol%, in each case using a chain transfer agent and The total molar amount of monomer in the stage of the crosslinking agent is not included.

Core-Shell Polymer Preparation The core-shell polymers disclosed herein comprise at least two polymers synthesized sequentially by free radical emulsion polymerization techniques known in 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 Monomer; and optionally c) one or more nonionic ethylenically unsaturated monomers, and/or d) one or more associative monomers, and/or e) one or more crosslinkers, all as above reveal. Chain transfer agents can also be used.

In one embodiment, the core monomer composition is pre-emulsified in the water and surfactant mixture prior to emulsion polymerization prior to addition to the reactor in the first vessel. In another embodiment, water and a surfactant are added to the reactor prior to the core monomer composition, and then emulsion polymerization occurs after the addition of the initiation system.

The emulsion polymerization mixture also includes one or more free radical initiators. In one embodiment, the one or more free radical initiators are present in an amount ranging from about 0.01% to about 3% by weight based on the total monomer weight. The polymerization can be carried out in an aqueous or aqueous alcohol medium of neutral to moderate alkaline pH.

Suitable surfactants for promoting emulsion polymerization include nonionic, anionic, amphoteric, cationic surfactants, and mixtures thereof. Most commonly, nonionic surfactants are utilized. As is well known in the art, the physical properties (e.g., viscosity, coatability, clarity, texture, and the like) of the neutralized polymer can be varied by appropriately selecting the hydrophobicity and hydrophilicity of the emulsifying surfactant.

FIELD adapted to facilitate nonionic surfactant in the emulsion polymer are well known and include (but are not limited to) a straight-chain or branched alcohol ethoxylates, C ₈ to C ₁₂ alkyl phenol alkoxylates Such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers and the like. Other useful nonionic surfactants include C ₈ to C ₂₂ fatty acid esters of polyoxyalkylene glycol, mono- and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C ₈ to _C22 fatty acid glycol esters, block copolymers of ethylene oxide and propylene oxide having an HLB value greater than about 12, ethoxylated octylphenol, and combinations thereof. In another embodiment, the linear alcohol alkoxylate comprises cetearyl alcohol sold by BASF under the tradenames PLURAFAC® C-17, PLURAFAC® A-38, and PLURAFAC® A-39 (cetitol and hard Polyethylene glycol ether of a mixture of aliphatic alcohols. In yet another embodiment, the polyoxyethylene polyoxypropylene block copolymer comprises a copolymer sold by BASF under the tradenames PLURONIC® F127 and PLURONIC® L35.

Other suitable nonionic surfactants include, but are not limited to, ethoxylated linear fatty alcohols such as DISPONIL® A 5060 (Cognis), Ethal LA-23, and Ethal LA-50 (Ethox Chemicals); branched paraffins Ethoxylates such as GENAPOL® X 1005 (Clariant Corp.), secondary C ₁₂ to C ₁₄ alcohol ethoxylates such as TERGITOL® S15-30 and S15-40 (Dow Chemical Co.); Oxylated octylphenol surfactants such as TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887 and 897 (Rhodia, Inc.), ICONOL® OP 3070 and 4070 (BASF Corp.), SYNPERONIC® OP 30 and 40 (Uniqema); block copolymers of ethylene oxide and propylene oxide, such as PLURONIC® L35 and F127 (BASF Corp.), and secondary C ₁₁ Alcohol ethoxylates such as EMULSOGEN® EPN 407 (Clariant Corp.). A number of other suppliers are found in the commodity literature.

The emulsion polymerization can be carried out in the presence of a suitable polymer stabilizer. Suitable polymeric stabilizers (also known as protective colloids) for use in the emulsion polymerization process of the present invention are water soluble polymers including, for example, synthetic polymers such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrole Pyridone, polyacrylamide, polymethacrylamide, carboxylate functional addition polymers, polyalkyl vinyl ethers and the like; water soluble natural polymers such as gelatin, pectin, alginate, Casein, starch, and the like; and modified natural polymers such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl modified hydroxyethylcellulose, and the like. In some cases, it is preferred to use a mixture of synthetic and natural protective colloids, such as a mixture of polyvinyl alcohol and casein. Other suitable natural polymers are mixed ethers such as methyl hydroxyethyl cellulose and carboxymethyl methyl cellulose. The polymeric stabilizer may be used in an amount up to about 10% by weight, or up to about 7.5 % by weight, or up to about 5% by weight, or up to about 2.5% by weight, or up to about 2, by weight of the total emulsion. weight%. In another embodiment, when a polymeric stabilizer is utilized, the amount of polymeric stabilizer included is in the range of from about 0.001% to about 10% by weight, or from about 0.01% by weight to about the total emulsion weight. Within the range of 7.5 wt%, or in the range of from about 0.1 wt% to about 5 wt%, or in the range of from about 0.5 wt% to about 2.5 wt%, or even in the range of from about 1 wt% to about 2 wt%.

In a typical polymerization reaction, in a reactor containing an aqueous emulsion of an emulsifying surfactant such as a nonionic surfactant, the first stage monomer is added as a mixture by injection or by stirring. The emulsion is deoxygenated by any convenient means, such as by bubbling nitrogen, and then the polymerization is initiated by a feed initiation system. As is well known in emulsion polymerization techniques, typical initiation systems can include thermal initiation systems or redox initiators such as sodium persulfate and sodium bisulfite, or any other suitable addition polymerization catalyst. The initiation system is divided into two parts and the two parts are added during the first stage and the second stage. The initiation system is divided into stages at a certain weight percentage. The total time added was 120 minutes. If the system has 20% monomer in stage 1 (core), the 20% initiation system is added within 24 minutes (20% of 120 minutes). The initiator was stopped feeding and the mixture was cooked for 30 minutes. At the end of the cooking, the second stage monomer (shell) is added as a mixture by batch addition or by stirring. Next, the initiator feed is resumed as described above, where the total initiator is typically fed within 120 minutes. The reaction product is stirred until the polymerization is complete, typically for a period of time ranging from about 2 to about 10 hours. If necessary, the monomer emulsion can be heated to a temperature in the range of from about 20 ° C to about 95 ° C prior to the addition of the initiator. Unreacted monomers can be removed by the addition of an initiator and other methods well known in emulsion polymerization techniques. The resulting polymer emulsion product can then be discharged from the reactor and packaged for storage or use. Optionally, the pH or other physical and chemical characteristics of the emulsion can be adjusted prior to discharge from the reactor. Typically, the product emulsion has a total solids (TS) content ranging from about 10% to about 50% by weight. Typically, the total emulsion polymer content of the product emulsion ranges from about 15% to about 40% by weight, typically no more than about 40% by weight.

Generally, the emulsion polymerization is carried out at a reaction temperature in the range of from about 20 to about 99 ° C, although higher or lower temperatures can also be used.

The emulsion polymerization can be carried out in an aqueous or aqueous alcohol medium.

A surfactant may be added to the monomer composition to form a pre-emulsion, or the surfactant may be added directly to the polymerization reactor during emulsion polymerization, or both. In one embodiment, the emulsion polymerization is carried out in the presence of a surfactant, the amount of the surfactant being in the range of from about 0.1% by weight to about 10% by weight based on the total emulsion weight, in another state The sample is in the range of from about 0.5% by weight to about 8% by weight, and in another aspect in the range of from about 1.0% by weight to about 5% by weight.

In free radical emulsion polymerization, a free radical initiator is utilized which generates free radicals during the polymerization process. As used herein, the initiation system is any free radical initiation system. The free radical initiator is present in an amount ranging from about 0.01% to about 3% by weight, based on the total monomer weight. In one embodiment, the initiation system is soluble in water to at least 0.1% by weight at 25 °C. Suitable initiators include, but are not limited to, peroxides, azo initiators, and redox systems such as tert-butyl hydroperoxide and isoascorbic acid, and metal ion based initiation systems. The initiator may also include inorganic and organic peroxides such as hydrogen peroxide, benzamidine peroxide, acetam peroxide and lauryl peroxide; organic hydroperoxides such as cumene hydroperoxide and third Butyl hydrogen peroxide. In one embodiment, inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate are preferred. In another embodiment, the initiator comprises a metal ion based initiation system comprising Fe and hydrogen peroxide, and a combination of Fe and other peroxides. Organic peroxyacids such as peracetic acid can be used. The peroxide and peroxyacid may optionally be activated with a reducing agent such as sodium bisulfite, sodium formaldehyde or ascorbic acid, transition metals, hydrazine and the like. A preferred system is a redox system consisting of sodium persulfate and sodium bisulfite. Azo initiators, especially water-soluble azo initiators, can 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-() N-pyrrolidinyl)-2-ethylpropane) dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl Base] acrylamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], and the like. Oil soluble free radical generators such as 2,2'-azobisisobutyronitrile and the like, and mixtures thereof, can also be used.

Depending on the case, other emulsion polymerization additives and processing aids well known in the art of emulsion polymerization may be included in the polymerization system, such as co-emulsifiers, solvents, buffers, chelating agents, inorganic electrolytes, polymer stabilizers, biocides, Defoamer and pH adjuster.

Although a typical two-stage polymer process has been generally described above, a multi-stage or multi-layer polymer can be formed via sequential emulsion polymerization of a monomeric material in the presence of polymer particles of a previously formed emulsion polymer.

To obtain the desired properties for any particular end use, in preparing a core-shell polymer as disclosed herein, one of the following can be adjusted: (i) the relative molar ratio of the individual monomers, and (ii) the core-shell polymerization. The percentage by mass of each of the core and shell phases, (iii) the choice of monomer, crosslinker or associative monomer in any layer, (iv) the monomer mixture, the surfactant solution, and the rate of addition of the initiator solution and ( v) the molar percentage of crosslinker in either layer, as long as the molar percentage of crosslinker in the core (first stage) is lower than the percentage of mole of crosslinker in the at least one shell (subsequent stage) layer.

Dry Rheology Modifier Composition In one aspect, the rheology modifier composition can be in the form of a dry rheology modifier. In one embodiment, the rheology modifier composition can be dried by spray drying.

The invention further relates to a method of preparing a rheology modifier composition comprising co-mixing a core-shell polymer with a spray-dried adjuvant and drying the resulting mixture.

In one aspect, the presence of a spray-dried adjuvant can promote spray drying. In some embodiments, the spray dried adjuvant can be a polysaccharide such as starch or cellulose. In some embodiments, the polysaccharide is present in the emulsion polymer composition as a chain transfer agent or emulsion stabilizer during the polymerization process. In some embodiments, the spray dried adjuvant is co-mixed in the emulsion polymerization product prior to spray drying.

The core-shell polymer which is subjected to emulsion polymerization as described above and then co-mixed with the spray-dried adjuvant polymer can be dried, preferably by spray drying, to provide a dry rheology modifier in a stable powder form. combination. The spray-dried adjuvant may be a polysaccharide, and suitable examples thereof include starch and cellulose, and derivatives thereof. Other suitable spray drying adjuvants include derivatives of polyvinyl acetate such as polyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymers, and other polyvinyl alcohol copolymers.

As used herein, the term "dry rheology modifier composition" means a composition comprising at least one core-shell polymer and at least one polysaccharide, the composition comprising less than 25 wt% water, in one implementation The example comprises less than 20 wt% water, in one embodiment less than 10 wt% water, in one embodiment less than 5 wt% water, and in one embodiment less than 2 wt% water, in One embodiment contains less than 1 wt% water, and in one embodiment contains less than 0.5 wt% water in anhydrous form.

The polysaccharide component enables the resulting composition to be dried to produce a dried rheology modifier composition containing less than 25% by weight water. Without being bound by theory, the higher glass transition temperature of the salty polysaccharide polymer makes 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-dried adjuvant is at least about 20% by weight of the dry rheology modifier composition, preferably at least about 25 wt% of the dry rheology modifier composition, and most Preferably, at least about 30% by weight of the dried rheology modifier composition. The maximum weight percentage of the polysaccharide polymer or other spray-dried adjuvant is no more than about 90% by weight of the dry rheology modifier composition, and in another embodiment is preferably the dried rheological modifier composition. Not more than about 85 wt%, and in yet another embodiment is preferably no more than about 80 wt% of the dried rheology modifier composition.

In yet another embodiment, the dried rheology modifier composition comprises a mixture of products of at least two different core-shell copolymer compositions.

In yet another embodiment, the dried rheology modifier composition comprises more than one polysaccharide polymer or other spray dried adjuvant.

Optionally, prior to the drying step, adding a second composition comprising a second core-shell polymer and optionally a second polysaccharide polymer or other spray-dried adjuvant, wherein the second composition The second core-shell polymer and optionally the second polysaccharide polymer or other spray dried adjuvant may each be the same or different from the at least one core-shell polymer and the at least one polysaccharide polymer in the initial polymer blend, respectively .

The particle size of the solid product can be adjusted using methods known in the art, such as milling.

Spray Drying Adjuvant Polymer In one aspect, the rheology modifier as disclosed herein can be co-mixed with the spray dried adjuvant polymer prior to spray drying. Suitable spray-dried adjuvant polymers include polysaccharide polymers including, but not limited to, starch and starch derivatives, cellulose and cellulose derivatives, and gums; and polyvinyl acetate derivatives.

Polysaccharide polymers Polysaccharides useful as spray-dried adjuvant polymers can be derived from plant, animal and microbial sources. Examples of such polysaccharides include starch, cellulose, gums (e.g., acacia, guar gum, and celery), alginate, pectin, carrageenan, inulin, and lysine, as well as the foregoing derivative. Those skilled in the art will recognize that polysaccharides may require depolymerization or derivatization to be water soluble. For example, it may be desirable to depolymerize starch to a molecular weight of 10 million or less to have water solubility. Similarly, cellulose derivatization, such as carboxymethyl cellulose, may be required to have water solubility.

The polysaccharide-based spray-dried adjuvant polymer may have a weight average molecular weight of 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.

Starch and Starch Derivatives Starch includes starches derived from corn and conventional corn hybrids such as waxy corn and high amylose (more than 40% amylose) corn, as well as other starches such as potato, tapioca, and wheat. , rice, peas, sago, oats, barley, semolina and leeks, including conventional hybrids or genetically engineered materials. Such starches may belong to natural varieties or hybrids produced by conventional breeding programs or by artificial genetic manipulation. Such hybrids include, but are not limited to, waxy forms (starch with less or no amylose) and high amylose cultivars. Waxy starch is generally defined as having about 5% or less amylose and sometimes containing about 2% or less amylose. In one embodiment, the waxy starch has about 95% or more of amylopectin. High amylose starch is defined as having about 40% or more of amylose (except for pea starch having a high amylose content of about 27% or more of amylose). In another embodiment, the high amylose starch has an amylose content of about 60% or more of the amylose. In addition, starches having altered chain lengths and branching points are also included in the present application.

In one embodiment, preferred polysaccharide starches and starch derivatives include, but are not limited to, heat and/or mechanically treated starch; starch oxidized, hydrolyzed or enzymatically degraded; and chemically modified starch. Such preferred polysaccharides include maltodextrin, dextrin, pyrodextrin, oxidized starch, cyclodextrin and substituted cyclodextrin, as well as higher molecular weight starches, or derivatives thereof. In another preferred embodiment, starch-based maltodextrin, waxy dextrin, waxy pyrodextrin, waxy oxidized starch, and higher molecular weight waxy starch, or derivatives thereof, are preferred. The best starch waxy maltodextrin. Chemical modification includes hydrolysis, esterification or etherification under the action of an acid, an enzyme, an oxidizing agent or heat. The chemically modified starch may be cationic, anionic, nonionic or amphoteric or hydrophobic after chemical modification.

In one embodiment, the polysaccharide is maltodextrin. Maltodextrin has a polymer having a d-glucose unit mainly linked by an α-1,4 bond and having a dextrose equivalent ("DE") of about 20 or less. Dextrose equivalent is a measure of the degree of hydrolysis of the starch. It is determined by measuring the amount of reducing sugar in the sample relative to dextrose (glucose). The DE system of dextrose 100 indicates 100% hydrolysis. The DE value provides the degree of hydrolysis (eg, 10 DE is more hydrolyzed than 5 DE maltodextrin). Maltodextrin is used in the form of a white powder or concentrated solution and is prepared by partially hydrolyzing the starch with an acid and/or an enzyme.

Suitable polysaccharides may further comprise corn syrup. Corn syrup is defined as a degraded starch product having a DE of from 27 to 95. Examples of specialty corn syrups include high fructose corn syrup and high maltose corn syrup. Although not strictly defined, monosaccharides and oligosaccharides such as galactose, mannose, sucrose, maltose, fructose, ribose, trehalose, lactose and the like can also be used as spray-dried adjuvants in the disclosed compositions and methods. And for the purposes herein, it is considered to be within the scope of spray-dried adjuvant polymers.

In one embodiment, the DE of the polysaccharide is about 65 or less, 45 or less, 20 or less, in another embodiment DE is about 15 or less, and in yet another embodiment DE is About 5 or less. In one embodiment, the DE of the polysaccharide is in the range of at least about 1 at the lower limit.

In one embodiment, the polysaccharide is a pregelatinized starch and a derivative thereof. Pregelatinized starches suitable herein have been treated with heat, moisture or chemical agents to destroy the natural particulate structure and to render the starch soluble in water below the gelatinization temperature of the native starch. For the purposes of this application, pregelatinized starch is also known as cold water soluble starch (CWS) and the terms are used interchangeably. For a review of how to prepare pregelatinized starch, see (Starch; Chemistry and Technology, R. L. Whistler, Second Edition, Academic Press, Inc. New York, 1984, pp. 670-673). Alternatively, such products can be prepared by co-jet cooking coupled to a spray dryer (see Kasica et al., U.S. Patent 5,571,552). Pregelatinization can be carried out by various methods including, but not limited to, drum drying, spray cooking or extrusion. In addition to pregelatinization, the starch suitable for use herein can be further modified to contain anionic, cationic, nonionic, 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 starch can be prepared in a granular form and then rendered soluble in cold water or can be cooked and subsequently reacted in solution to produce a polymer.

Cellulose and Cellulose Derivatives In one embodiment, the polysaccharide is cellulose and/or a derivative thereof, such as carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxymethyl Hydroxyethyl cellulose (CMHEC), hydroxypropyl cellulose, sulfoethyl cellulose and its derivatives, ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), and Hydrophobic modified ethyl hydroxyethyl cellulose HM-EHEC, some of which were purchased from AkzoNobel. Polysaccharides also include cellulose derivatives, including plant heteropolysaccharides, commonly referred to as hemicellulose, which are by-products of the pulp and paper industry. Hemicelluloses include xylan, glucuronoxylan, arabinoxylan, glucomannan, and xyloglucan. Xylan is the most common heteropolysaccharide and is preferred. Polysaccharides, such as degradation products of cellulose, such as cellobiose, are suitable for preparing polymers as disclosed herein. Polysaccharides also include inulin and its derivatives, such as carboxymethyl inulin. In one embodiment, preferred cellulosic materials are carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl cellulose, ethyl Hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC) and hydrophobically modified ethyl hydroxyethyl cellulose (HM-EHEC).

Gum suitable for polysaccharides including guar gum, unwashed guar gum, washed guar gum, cationic guar gum, carboxymethyl guar gum (CM guar gum) , hydroxyethyl guar gum (HE guar gum), hydroxypropyl guar gum (HP guar gum), carboxymethyl hydroxypropyl guar gum (CMHP guar gum), hydrophobic Modified guar gum (HM guar gum), hydrophobic modified carboxymethyl guar gum (HMCM guar gum), hydrophobic modified hydroxyethyl guar gum (HMHE guar) Gum), hydrophobically modified hydroxypropyl guar gum (HMHP guar gum), cationic hydrophobic modified hydroxypropyl guar gum (cationic HMHP guar gum), hydrophobically modified carboxy Methyl hydroxypropyl guar gum (HMCMHP guar gum), hydrophobically modified cationic guar gum (HM cationic guar gum), guar gum hydroxypropyltrimonium chloride, hydroxy Propyl guar gum hydroxypropyl triammonium chloride.

Polyvinyl acetate derivatives Suitable for polyvinyl acetate and its derivatives including polyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymer and vinyl acetate copolymer, and polyvinyl alcohol/polyvinyl acetate The graft copolymer, as well as polyvinylpyrrolidone. The derivative of polyvinyl acetate may be anionic such as a copolymer with an anionic ethylenically unsaturated monomer or a nonionic such as a copolymer with a nonionic ethylenically unsaturated monomer.

The polyvinyl acetate derivative may be a fully or partially saponified and/or modified polyvinyl alcohol having a degree of hydrolysis of preferably from about 70 to 100 mol%, particularly from about 80 to 98 mol%, and in a 4% aqueous solution. The Hoppler viscosity is preferably from 1 to 50 mPas, especially from about 3 to 40 mPas (measured at 20 ° C according to DIN 53015). If the polyvinyl acetate-based polymer reacts to form a dry emulsion rheology modifier, it may have a weight average molecular weight of about 1,000,000 or less, or 500,000 or less, or about 100,000 or less. The polyvinyl acetate-based polymer may have a weight average molecular weight of about 100,000 or less, or about 50,000 or less, or about 10,000 or less.

In one embodiment of the invention, the protective water soluble polymer is selected from the group consisting of polyvinylpyrrolidone and derivatives. A polyvinylpyrrolidone homopolymer is preferred, but a copolymer can also be used. When polyvinylpyrrolidone is used, the polymer can have any molecular weight as long as the rheology modifier remains effective. For example, when polyvinylpyrrolidone is used, it may specifically be PVP K-15 (average molecular weight 10,000), K-30 (average molecular weight 40,000) or K-90 (average molecular weight is made by Ashland). 360,000).

The weight average molecular weight of the spray-dried adjuvant polymer as starch can be determined by the following procedure:
A 2.00 mg/ml starch sample was prepared in a solution of 0.03 M NaCl in dimethylformamide (DMSO). The starch sample solution was heated at 100 ° C for 60 minutes and became clear after heating. The solutions were filtered using a 0.45 micron filter. The molecular weight was measured by gel permeation chromatography using multi-angle light scattering ("GPC/MALS") detection as follows:
String Penogel Linear 2 30 cm × 7.8mm
Temperature 60 ° C
Solvent 0.03M NaCl in DMSO solution flow rate 0.60 ml / min
Detecting Wyatt Heleos 18 Angle MALS and Optilab Rex Refractive Index

The dried rheology modifier compositions disclosed herein can comprise an anticaking agent. Examples of anti-caking agents include, but are not limited to, kaolin, aluminosilicate, cerium oxide, aluminum cerium oxide, calcium carbonate, magnesium carbonate, magnesium sulfate, talc, gypsum, cerium oxide, and cerium, and mixture. The particle size of the anti-caking agent is preferably in the range of 100 nm to 10 μm. More than one anti-caking agent can be used.

When the core-shell rheology modifier of the present invention is dried in the presence of a spray dried adjuvant polymer, a core-shell polymer is prepared as described above. In one embodiment, a spray dried adjuvant polymer, such as starch, may be present during the polymerization process. In another embodiment, a spray dried adjuvant polymer can be added to the prepared core-shell emulsion composition. The core-shell polymer composition can be diluted prior to the addition of the spray dried adjuvant polymer. In one embodiment, an aqueous composition having a spray dried adjuvant polymer is added to the core-shell polymer composition in a suitable mixing amount. Alternatively, the core-shell polymer composition can be added to an aqueous composition having a spray dried adjuvant polymer. In one embodiment, the dried spray dried adjuvant polymer is added to the core-shell polymer composition while being diluted in water. The weight percentage of the core-shell in the core-shell composition may range from 5 to 50% and preferably from 10 to 30%. The solids in the aqueous composition having the spray dried adjuvant polymer may range from 5 to 50% and preferably from 10 to 30%. The solids in the aqueous blend of the core-shell polymer and the spray-dried adjuvant polymer may range from 5 to 50%, preferably from 10 to 30%, and most preferably from 15 to 25%. . This blend can be dried as it is or, if necessary, further diluted prior to drying. A preferred drying method is spray drying. However, other methods such as drum drying, tray drying, fluidized bed drying, and the like can also be used. The spray dried adjuvant polymers described herein will be suitable for use in any of these alternative drying methods.

Product Formulations In the following description of product formulations which may be prepared using the rheology modifiers disclosed herein, the term "rheological modifier" is intended to include in the form of a liquid emulsion or in common, unless otherwise stated. The core-shell polymer is dried in solid form in the presence or absence of a mixed spray dried adjuvant polymer.

A product formulation comprising a rheology modifier composition as disclosed herein can be selected from the group consisting of personal care products, home care products, healthcare products, institutional and industrial care products, adhesives, coatings, agriculture, for the electronic components industry. Formulations and formulations used in the construction industry, and other applications. The application further relates to the use of a rheology modifier composition as disclosed herein as a component of such a product formulation and as an active ingredient of a product formulation.

As used herein, "home care products" include, but are not limited to, used in household dwellings for surface cleaning or maintenance of sanitary conditions, such as products used in kitchens and bathrooms (eg, hard surface cleaners, furniture polishes, manuals). And automatic dishwashing formulations, toilet bowl cleaners and disinfectants), as well as laundry products for fabric care and cleaning (eg detergents, fabric conditioners, pre-treatment detergents), and the like.

As used herein, the term "health products" includes, but is not limited to, pharmaceuticals (controlled release medicines); cosmeceutical products; oral care (mouth and teeth) products, such as oral suspensions, mouthwashes, toothpastes. , tooth powders and analogues; and over-the-counter products and devices (surface and transdermal) for external use on the skin, including human and animal skin, scalp, nails and mucous membranes, such as patches, plasters and the like, for improvement Health-related or medical conditions, for daily maintenance of hygiene or health, and similar applications.

As used herein, the term "institutional and industrial care" ("I&I") includes, but is not limited to, in institutional and industrial environments, textile treatment (eg textile conditioners, carpets and bedding cleaners), car care (eg manual and Automatic car wash cleaners, tire polishes, leather conditioners, liquid vehicle polishes, plastic polishes and conditioners), paints and coatings, and products for surface cleaning or maintenance in similar situations.

In agricultural applications, the disclosed rheology modifier compositions are useful in agrochemical formulations. It can stabilize, thicken, disperse or suspend agrochemical formulations due to its rheological properties. A particularly useful agrochemical formulation is a suspension concentrate (SC). Another particularly useful agrochemical formulation is a solid formulation of wettable powder (WP), water dispersible granules (WDG), and water soluble granules (WSG). When the agrochemical formulation comprising the disclosed rheology modifier composition is diluted in water, the disclosed rheology modifier composition can stabilize or suspend the agrochemical in a dilute aqueous system.

In oil field applications, the disclosed rheology modifier compositions can be used in formulations used in fracturing operations. In some applications, it is desirable to use a liquid composition that is viscoelastic. Such compositions can be used, for example, to stimulate an oil well that is hindered by a flow path resulting in insufficient hydrocarbon production. This technique is known as (hydraulic) fracturing and the specialized fluid used in the art is referred to as a fracturing fluid. For such fracturing processes, the compositions are typically injected into the formation via a wellbore under sufficient pressure to create fractures in the formation rock, thereby creating channels that allow hydrocarbons to more easily flow through the channels into the wellbore. . In one embodiment, the fracturing fluid should produce a very small pressure drop in the conduit within the wellbore during placement and have a suitable viscosity to carry the proppant (sand) material that prevents the fracture from closing. In addition, the fracturing fluid should have a very low leak rate to avoid migration of the fluid into the formation rock, whereby fractures can be clearly generated and propagated and should be degraded to avoid leaving residual material that may prevent hydrocarbons from accurately flowing into the wellbore.

Other formulations that can be used with the disclosed rheology modifiers include binders, asphalt emulsions, paints and coatings, super adsorbents, and other industrial applications.

In one embodiment, the rheology modifier composition added to the formulations may be at least about 0.1% modifier, more preferably at least about 0.5% by weight of the formulation, based on the weight of the formulation. And preferably at least about 1.0% modifier by weight of the formulation. The rheology modifier composition added to such formulations may be up to about 20% modifier based on the weight of the formulation, more preferably up to about 15% modifier by weight of the formulation, and most preferably The weight of the formulation is up to about 10% modifier.

Rheology modifiers can be used in aqueous protective coating compositions. The desired level of such rheology modifier increases and maintains viscosity under specific processing conditions and end use conditions. In particular, rheology modifiers can be used in all types of coatings, such as decorative and protective coatings. Rheology modifiers can be used as rheology modifiers in water-based protective coating compositions. Water-based protective coating compositions are commonly referred to as latex paints or dispersion paints and have been around for many years. Adjusting the rheological properties of such aqueous protective coating compositions is challenging because the coating composition must provide good flatness and excellent sag resistance, and its viscosity should not be too low or too high, so that Can be easily applied.

The polymers disclosed herein can be used in paper coating applications. Paper coating formulations impart certain qualities to the paper, including weight, surface gloss, smoothness, or low ink absorbency. The uniform coating on the paper promotes enhanced printing surfaces and properties such as coverage, smoothness and gloss can 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 paper are affected by the base sheet (fiber type, sheet formation, internal sizing and substrate weight), coating material (pig type, binder type, rheology modifier, water retention aid, Lubricants, defoamers, etc.), coating formulations (ratio of coating components, solids and pH), coating process (type and speed of coating application), coating weight, drying conditions (dryer type, drying temperature, Effect of drying time and final moisture content).

Paper coating formulations typically contain three main components: pigments, binders, and additives. The pigment improves the printing and optical properties of the sheet, the binder causes the pigment particles to adhere to each other and to the sheet, and the additive aids in the coating process or enhances sheet properties. An important additive used in paper coating formulations is a rheology modifier. Rheology modifiers are used to achieve the desired rheological properties and improved flow during the coating process.

The rheology modifier compositions disclosed herein, particularly those rheology modifiers containing an acid swellable polymer, expand when neutralized in a coating formulation, thereby increasing viscosity. This increase in viscosity helps to control the pick-up rate on the applicator roll, affects the flow characteristics during the metering process, and changes the fixing and leveling characteristics after the metering step in the paint process. The ratio of hydrophilic monomer to hydrophobic monomer in the polymer affects the water holding characteristics and the degree of interaction with the binder. The molecular weight of the polymer and its branching affect the low shear viscosity and high shear viscosity profile.

Rheology modifier compositions containing hydrophobically modified acid swellable polymers can also be used in paper coating applications. These products are very effective in lightweight coatings (LWC). These products are used in high solids carbonate coatings that require water retention and produce very low shear viscosity.

As used herein, the term "personal care product" includes, but is not limited to, cosmetics, toiletries, cosmetic preparations, skin care auxiliaries, insect repellents, skin, hair and scalp suitable for use on the body, including humans and animals. Personal hygiene and cleaning products for nails. Personal care applications include, but are not limited to, formulations for hair styling gels, skin creams, tanning lotions, sunscreens, moisturizers, toothpastes, medical and first aid ointments, cosmetic ointments, suppositories, cleansing Agents, lip glosses, mascaras, hair dyes, moisturizers, shampoos, body soaps and deodorants, hair care and styling formulations, shaving preparations, depilatory and hand sanitizers, including alcohol-based hand sanitizers.

Suitable personal care applications also include formulations for use on the skin, eyelashes or eyebrows, including but not limited to cosmetic compositions such as mascara, facial foundation, eyeliner, lipstick and make-up products; skin care compositions, Such as moisturizing lotions and creams, skin treatment products, skin protection products in the form of lotions, liquids, sticks or gels; sun care products such as sunscreens, sunscreen lotions, lotions, creams, sunscreen lotions, Liquid/alcohol sunscreen spray, sunscreen water-based gel, broad-spectrum sunscreen containing UVA and UVB active agents, sunscreen containing organic and inorganic active agents, sunscreen containing a combination of organic and inorganic active agents, tanning products, Self-tanning products and after-sun products. Particularly suitable compositions are personal care lotions, and more particularly, sun care compositions such as sunscreen lotions and sunscreen lotions. The personal care compositions can be in any form including, but not limited to, sprays, lotions, lotions, gels, liquids, sticks, waxes, pastes, powders, and creams.

Personal care compositions may also include other optional ingredients commonly used in the industry, and such components will vary greatly depending on the type of composition and the desired functionality and characteristics. Such components include, but are not limited to, thickeners, suspending agents, emulsifiers, UV filters, sunscreen actives, humectants, moisturizers, emollients, oils, waxes, solvents, chelating agents, vitamins, Antioxidants, botanical extracts, polyoxyxides, neutralizers, preservatives, fragrances, dyes, pigments, conditioners, polymers, antiperspirant actives, anti-acne agents, anti-dandruff actives, interfacial activity Agent, exfoliating agent, depilatory active ingredient, film former, propellant, tanning accelerator, hair fixative and color former. These polymers are compatible with most of the other components used in conventional personal care compositions. For example, the sunscreen composition can contain at least one component selected from the group consisting of organic UV filters, inorganic UV actives, UVA and/or UVB sunscreen actives, octinoxate, Octisalate, oxybenzone, homosalate, octocrylene, avobenzene, titanium dioxide, starch, conditioners, emulsifiers, other streams Varnishing agents and thickeners, neutralizers, emollients, solvents, film formers, moisturizers, antioxidants, vitamins, chelating agents, preservatives, fragrances and zinc oxide. The 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, colorings. Agents and insecticides.

Personal care, home care, healthcare, agricultural, and I&I care compositions comprising segmented core-shell polymers can be formulated at a pH in the range of from about 0.5 to about 12. The desired pH of the compositions will depend on the particular end product application. In general, certain personal care applications require a pH range of from about 3 to about 7.5 in one aspect and from about 3.5 to about 6 in another aspect. The segmented core-shell/surfactant compositions, when formulated at low pH, produce a clear formulation while maintaining the desired rheological properties (e.g., viscosity and yield value). In another aspect, the segmented core-shell polymer/surfactant compositions, when formulated at a pH of about 6 and lower, result in a clear formulation while maintaining the desired composition comprising the composition. Rheological properties. In yet another aspect, the segmented core-shell/surfactant compositions, when formulated at a pH of about 5.0 and lower, produce a clear formulation while maintaining the desired flow of the composition comprising the same Variable characteristics. In another aspect, the segmented core-shell polymer/surfactant compositions, when formulated at a pH of from about 3.5 to about 4.5, produce a clear formulation while maintaining the desired composition thereof. Rheological properties.

In general, the range of pH values desired for home care applications will range from 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 disclosed herein can be adjusted by any combination of acidic and/or basic pH adjusting agents known in the art.

The polymers of the invention supplied are typically in the alkaline pH range. The polymer in the formulation must be activated by lowering the pH using an acidic material. A variety of acidic materials can be used as neutralizing agents/pH adjusters. Such acidic materials include organic acids and inorganic acids such as acetic acid, citric acid, tartaric acid, alpha-hydroxy acid, beta-hydroxy acid, salicylic acid, lactic acid, glycolic acid and natural fruit acid, or inorganic acids such as hydrochloric acid and nitric acid. , sulfuric acid, aminosulfonic acid, phosphoric acid, and combinations thereof. Other acidic materials may be used singly or in combination with the above inorganic and organic acids. Such materials include materials that are capable of reducing the pH of the composition when combined in a composition comprising a segmented core-shell polymer. The skilled artisan will recognize that an acidic pH adjusting agent can provide more than one function. For example, acidic preservative compounds and acid-based cosmetic medicinal compounds (eg, alpha-hydroxy acids and beta-hydroxy acids) provide not only their primary preservatives and cosmetic medicinal properties, but they can also be used to reduce or maintain The pH of the formulation.

Buffering agents can be used in the disclosed compositions. Suitable buffering agents include, but are not limited to, alkali or alkaline earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, 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 used in any amount necessary to obtain and/or maintain the desired pH of the composition.

The core-shell polymers disclosed herein can be formulated in the presence or absence of at least one surfactant. Such compositions may comprise optional additives, adjuvants, and any combination of benefit agents suitable for the personal care, home care, healthcare, and institutional and industrial care products known in the art. The selection and amount of each optional component employed will vary with the purpose and nature of the final product and can be readily determined by one skilled in the art of the formulation and from the literature. It will be appreciated that various additives, adjuvants, and benefit agents, as well as the components set forth herein, can be used in the composition for more than one function, such as surfactants, emulsifiers, solubilizers, conditioners, emollients, moisturizers. Agents, lubricants, pH adjusters and acid based preservatives.

Although the overlapping weight ranges of the various components and ingredients that may be included in the compositions have been set forth in the selected embodiments and aspects disclosed herein, it is apparent that the disclosed personal care, home care, medical care The specific amount of each component in the health and I&I care compositions will be selected from the range disclosed herein, thereby adjusting the amount of each component such that the sum of all components in the composition will total 100% by weight. The amount used will vary with the purpose and nature of the desired product and can be readily determined by those skilled in the art of formulation and from the literature.

Optional additives and adjuvants include, but are not limited to, insoluble materials, pharmaceutical and cosmetic active agents, chelating agents, conditioning agents, diluents, solvents, fragrances, humectants, lubricants, solubilizers, emollients, shading Agents, colorants, antidandruff agents, preservatives, coating aids, emulsifiers, sunscreens, fixed polymers, botanicals, viscosity modifiers and the like, as well as for enhancing and maintaining the personal care required, A variety of other optional components of the characteristics of home care, healthcare, agriculture, and I&I care compositions.

When used in personal care formulations, such as hair care and styling formulations, such as styling gels, optional additional ingredients may be added to provide a variety of other additional characteristics. Various other additives, such as active and functional ingredients, can be included in the personal care formulations as defined herein. Such ingredients include, but are not limited to, emollients, humectants, thickeners, electrolytes and salt surfactants, UV inhibitors, immobilized polymers, preservatives, pigments, dyes, colorants, alpha hydroxy acids, Aesthetic enhancers such as starch flavors and fragrances, film formers (water repellents), disinfectants, antifungals, antimicrobials and other drugs, and solvents. Additionally, the conditioning agent can be used in combination with the disclosed polymers, such as cationic guar gum, cationic hydroxyethyl cellulose, cationic synthetic polymers, and cationic fatty amine derivatives. These blends help provide higher affinity and effective conditioning properties to the hair. Electrolytes and salts are particularly useful for increasing the viscosity of shampoos and improving their suspension characteristics.

Some non-limiting examples of polymers that can be used in personal care formulations with the rheology modifier compositions disclosed herein are polyoxyethylated vinyl acetate/crotonic acid copolymers, vinyl acetate crotonic acid (90). /10) Copolymer, vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer, N-octyl acrylamide/methyl acrylate/hydroxypropyl methacrylate/acrylic acid/methacrylic acid third Alkylaminoethyl ester copolymer, and methyl vinyl ether/maleic anhydride (50/50) copolymer monobutylated with butanol or ethanol, acrylic acid/ethyl acrylate/N-tert-butyl- Acrylamide terpolymer, and poly(methacrylic acid/acrylamidomethylpropanesulfonic acid), acrylate copolymer, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymerization , acrylate/octyl acrylamide copolymer, VA/crotonate/vinyl neodecanoate copolymer, poly(N-vinylacetamide), poly(N-vinylformamide), Modified corn starch, sodium polystyrene sulfonate, poly quaternary ammonium such as polytetramine-4, polytetraamethylene-7, polytetraammonium-10, poly Ammonium-11, polytetraamethylene-16, polytetraammonium-28, polytetraammonium-29, polytetraammonium-46, polyether-1, polyurethane, VA/acrylate Lauryl methacrylate copolymer, adipic acid/dimethylaminohydroxypropyl diethyl acrylate/acrylate copolymer, methacryloylethylbetaine/acrylate copolymer, PVP/methyl Dimethylaminoethyl acrylate copolymer, PVP/DMAPA acrylate copolymer, PVP/vinyl caprolactam/DMAPA acrylate copolymer, vinyl caprolactam/PVP/dimethylamine methacrylate Ethyl ester copolymer, VA / butyl maleate / isobornyl acrylate copolymer, VA / crotonate copolymer, acrylate / acrylamide copolymer, VA / crotonate / vinyl propionate Copolymer, vinyl pyrrolidone/vinyl acetate/vinyl propionate terpolymer, VA/crotonate, cationic and amphoteric guar gum, polyvinylpyrrolidone (PVP), polyvinyl Pyrrolidone/vinyl acetate copolymer, PVP acrylate copolymer, vinyl acetate/crotonic acid/vinyl propionate, acrylate/acrylamide, acrylic acid /octyl acrylamide, acrylate/hydroxy acrylate copolymer, and alkyl methyl ether/maleic anhydride alkyl ester, diethylene glycol / cyclohexane dimethanol / isophthalate / Sulfoisophthalate copolymer, vinyl acetate/butyl maleate and isobornyl acrylate copolymer, vinyl caprolactam/PVP/dimethylaminoethyl methacrylate, Vinyl acetate/alkyl maleate half ester/N-substituted acrylamide terpolymer, vinyl caprolactam/vinyl pyrrolidone/methyl methacrylate fluorenyl amide Propyltrimethylammonium terpolymer, methacrylate/acrylate copolymer/amine salt, polyvinyl caprolactam, polyurethane, hydroxypropyl guar gum, hydroxypropyl Guar gum hydroxypropyltrimethylammonium chloride, poly(methacrylic acid/acrylamidomethylpropane sulfonic acid), polyurethane/acrylate copolymer and hydroxypropyltrimethyl chloride Alkaloid guar gum, especially acrylate copolymer, octyl acrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylate/octyl propylene oxime Amine copolymer, VA/crotonate/vinyl neodecanoate copolymer, poly(N-vinylacetamide), poly(N-vinylformamide), polyurethane, modified corn Starch, sodium polystyrene sulfonate, polytetraamethylene-4, polytetraammonium-10, and polyurethane/acrylate copolymer.

Suitable cationic polymers which are useful in formulations comprising the disclosed rheology modifier compositions are those which are best known under the CTFA class name polyquaternary ammonium. Some examples of such polymers are polytetra-ammonium 6, poly-quaternary ammonium 7, poly-quaternary ammonium 10, polytetra-ammonium 11, poly-quaternary ammonium 16, poly-quaternary ammonium 22, and poly-quaternary ammonium 28. Poly quaternary ammonium 4, poly quaternary ammonium 37, quaternary ammonium salt-8, quaternary ammonium salt-14, quaternary ammonium salt-15, quaternary ammonium salt-18, quaternary ammonium salt-22, quaternary ammonium Salt-24, quaternary ammonium salt-26, quaternary ammonium salt-27, quaternary ammonium salt-30, quaternary ammonium salt-33, quaternary ammonium salt-53, quaternary ammonium salt-60, quaternary ammonium salt -61, quaternary ammonium salt-72, quaternary ammonium salt-78, quaternary ammonium salt-80, quaternary ammonium salt-81, quaternary ammonium salt-82, quaternary ammonium salt-83 and quaternary ammonium salt- 84.

Cellulose-type polymers of natural origin known from the Polymer JR® type from Amerchol, polytetra-ammonium 10 or cationic guar gum known from the trade name Jaguar® by Rhone-Poulenc, and guar The hydroxypropyltrimethylammonium chloride, chitosan and chitin may also be included in the personal care formulation as a cationic natural polymer in a formulation comprising the disclosed rheology modifier composition.

Rheology modifiers can be used in personal care compositions, and such personal care compositions can also include cosmetically acceptable ingredients. The ingredient may be an emollient, a fragrance, an exfoliating agent, a drug, a whitening agent, a acne therapeutic, a preservative, a vitamin, a protein, a cleanser or a conditioner.

Examples of detergents suitable for use in the compositions herein include, but are not limited to, sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), ammonium lauryl ether sulfate (ALES), alkanolamines, sulphur Acid alkyl aryl ester, alkyl aryl sulfonic acid, amine oxide, amine, sulfonated amine and decylamine, betaine, block polymer, carboxylated alcohol or alkylphenol ethoxylate, sulfonic acid diphenyl Ester derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines and/or decylamines, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters (except Ethylene) Alcohol, glycerin, etc., fluorocarbon-based surfactant, glyceride, ethylene glycol ester, heterocyclic compound, imidazoline and imidazoline derivative, isethionate, lanolin-based derivative , lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, olefin sulfonates, phosphates, phosphorus-containing organic derivatives, polymers (polysaccharides, acrylic acid, acrylonitrile) Amine, propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated Alkyl phenols, protein-based surfactants, quaternary ammonium surfactants, creatinine derivatives, polyoxo-based surfactants, soaps, sorbitan derivatives, sucrose and glucose esters and derivatives Sulfates and sulfonates of oils and fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, benzene, different Sulfonates of propylbenzene, toluene and xylene, sulfonate of condensed naphthalene, sulfonate of dodecyl and tridecylbenzene, sulfonate of naphthalene and alkylnaphthalene, sulfonate of petroleum, Sulfosuccinyl glutamate, sulfosuccinate and derivatives.

In one embodiment, particularly in the case of formulating shampoos or cleansing formulations, such as body cleansers, the formulation further comprises a sulfate-free surfactant. Examples of sulfate-free surfactants include, but are not limited to, ethoxylated alkyl phenols, ethoxylated amines and/or guanamines, ethoxylated fatty acids, ethoxylated fatty esters, and oils, Fatty esters (except ethylene glycol, glycerol, etc.), fluorocarbon-based surfactants, glycerides, ethylene glycol esters, heterocyclic compounds, imidazolines and imidazolines, isethionates, based on wool Fat derivatives, lecithin and lecithin derivatives, lignin and lignin derivatives, methyl esters, monoglycerides and derivatives, phosphates, phosphorus-containing organic derivatives, polymers (polysaccharides, acrylic acid, acrylamide) , propoxylated and ethoxylated fatty acids, propoxylated and ethoxylated fatty alcohols, propoxylated and ethoxylated alkyl phenols, protein-based surfactants, quaternary ammonium interfacial activity Agent, creatinine derivative, polyoxon-based surfactant, α-olefin sulfonate, alkyl aryl sulfonate, sulfonate of oil and fatty acid, sulfonate of ethoxylated alkylphenol , benzene, cumene, toluene and xylene sulfonate, condensed naphthalene sulfonate, dodecyl and ten Sulfonates of trialkylbenzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfonates of petroleum and derivatives thereof. In one embodiment, the sulfate-free surfactant is a sulfonate or ethoxylate.

In another embodiment, the formulation contains a sulfated surfactant. Some non-limiting examples of sulfated surfactants are sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), alkanolamines, alkyl aryl sulfonic acids, sulfates of oils and fatty acids, ethoxylated Sulfates of alkylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfosuccinaminates, sulfosuccinates and derivatives thereof.

In other embodiments, the personal care formulation comprising the disclosed rheology modifier is a hair setting or styling formulation, such as a hair gel, mousse, spray, cream, wax or styling lotion. Surprisingly, it has been discovered that some embodiments of the rheology modifiers disclosed herein can be formulated into such hair fixing and styling formulations, thereby not only producing the desired rheological modification, but also producing particle suspension characteristics and hair retention characteristics. . When the disclosed rheology modifiers are used in such formulations, other additives conventionally used to provide such functionality can be reduced or even removed.

In addition to the polymers disclosed herein, the personal care compositions may include other ingredients as appropriate. Some non-limiting examples of such ingredients include, but are not limited to, conditioning agents such as polyoxyphthalic oils, i.e., volatile or non-volatile, natural and synthetic oils. Suitable polyoxyxides which may be added to such compositions include dimethylpolyoxane from Dow Corning, dimethylpolyoxyalkanol, polydimethyloxane, polyoxane having various DC fluid ranges oil. It can also be used with natural oils such as olive oil, almond oil, avocado oil, wheat germ oil, castor oil; and 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 oleoresin Acid ester. Some examples of nonionic modifiers are polyols such as glycerol, ethylene glycol and derivatives, polyethylene glycol (which may be from Union Carbide under the trade name Carbowax® PEG and known from the Polyox® WSR series from Amerchol) , polyglycerol, polyethylene glycol mono- or di-fatty acid ester.

Preservatives can be used in personal care formulations to provide long term storage stability. These preservatives may be selected from the group consisting of methylparaben, propylparaben, butylparaben, DMDM carbendazim, imidazolidinyl urea, glutaraldehyde, phenoxyethanol, benzza Benzalkonium chloride, methane ammonium chloride, benzethonium chloride, benzyl alcohol, chlorobenzyl alcohol, methyl chloroisothiazolone, methyl isothiazolinone, sodium benzoate, chlorinated Acetamide, triclosan, iodopropynyl butyl carbamate, sodium pyrithione, and zinc pyrithione.

The rheology modifier compositions disclosed herein can also be used in liquid detergent compositions, including one or more surfactants, such as selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic Surfactant surfactant. In one embodiment, preferred surfactants are suitable for use in isotropic liquid cleanser compositions and are a mixture of anionic and nonionic surfactants, although it will be understood that any surfactant may be used alone or Used in combination with any other surfactant. Such liquid detergent systems, as well as the surfactants used therein, are described in US 6,462,013, which is incorporated herein by reference in its entirety.

Liquid detergent compositions comprising the disclosed rheology modifier compositions can also be used in liquid detergent compositions and can further comprise at least one additive, as appropriate. Suitable additives may include, for example, synergists, dispersants, polymers, ion exchangers, alkalis, corrosion resistant materials, anti-redeposition materials, antistatic agents, optical brighteners, perfumes, fragrances, dyes, fillers, oils , chelating agents, enzymes, fabric brighteners, brighteners, foaming control agents, solvents, solubilizers, bleaches, bleach precursors, buffers, detergents, antifouling agents, fabric softeners, and shading Agent. In general, such additives and amounts thereof are known to those skilled in the art.

Formulation Surfactant In one aspect, the stable aqueous composition comprises a segmented core-shell rheology modifier and a surfactant as disclosed herein. Suitable surfactants include anionic, cationic, amphoteric and nonionic surfactants, as well as mixtures thereof. Such compositions can be used, for example, to contain various components such as substantially insoluble materials that require suspension or stabilization (eg, polyoxyxides, oily materials, pearlescent materials, aesthetic and cosmetic medical beads and particles, bubbles, exfoliating agents). Agents and the like) in personal care cleansing compositions.

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 sulfonates, alkyl aryl sulfonates, alpha olefin sulfonates, alkyl decyl sulfonates, Alkyl polyether sulfate, alkyl guanamine ether sulfate, alkyl monoglyceryl ether sulfate, alkyl monoglyceride sulfate, alkyl monoglyceride sulfonate, alkyl succinate, alkane Sulfosuccinate, alkylsulfosuccinamide, alkyl ether sulfosuccinate, alkyl sulfonyl sulfosuccinate; alkyl sulfoacetate, alkyl phosphate, alkane Ether ether phosphate, alkyl ether carboxylate, alkyl guanamine ether carboxylate, N-alkyl amino acid, N-decyl amino acid, alkyl peptide, N-mercapto taurate An alkyl isethionate, a carboxylate, wherein the indenyl is derived from a fatty acid; and an alkali metal, alkaline earth metal, ammonium, amine, and triethanolamine salt thereof.

In one aspect, the cationic portion of the salt is selected from the group consisting of sodium, potassium, magnesium, ammonium, monoethanolamine salts, diethanolamine salts, and triethanolamine salts, as well as monoisopropylamine salts, diisopropylamine salts, and triisopropylamine salts. The alkyl and sulfhydryl groups in the aforementioned surfactants contain from about 6 to about 24 carbon atoms in one aspect, from 8 to 22 carbon atoms in another aspect, and about 12 in another aspect. Up to 18 carbon atoms and can be unsaturated. The aryl group in the surfactant is selected from phenyl or benzyl. The above ether-containing surfactant may contain from 1 to 10 ethylene oxide and/or propylene oxide units per surfactant molecule in one aspect and each surfactant molecule in another aspect. 1 to 3 ethylene oxide units.

Examples of suitable anionic surfactants include lauryl ether sulfate ethoxylated with 1, 2 and 3 mol of ethylene oxide, tridecyl polyether sulfate, myristyl sulfate, C ₁₂ -C ₁₃ alkanol ether sulfate, C ₁₂ -C ₁₄ alkanol ether sulfate and C ₁₂ -C ₁₅ alkanol ether sulfate sodium, potassium, lithium, magnesium and ammonium salts; sodium, potassium, lithium , magnesium, ammonium and triethanolamine lauryl sulfate, cocoyl sulfate, tridecyl sulfate, myristyl sulfate, cetyl sulfate, cetearyl sulfate, stearyl sulfate , oil-based sulfate and tallow sulfate, disodium lauryl sulfosuccinate, disodium lauryl ether sulfosuccinate, sodium cocoyl isethionate, sodium C ₁₂ -C ₁₄ olefin sulfonate, Sodium lauryl ether-6, sodium methacrylate, sodium taurate, sodium cocoyl glycinate, sodium myristate, sodium dodecyl benzene sulfonate, cocoyl ketone Sodium sarcosinate, sodium cocoyl glutamate, potassium myristyl glutamate, triethanolamine monolauryl phosphate, and fatty acid soaps, including saturations containing from about 8 to about 22 carbon atoms Sodium, potassium, ammonium and triethanolamine salts of unsaturated fatty acids.

The cationic surfactant can be any of the cationic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable types of cationic surfactants include, but are not limited to, alkylamines, alkylimidazolines, ethoxylated amines, quaternary ammonium compounds, and quaternized ammonium esters. In addition, alkylamine oxides can be used as cationic surfactants at low pH.

Alkyl amine surface active agent may be a substituted or unsubstituted primary, secondary and tertiary C ₁₂ -C ₂₂ fatty alkyl amine salts of, and sometimes referred to as "amino acyl amine" of the material. Non-limiting examples of alkylamines and salts thereof include dimethyl cocoamine, dimethyl palmamine, dioctylamine, dimethyl stearylamine, dimethyl soyamine, soyamine, myristylamine, Tridecylamine, ethyl stearylamine, N-tallow lipid propane diamine, ethoxylated stearylamine, dihydroxyethyl stearylamine, arachidyl behenamide, dimethyl laurylamine, stearic acid Amine hydrochloride, soyamine chloride, stearylamine, N-tallow lipid propane diamine dichloride and amine-terminated dimethyl polyoxane (INCI name of polyoxyl polymer) Amino functional groups are capped, such as aminoethylaminopropyl decane.

Non-limiting examples of guanamine amines and salts thereof include stearyl propyl dimethyl dimethylamine, stearyl propyl dimethyl citrate citrate, palm oil amidopropyl diethylamine and Cocoaminopropyl dimethylamine lactate.

Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazolines such as stearyl hydroxyethyl imidazoline, cocoyl hydroxyethyl imidazoline, ethyl hydroxymethyl oleooxazoline And similar.

Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 tallowamine, quaternary ammonium salt-52, and the like.

Among the quaternary ammonium compounds which can be used as the cationic surfactant, some correspond to the formula: (R ⁵ R ⁶ R ⁷ R ⁸ N ⁺ )E ⁻ , wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ Independently selected from aliphatic groups having from 1 to about 22 carbon atoms, or aromatic groups, alkoxy groups, polyoxyalkylene groups, alkyl decylamino groups, hydroxyalkyl groups, aryl groups or in alkyl groups An alkylaryl group having from 1 to about 22 carbon atoms in the chain; and E ⁻ is a salt anion such as a halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, Anion of phosphate, nitrate, sulfate and alkyl sulfate. The aliphatic group may contain an ether bond, an ester bond, and other groups such as an amine group in addition to a carbon atom and a hydrogen atom. Longer chain aliphatic groups, such as aliphatic groups having about 12 carbons or more, may be saturated or unsaturated. In one aspect, the aryl group is selected from the group consisting of phenyl and benzyl.

Exemplary quaternary ammonium surfactants include, but are not limited to, cetyltrimethylammonium chloride, cetylpyridinium chloride, cetyldimethylammonium chloride, dihexadecane chloride Dimethylammonium, stearyl dimethylbenzylammonium chloride, di(octadecyl)dimethylammonium chloride, di(octadecyl)dimethylammonium chloride, chlorination Di(docosyl)dimethylammonium chloride, di(hexadecyl)dimethylammonium chloride, di(hexadecyl)dimethylammonium acetate, benzalkonium trimethylammonium chloride, Benzalkonium chloride, benzethonium chloride and bis(cocoalkyl)dimethylammonium chloride, di-animal dimethylammonium chloride, di(hydrogenated tallow) dimethylammonium chloride, acetic acid II Hydrogenated tallow) dimethylammonium, di-animal acid dimethylammonium methyl sulfate, dipropylammonium phosphate diammonium phosphate and di-animal acid dimethylammonium nitrate.

At low pH, the amine oxide can be protonated and behave like an N-alkylamine. Examples include, but are not limited to, dimethyl-dodecylamine oxide, oleyl bis(2-hydroxyethyl)amine oxide, dimethyltetradecylamine oxide, bis(2-hydroxyethyl) -tetradecylamine oxide, dimethylhexadecylamine oxide, behenamide oxide, cocoamine oxide, mercaptotetradecylamine oxide, dihydroxyethyl C12 - 15 alkoxypropylamine oxide, dihydroxyethyl cocoamine oxide, dihydroxyethyl laurylamine oxide, dihydroxyethyl stearylamine oxide, dihydroxyethyl tallow amine oxide, Hydrogenated palm kernel amine oxide, hydrogenated tallow amine oxide, hydroxyethyl hydroxypropyl C ₁₂ -C ₁₅ alkoxypropylamine oxide, laurylamine oxide, myristylamine oxide, cetylamine Oxide, oil sulfhydryl propylamine oxide, oleylamine oxide, palmamine oxide, PEG-3 laurylamine oxide, dimethyl laurylamine oxide, triphosphonium methylamine oxide Potassium, soybean oil, guanamine propylamine oxide, cocoamine propylamine oxide, stearylamine oxide, tallow amine oxide, and mixtures thereof.

Amphoteric or zwitterionic surfactants contain acidic and basic moieties and can be used as molecules for acids or bases. Suitable surfactants can be any of the amphoteric surfactants known or previously used in the art of aqueous surfactant compositions. Exemplary amphoteric surfactant species include, but are not limited to, amino acids (eg, N-alkylamino acids and N-decylamino acids), betaines, sulfobetaines, and alkyl amphocarboxylates.

Suitable amino acid surfactants include surfactants represented by the formula:

Wherein R ¹⁰ represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or a fluorenyl group having a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms, Y-based hydrogen or methyl group, and 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 , -CH ₂ C ₆ H ₄ OH, -CH ₂ OH, -CH(OH)CH ₃ , -(CH ₂ ) ₄ NH ₂ , -(CH ₂ ) ₃ NHC(NH)NH ₂ , -CH ₂ C(O)O ⁻ M ⁺ , -(CH ₂ ) ₂ C(O)O ⁻ M ⁺ . M is a salt cation. In one aspect of the, R ¹⁰ represents a straight-chain or branched are selected from C ₁₀ to C ₂₂ alkyl group, a linear or branched C ₁₀ to C ₂₂ alkenyl group, a R ¹¹ C (O) - represents the acyl group a group wherein R ^{11 is} selected from a linear or branched C ₉ to C ₂₂ alkyl group, a straight or branched chain C ₉ to C ₂₂ alkenyl group. In one aspect, M ^{+ is} selected from the group consisting of sodium, potassium, ammonium, and triethanolamine (TEA).

The amino acid surfactant may be composed of an α-amino acid such as alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, Alkylation and deuteration of serine, tyrosine and valine. Representative N-decylamino acid surfactants are, but are not limited to, mono- and dicarboxylic acid salts of N-deuterated glutamic acid (eg, sodium, potassium, ammonium, and TEA), such as cocoon Sodium glutamate, sodium lauryl glutamate, sodium myristyl glutamate, sodium palmitate glutamate, sodium stearyl glutamate, disodium cocoyl glutamate, Disodium stearyl glutamate, potassium cocoyl glutamate, potassium lauryl glutamate and potassium myristate; carboxylic acid salt of N-deuterated alanine (eg sodium, Potassium, ammonium and TEA), such as sodium cocoyl propylamine and TEA lauryl propylamine; carboxylates of N-deuterated glycine (eg sodium, potassium, ammonium and TEA), such as cocoon Sodium glycyrrhizinate and potassium cocoyl glycinate; N-deuterated sarcosine carboxylates (eg, sodium, potassium, ammonium, and TEA), such as sodium lauryl sarcosinate, cocoyl Sodium Creatine, sodium myristate, sodium oleate, and ammonium laurate; and mixtures of the foregoing surfactants.

The betaine and sultaine which can be used in the disclosed compositions are selected from the group consisting of alkyl betaines, alkyl amino betaines and alkyl guanyl betaines represented by the formula, and the corresponding sultaines ( Sulfobetaine/sultaine):

Wherein R ¹² is C ₇ -C ₂₂ alkyl or alkenyl, each R ^{13 is} independently C ₁ -C ₄ alkyl, R ¹⁴ is C ₁ -C ₅ alkyl or hydroxy substituted C ₁ -C ₅ An alkyl group, n is an integer of 2 to 6, an A carboxylate group or a sulfonate group, and M is a salt cation. In one aspect, R ¹² is C ₁₁ -C ₁₈ alkyl or C ₁₁ -C ₁₈ alkenyl. In one aspect, R ¹³ is methyl. In one aspect, R ¹⁴ is a methylene, ethyl or hydroxypropyl group. In one aspect, n is 3. In another aspect, M is selected from the group consisting of sodium, potassium, magnesium, ammonium, and monoethanolamine cations, diethanolamine cations, and triethanolamine cations.

Examples of suitable betaines include, but are not limited to, lauryl betaine, cocobetaine, oleyl betaine, cocoyl cetyl dimethyl betaine, lauryl decyl propyl betaine, Cocoaminopropyl propyl betaine and cocoamidopropyl hydroxy sultaine.

Alkyl amphocarboxylates such as alkyl amphoacetates and alkyl amphopropionates (monosubstituted disubstituted carboxylates) can be represented by the formula:

Wherein R ¹² lines C ₇ -C ₂₂ alkyl or alkenyl group, R ¹⁵ based ^{_{-CH 2 C (O) O -}} M +, -CH 2 CH 2 C (O) O - M + or -CH ₂ CH (OH CH ₂ SO ₃ ⁻ M ⁺ , R ¹⁶ is hydrogen or —CH ₂ C(O)O ⁻ M ⁺ , and M is selected from the group consisting of sodium, potassium, magnesium, ammonium, and cations of monoethanolamine, diethanolamine, and triethanolamine.

Exemplary alkyl amphocarboxylates include, but are not limited to, sodium cocoamphoacetate, sodium lauryl amphoacetate, sodium octanoic acid acetate, disodium cocoamphodiacetate, disodium lauryl amphoacetate, octyl Amphodisodium diacetate, disodium octyldiamine diacetate, disodium cocoamphodipropionate, disodium lauryl dipropionate, disodium octyl amphoteric dipropionate and disodium octadecyl dipropionate .

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 -C ₁₈ ) primary or secondary linear or branched chain acids, alcohols or phenols; alkyl ethoxylates; alkylphenol alkoxy groups Compounds (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 copolymer. Other suitable nonionic surfactants include monoalkyl or dialkyl alkanolamines; alkyl polyglucosides (APG); sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; Polyoxyethylene sorbitol ester; polyoxyethylene acid and polyoxyethylene alcohol. Other examples of suitable nonionic surfactants include coco monoethanolamine or diethanolamine, coco glucoside, decyl diglucoside, lauryl diglucoside, coco diglucoside, poly Sorbitol esters 20, 40, 60 and 80, ethoxylated linear alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG-100 stearate, lauryl ether 7 and oleyl alcohol ether 20.

In another embodiment, the nonionic surfactant includes, but is not limited to, alkoxylated methyl glucosides such as methylglycol-10, methylglycol-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® E20, Glucam® P10 and Glucam® P20, respectively; and hydrophobically modified alkoxylates Methylated glucosides such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate and PEG-20 methyl glucose sesquistearate, respectively under the trade name Glucamate® DOE- 120. GlucamateTM LT and GlucamateTM SSE-20 are available from Lubrizol Advanced Materials, Inc. and are also suitable. Other exemplary hydrophobically modified alkoxylated methyl glucosides are disclosed in U.S. Patent Nos. 6,573,375 and 6,727,357, the disclosures of each of each of each of

Other surfactants that can be used in the disclosed compositions are described in more detail in WO 99/21530, U.S. Patent No. 3,929,678, U.S. Patent No. 4,565,647, U.S. Patent No. 5,720,964, and U.S. Patent No. 5,858,948. Further, suitable surfactant in the complete hereby incorporated by McCutcheon 's Emulsifiers and Detergents (North American and International Edition, Schwartz, Perry and Berch) are also described.

Although the amount of surfactant used in the composition comprising the disclosed segmented core-shell polymer can vary widely depending on the desired application, it includes personal care, home care, healthcare, and institutions including surfactants. And the usual amount of the industrial care composition is generally in the range of from about 1% by weight to about 80% by weight in one aspect, and in the range of from about 3% by weight to about 65% by weight in another aspect. In yet another aspect, in the range of from about 5% by weight to about 30% by weight, in another aspect, in the range of from about 6% by weight to about 20% by weight, and in the range of from about 8% by weight to about 16% by weight Within the range of %.

In one aspect, the personal care, home care, healthcare, agricultural, and I&I care compositions disclosed herein comprise a combination of a segmented core-shell polymer and at least one anionic surfactant. In another aspect, the compositions comprise a segmented core-shell polymer and at least one anionic surfactant and at least one amphoteric surfactant. In one aspect, the anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl polyether sulfates, and mixtures thereof, wherein the alkane The group contains 10 to 18 carbon atoms, the aryl group is a phenyl group, and the ether group contains 1 to 10 mol 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.

In one aspect, the amphoteric surfactant is selected from the group consisting of alkyl betaines, alkyl amino betaines, alkyl amidine betaines, and mixtures thereof. Representative betaines include, but are not limited to, lauryl betaine, cocobetaine, cocoyl cetyl dimethyl betaine, cocoamidopropyl betaine, cocoamine propyl Hydroxysulfobetaine and mixtures thereof.

EXAMPLES The following examples are intended to illustrate various embodiments of the disclosed rheology modifiers and formulations containing such rheology modifiers, and are not intended to limit the scope of the appended claims.

In the examples and the attached tables, the following materials and abbreviations are used.
DMAEMA - N,N-dimethylaminoethyl methacrylate (from SNF Cosmetics)
EA - ethyl acrylate
EGDMA - ethylene glycol dimethacrylate
TMPTA - Trimethylolpropane triacrylate (from Alfa Aesar)
TMP(9 EO)TA-trimethylolpropane ethoxylated (9) triacrylate (KomerateKomerate TO-93)

In each of the following Examples 1-11, the core polymer and the shell polymer were composed of ethyl acrylate, N,N-dimethylaminoethyl methacrylate and cetyl 20 EO itaconate. Manufacturing of Mobilis at 71.6/27.8/0.6. In the case where a crosslinking agent is used in the shell, mol% is based on the molar amount of ethyl acrylate and N,N-dimethylaminoethyl methacrylate and cetyl 20 EO coating excluding the crosslinking agent. The total amount of colate is reported.

Example 1 - 20/80 core/shell (wt%); 0.15 mol% crosslinker contained in the shell. A 1 liter reaction vessel was charged with 658.82 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 nonionic surfactant (Stepan Company) and 8.30 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 25.2 grams of ethyl acrylate (0.252 mol) and 2.57 grams of cetyl 20 EO itaconate-associated monomer (0.002 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 15.4 g of DMAEMA (0.098 mol) and 2.33 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3241 grams of sodium persulfate and 41.30 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 24 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 100.9 g of ethyl acrylate (1.008 mol), 10.24 g of cetyl 20 EO itaconate associative monomer (0.008 mol) and 0.6213 g of TMPTA (0.002 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 61.4 g of DMAEMA (0.391 mol) and 9.3 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 96 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7878 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.9% solids with a pH of 8.31.

Example 2 - 20/80 core/shell (wt%); 0.05 mol% crosslinker in the shell. To a 1 liter reaction vessel was charged 658.83 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 25.2 grams of ethyl acrylate (0.252 mol) and 2.57 grams of cetyl 20 EO itaconate-associated monomer (0.002 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 15.4 g of DMAEMA (0.098 mol) and 2.3 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3228 grams of sodium persulfate and 41.34 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.36 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 24 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 101.0 g of ethyl acrylate (1.008 mol), 10.24 g of cetyl 20 EO itaconate associative monomer (0.008 mol) and 0.2113 g of TMPTA (0.0007 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 61.4 g of DMAEMA (0.391 mol) and 9.3 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 96 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7921 grams of sodium persulfate and 23.97 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.1% solids at pH 8.23.

Example 3 - 80/20 core/shell (wt%); 0.15 mol% crosslinker in the shell. To a 1 liter reaction vessel was charged 658.82 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.30 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 100.9 g of ethyl acrylate (1.008 mol) and 10.25 g of cetyl 20 EO itaconate-associated monomer (0.008 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 61.4 g of DMAEMA (0.391 mol) and 9.3 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3207 grams of sodium persulfate and 41.32 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.32 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 96 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 25.2 grams of ethyl acrylate (0.252 mol), 2.56 grams of cetyl 20 EO itaconate associative monomer (0.002 mol) and 0.1214 g of TMPTA (0.0005 mol) were applied at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 15.4 grams of DMAEMA (0.098 mol) and 2.3 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 24 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7887 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.5% solids at pH 8.23.

Example 4 - 80/20 core/shell (wt%); 1.15 mol% crosslinker contained in the shell. A 1 liter reaction vessel was charged with 658.82 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 100.9 grams of ethyl acrylate (1.008 mol) and 10.2 grams of cetyl 20 EO itaconate-associated monomer (0.008 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 61.4 g of DMAEMA (0.391 mol) and 9.3 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3206 grams of sodium persulfate and 41.35 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.34 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 96 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 25.2 grams of ethyl acrylate (0.252 mol), 2.56 grams of cetyl 20 EO itaconate-associated monomer (0.002 mol) and 0.1622 grams of TMPTA (0.005 mol) were applied at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 15.4 grams of DMAEMA (0.098 mol) and 2.3 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 24 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7914 grams of sodium persulfate and 24.07 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.4% solids at pH 8.17.

Example 5 - 70/30 core/shell (wt%); 0.15 mol% crosslinker in the shell. A 1 liter reaction vessel was charged with 658.81 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.57 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 88.3 grams of ethyl acrylate (0.882 mol) and 8.97 grams of cetyl 20 EO itaconate-associated monomer (0.007 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 53.8 grams of DMAEMA (0.342 mol) and 8.16 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 84 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 37.9 g of ethyl acrylate (0.378 mol), 3.85 g of cetyl 20 EO itaconate associative monomer (0.003 mol) and 0.1916 g of TMPTA (0.0006 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 23.0 grams of DMAEMA (0.147 mol) and 3.50 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 36 minutes, the initiator solutions A and B were resumed and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7911 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.8% solids at pH 8.14.

Example 6 - 70/30 core/shell (wt%); 1.15 mol% crosslinker contained in the shell. A 1 liter reaction vessel was charged with 658.84 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 88.3 grams of ethyl acrylate (0.882 mol) and 8.97 grams of cetyl 20 EO itaconate-associated monomer (0.007 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 53.8 grams of DMAEMA (0.342 mol) and 8.16 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 84 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 37.9 g of ethyl acrylate (0.378 mol), 3.85 g of cetyl 20 EO itaconate associative monomer (0.003 mol) and 1.7422 g of TMPTA (0.006 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 23.0 grams of DMAEMA (0.147 mol) and 3.51 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 36 minutes, the initiator solutions A and B were resumed and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7890 grams of sodium persulfate and 23.96 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.7% solids at pH 8.16.

Example 7 - 85/15 core/shell (wt%); 2.8 mol% crosslinker in the shell. A 1 liter reaction vessel was charged with 658.81 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 107.3 g of ethyl acrylate (1.071 mol) and 10.89 g of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 65.3 g of DMAEMA (0.415 mol) and 9.91 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3240 grams of sodium persulfate and 41.31 grams of water. Initiator B was prepared using 3.92 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 102 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 18.9 g of ethyl acrylate (0.189 mol), 1.92 g of cetyl 20 EO itaconate associative monomer (0.002 mol) and 2.1818 g of TMPTA (0.007 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 11.5 grams of DMAEMA (0.073 mol) and 1.78 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 18 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7914 grams of sodium persulfate and 23.96 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.6% solids at pH 8.13.

Example 8 - 90/10 core/shell (wt%); 2.8 mol% crosslinker in the shell. A 1 liter reaction vessel was charged with 658.83 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.6 grams of ethyl acrylate (1.134 mol) and 11.53 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.28 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4487 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.17 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7919 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.5% solids with a pH of 8.17.

Example 9 - 95/5 core/shell (wt%); 2.8 mol% crosslinker in the shell. A 1 liter reaction vessel was charged with 617.62 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 9.92 grams of Polystep® TD 507 and 7.78 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 112.4 grams of ethyl acrylate (1.123 mol) and 11.40 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 68.4 g of DMAEMA (0.435 mol) and 10.38 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.2405 grams of sodium persulfate and 38.76 grams of water. Initiator B was prepared using 3.70 grams of 41% sodium bisulfite and 34.99 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 114 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, using the subsurface feed, 5.9 g of ethyl acrylate (0.059 mol), 0.60 g of cetyl 20 EO itaconate associative monomer (0.0005 mol) and 0.6821 g of TMPTA (0.0023 mol) at 20 ml/min. The monomer mixture is added to the reactor. Next, a mixture of 3.6 grams of DMAEMA (0.023 mol) and 0.56 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 6 minutes, the initiator solutions A and B were resumed and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7404 grams of sodium persulfate and 22.52 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.5% solids at pH 8.27.

Example 10 - 95/5 core/shell (wt%); 5.6 mol% crosslinker in the shell. To a 1 liter reaction vessel was charged 617.64 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 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 mol) and 11.41 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 68.4 g of DMAEMA (0.435 mol) and 10.38 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.2387 grams of sodium persulfate and 38.80 grams of water. Initiator B was prepared using 3.68 grams of 41% sodium bisulfite and 35.02 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 114 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes.

Next, 5.9 g of ethyl acrylate (0.059 mol), 0.60 g of cetyl 20 EO itaconate associative monomer (0.0005 mol) and 1.3616 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 3.6 grams of DMAEMA (0.023 mol) and 0.56 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 6 minutes, the initiator solutions A and B were resumed and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7407 grams of sodium persulfate and 22.48 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 20.5% solids at pH 8.27.

Example 11 - Evaluation of Viscosity and Clarity, 2 wt% of Living Polymer In a 250 ml beaker, 4 g of the active polymer from Examples 1-8, respectively, was diluted with 196 g of water. These solutions were mixed for 5 minutes at 400 rpm using a jiffy mixer. Next, the solutions were neutralized using 2 grams of 70 wt% glycolic acid. The final pH of the resulting solution is between 3 and 3.5. The viscosity was measured using a Brookfield DV-I+ viscometer at 25 °C using a spindle 4 at 10 rpm. Next, the clarity of the solution was measured using HACH 2100AN turbidity measurement. The results are set forth in Table 1.
Table 1

These data indicate that the cationic core-shell polymers disclosed herein are good rheology modifiers and have good clarity.

Example 12 - Comparative Example - nuclear - shell, no crosslinker <br/> vessel was charged 658.82 grams of water and heated to 65.6 deg.] C and lower surface of the reactor filled with nitrogen to 1 liter. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507, 12.80 grams of cetyl 20 EO itaconate-associated monomer, and 8.30 grams of 5% sodium hydroxide were added to the reactor. Next, the reactor was heated to 71.1 ° C and cooked for 20 minutes until all of the associative monomers were dissolved. Immediately after all of the associative monomers were dissolved, the reactor was cooled to 55.6 °C. When the temperature was lowered to 62.8 ° C, 126.2 grams of ethyl acrylate was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 76.8 grams of DMAEMA and 11.64 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3237 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. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7922 grams of sodium persulfate and 24.10 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.23.

Example 13 - Evaluation of viscosity, clarity and suspension, body cleansing formulation containing 1.75 wt% active polymer.
A solution of 200 grams of surfactant-based formulation was prepared by adding 16.83 grams of the polymer emulsion of the example shown (3.5 grams of active polymer) to 59.77 grams of deionized water in a 250 ml beaker. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 gram of Jojoba bead (Florabeads Johorba 28/60 Burnt Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in an oven at 45 ° C for long-term monitoring. The results are set forth in Table 2.
Table 2

Example 14 Evaluation of viscosity and clarity, body cleansing formulation containing 1.0 wt% active polymer.
A typical surfactant-based formulation of 200 grams was prepared by adding 9.71 grams of polymer (2.0 grams of active polymer) to 68.89 grams of deionized water in a 250 ml beaker. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 g of jojoba beads (Florabeads Jojoba 28/60 Coke Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in an oven at 45 ° C for long-term monitoring. Viscosity, pH and clarity are set forth in Table 3.
table 3

Example 15 Evaluation of viscosity and clarity, body cleansing formulation containing 1.4 wt% active polymer.
A typical body cleansing formulation of 200 grams was prepared by adding 13.59 grams of polymer (2.0 grams of active polymer) to 64.01 grams of deionized water in a 250 ml beaker. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 g of jojoba beads (Florabeads Jojoba 28/60 Coke Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in an oven at 45 ° C for long-term monitoring. Viscosity, pH and clarity are set forth in Table 4.
Table 4

Example 16 evaluation of viscosity, clarity and suspension state, body composition containing 3.0 wt% active polymer.
A typical body cleansing formulation of 200 grams was prepared by adding 48.16 grams of polymer (6 grams of active polymer) to 28.44 grams of deionized water in a 250 ml beaker. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 g of jojoba beads (Florabeads Jojoba 28/60 Coke Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in an oven at 45 ° C and monitored over the next 3 months. The results are set forth in Table 5.
table 5

Example 17 Evaluation of viscosity, clarity and suspension state, body composition containing 1.5 wt% of active polymer.
A typical body cleansing formulation of 200 grams was prepared by adding 14.49 grams of polymer (3 grams of active polymer) to 62.11 grams of deionized water in a 250 ml beaker. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 g of jojoba beads (Florabeads Jojoba 28/60 Coke Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in a 45 ° C oven and monitored. The results are set forth in Table 6.
Table 6

Example 18 Evaluation of Viscosity, Clarity and Suspension, Body Cleansing Formulation Containing 2 wt% of Active Polymer 19.32 Gm of Polymer (4 Gg of Living Polymer) was added to 57.28 G of deionized water in a 250 ml beaker Prepare 200 grams of typical body cleansing formulation. Insert the smaller 11⁄2吋 Giffy mixer blade into the beaker and attach it to the overhead mixer. The batch was mixed using a vortex extending into the middle of the beaker. Thereafter, 100 grams of sodium lauryl ether sulfate (25.2% of active Standapol ES-2 from BASF) was added. Let it mix for 15 minutes. Next, 14.8 grams of cocoamidopropyl betaine (Crodateric CAB 30, Croda Inc.) was added and mixed for an additional 15 minutes. Next, 0.1 gram of tetraethylammonium diacetate tetraacetate was added and the batch was mixed until homogeneous. 0.5 grams of sodium benzoate was added to the batch and mixed until homogeneous. Next, the pH was adjusted to 5.0 +/- 0.2 using 20% citric acid as needed. The batch was mixed for 15 minutes and then held for 24 hours before it was centrifuged. The viscosity was measured using a Brookfield DV-I+ viscometer using a spindle 6 at 10 rpm and clarity using HACH 2100AN turbidity measurement. Next, 30 g of the batch was poured into a 50 ml glass jar, and 0.4 g of jojoba beads (Florabeads Jojoba 28/60 Coke Orange, Floratech) was added thereto. The beads are gently incorporated into the batch until it is evenly distributed throughout the batch. Next, the glass jar was stored in an oven at 45 ° C for long-term monitoring. The results are presented in Table 7.
Table 7

Examples 19-20 Suspension of Insecticides The following examples show insecticide suspension concentrates for agricultural applications formulated with the polymers of the present invention.

Solid insecticides (Tebuconazole, Azoxystrobin, Diuron) were first wet milled to a particle size of about 5 microns in a bead mill (Eiger Torrance MiniMoto 250). The composition of the ground samples is shown in Table 8, indicated by weight %.
Table 8

The ground sample is used as a matrix for the suspension concentrate. Two suspension concentrates were prepared by adding the polymer of the present invention to the ground samples MS-1 and MS-2 with stirring and adjusting the sample to about pH 4.5. Water is then added to the ground sample. The amounts of each component are listed in Table 9.
Table 9

As shown in Table 10, after storage for two weeks at 50 °C, Examples 19 and 20 did not exhibit solid material settling at the bottom of their container, and it also did not exhibit top surface settling from the suspension concentrate.
Example 10

Example 21 - Rheology Modifiers for Fabric Conditioners Current fabric softeners are generally divided into two classes, conventional and concentrated. These softener formulations will typically contain a quaternary ammonium functionalized material, some form of fragrance, and a rheology modifier.

Including the disclosed rheology modifier will increase the viscosity. Arquad 2HT75 was purchased from Akzo Nobel Surface Chemistry LLC, and Armosoft DEQ was purchased from Akzo Nobel Surface Chemistry LLC.

The viscosity was tested at 25 ° C using a Brookfield viscometer using 10 rpm. The results are set forth in Table 11.
Table 11

Examples 22 - 50 wt% starch and 90/10 core / shell (wt%); shell containing 2.8 mol% crosslinker 579.60 grams of water was charged to a 1 liter reaction vessel and heated to 65.6 deg.] C and charged with lower surface 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 reaction vessel using a funnel. When the temperature reached 65.6 ° C, the surface was continuously filled with nitrogen for one hour and then moved to the surface. Next, 3.72 grams of Polystep® TD 507 and 0.79 grams of triethanolamine (Aldrich) were added to the reactor.

A monomer mixture of 39.8 grams of ethyl acrylate (0.397 mol) and 3.42 grams of cetyl 20 EO itaconate-associated monomer (0.003 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 24.2 grams of DMAEMA (0.154 mol) and 3.67 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 4.4 g of ethyl acrylate (0.044 mol), 0.40 g of cetyl 20 EO itaconate associative monomer (0.0003 mol) and 0.5098 g of TMPTA (0.002 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 2.7 g of DMAEMA (0.049 mol) and 0.41 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.2927 grams of sodium persulfate and 14.02 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 15.2% solids at pH 8.25.

Example 23 - 90/10 core/shell (wt%); 2.8 mol% EGDMA (ethylene glycol dimethacrylate) was used as a crosslinker to charge 658.83 g of water into a 1 liter reaction vessel and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.6 grams of ethyl acrylate (1.134 mol) and 11.53 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 grams of ethyl acrylate (0.126 mol), 1.28 grams of cetyl 20 EO itaconate-associated monomer (0.001 mol) and 1.00874487 grams from Sartomer 206 were used at 20 ml/min using a subsurface feed. A monomer mixture of ethylene glycol dimethacrylate (0.005 mol) was added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.17 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7919 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.4% solids at pH 8.24.

Example 24 - 90/10 core/shell (wt%); 2.8 mol% Komerate-TO93 (TMP(EO)9TA) was used as a crosslinker to charge 658.85 g of water into a 1 liter reaction vessel and heated to 65.6 °C The surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.33 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.6 grams of ethyl acrylate (1.134 mol) and 11.54 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.50 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3212 grams of sodium persulfate and 41.35 grams of water. Initiator B was prepared using 3.95 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.29 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 3.5124 g of Komerate-TO93 (20 mmol/min) were used at 20 ml/min. A 0.005 mol) monomer mixture was added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.16 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7923 grams of sodium persulfate and 24.02 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.25.

Example 25 - 10/90 core/shell (wt%); 0.15 mol% crosslinker in the shell. To a 1 liter reaction vessel was charged 658.86 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.30 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 12.6 grams of ethyl acrylate (0.126 mol) and 1.28 grams of cetyl 20 EO itaconate-associated monomer (0.001 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.21 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3254 grams of sodium persulfate and 41.31 grams of water. Initiator B was prepared using 3.90 grams of 41% sodium bisulfite and 37.30 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 12 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 113.6 g of ethyl acrylate (1.136 mol), 11.57 g of cetyl 20 EO itaconate associative monomer (0.009 mol) and 0.704 g of TMPTA (0.002 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.51 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 108 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7925 grams of sodium persulfate and 23.99 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.3% solids at pH 8.33.

Example 26 - 90/10 core/shell (wt%); 2.8 mol% crosslinker in the shell and 0.05 mol% crosslinker in the core. 658.85 g water was charged into a 1 liter reaction vessel and heated to 65.6 °C. The surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.57 grams of Polystep® TD 507 and 8.32 grams of 5% sodium hydroxide were added to the reactor.

113.7 grams of ethyl acrylate (1.134 mol), 11.51 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) and 0.2612 g (0.0009 mol) of TMPTA at 20 ml/min using a subsurface feed The bulk mixture is added to the reactor. While maintaining the temperature at 55.6 ° C, a mixture of 69.2 g of DMAEMA (0.44 mol) and 10.51 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.26 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4490 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.20 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7902 grams of sodium persulfate and 23.96 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.4% solids at pH 8.27.

Example 27 - 90/10 core/shell (wt%); 2.8 mol% crosslinker in shell and C22 associative monomer containing 25 mol EO itaconate was charged to 658.86 g of water in a 1 liter reaction vessel and Heat to 65.6 ° C and fill the surface with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.60 grams of Polystep® TD 507 and 8.35 grams of 5% sodium hydroxide were added to the reactor.

Adding 113.6 grams of ethyl acrylate (1.134 mol) and 12.53 grams of a monomer mixture containing 25 mol of EO itaconate-associated monomer C22 (0.009 mol) to the reactor at 20 ml/min using a subsurface feed . While maintaining the temperature at 55.6 ° C, a mixture of 69.2 grams of DMAEMA (0.44 mol) and 10.48 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3212 grams of sodium persulfate and 41.30 grams of water. Initiator B was prepared using 3.90 grams of 41% sodium bisulfite and 37.31 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 12 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.65 g of C22 associative monomer (0.001 mol) containing 25 mol of EO itaconate, and 1.4479 g of TMPTA (0.005) at 20 ml/min were used. A monomer mixture of mol) is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.19 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 108 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7924 grams of sodium persulfate and 23.99 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.3% solids at pH 8.30.

Example 28 - 90/10 core/shell (wt%); 2.8 mol% crosslinker in the shell and C22 associative monomer containing 20 mol EO itaconate was charged into a 1 liter reaction vessel with 658.83 grams of water and Heat to 65.6 ° C and fill the surface with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

Adding 113.6 grams of ethyl acrylate (1.134 mol) and 11.53 grams of a monomer mixture of 20 mol of EO itaconate C22 associative monomer (0.009 mol) to the reactor at 20 ml/min using a subsurface feed . While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 12 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.4828 g of C22 associative monomer (0.001 mol) containing 20 mol of EO itaconate and 1.4487 g of TMPTA (0.005) at 20 ml/min were used. A monomer mixture of mol) is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.17 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 108 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7919 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.25.

Example 29 - 90/10 core/shell (wt%); shell containing 2.8 mol% crosslinker; no associative monomer in the core loaded into 658.84 g water in a 1 liter reaction vessel and heated to 65.6 ° C and surface Filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.34 grams of 5% sodium hydroxide were added to the reactor.

113.6 grams of ethyl acrylate (1.134 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.2 grams of DMAEMA (0.44 mol) and 10.52 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3214 grams of sodium persulfate and 41.31 grams of water. Initiator B was prepared using 3.89 grams of 41% sodium bisulfite and 37.31 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.28 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4466 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.19 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7928 grams of sodium persulfate and 24.03 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.3% solids at pH 8.24.

Example 30 - 90/10 core/shell (wt%); 2.8 mol% crosslinker; no associative monomer in the shell. Put 658.86 grams of water into a 1 liter reaction vessel and heat to 65.6 ° C and fill the surface. Nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.57 grams of Polystep® TD 507 and 8.33 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.6 grams of ethyl acrylate (1.134 mol) and 11.56 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.2 g of DMAEMA (0.44 mol) and 10.54 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3198 grams of sodium persulfate and 41.32 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, a monomer mixture of 12.6 g of ethyl acrylate (0.126 mol) and 1.4477 g of TMPTA (0.005 mol) was added to the reactor at 20 ml/min using a subsurface feed. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.16 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7915 grams of sodium persulfate and 23.95 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.4% solids at pH 8.34.

Example 31 - 90/10 core/shell (wt%); 2.8 mol% crosslinker; less DMAEMA in shell
A 1 liter reaction vessel was charged with 658.83 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.7 grams of ethyl acrylate (1.134 mol) and 11.55 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.2 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3216 grams of sodium persulfate and 41.32 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.31 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 13.2 g of ethyl acrylate (0.131 mol), 1.46 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4521 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 6.8 g of DMAEMA (0.044 mol) and 0.94 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7903 grams of sodium persulfate and 23.89 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.27.

Example 32 - 90/10 core/shell (wt%); 2.8 mol% crosslinker; shell containing more DMAEMA
A 1 liter reaction vessel was charged with 658.85 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.30 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 113.6 grams of ethyl acrylate (1.134 mol) and 11.53 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3223 grams of sodium persulfate and 41.36 grams of water. Initiator B was prepared using 3.94 grams of 41% sodium bisulfite and 37.35 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.1 g of ethyl acrylate (0.121 mol), 1.28 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4512 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 8.5 grams of DMAEMA (0.054 mol) and 1.16 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7905 grams of sodium persulfate and 24.04 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.5% solids at pH 8.31.

Example 33 - 90/10 core/shell (wt%); 2.8 mol% crosslinker; less DMAEMA in the core
A 1 liter reaction vessel was charged with 658.83 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 118.2 grams of ethyl acrylate (1.2 mol) and 11.5253 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 61.9 g of DMAEMA (0.39444 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.6 g of ethyl acrylate (0.126 mol), 1.28 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4487 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.17 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7919 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.25.

Example 34 - 90/10 core/shell (wt%); 2.8 mol% crosslinker; more DMAEMA in the core
A 1 liter reaction vessel was charged with 658.83 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.59 grams of Polystep® TD 507 and 8.31 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 108.7 grams of ethyl acrylate (1.086134 mol) and 11.53 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 69.1 g of DMAEMA (0.44 mol) and 10.49 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 12.61 g of ethyl acrylate (0.121 mol), 1.27 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4509 g of TMPTA (0.005 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 7.7 g of DMAEMA (0.049054 mol) and 1.17 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7879 grams of sodium persulfate and 23.98 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.3% solids at pH 8.29.

Example 35 - 90/10 core/shell (wt%); shell containing 2.8 mol% crosslinker; no association monomer and less DMAEMA
A 1 liter reaction vessel was charged with 658.82 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.57 grams of Polystep® TD 507 and 8.30 grams of 5% sodium hydroxide were added to the reactor.

118.2 grams of ethyl acrylate (1.181 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 61.9 g of DMAEMA (0.39 mol) and 8.45 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3198 grams of sodium persulfate and 41.31 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.31 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, a monomer mixture of 13.1 grams of ethyl acrylate (0.131 mol) and 1.4489 grams of TMPTA (0.005 mol) was added to the reactor at 20 ml/min using a subsurface feed. Next, a mixture of 6.9 g of DMAEMA (0.044 mol) and 0.95 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7914 grams of sodium persulfate and 23.92 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.5% solids at pH 8.29.

Example 36 - 90/10 core/shell (wt%); shell containing 2.8 mol% crosslinker; no association monomer and more DMAEMA
A 1 liter reaction vessel was charged with 658.85 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.32 grams of 5% sodium hydroxide were added to the reactor.

108.7 grams of ethyl acrylate (1.084 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 76.7 g of DMAEMA (0.488 mol) and 11.21 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added 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 reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, a monomer mixture of 12.1 g of ethyl acrylate (0.121 mol) and 1.4503 g of TMPTA (0.005 mol) was added to the reactor at 20 ml/min using a subsurface feed. Next, a mixture of 8.5 g of DMAEMA (0.054 mol) and 1.18 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7911 grams of sodium persulfate and 24.19 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.2% solids at pH 8.26.

Example 37 - 10/90 core/shell (wt%); 0.15 mol% crosslinker in the shell; 0.05 mol% crosslinker in the core; 658.85 g water was charged into a 1 liter reaction vessel and heated to 65.6 ° C and The surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.57 grams of Polystep® TD 507 and 8.33 grams of 5% sodium hydroxide were added to the reactor.

Next, 12.6 g of ethyl acrylate (0.126 mol), 11.54 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 0.0258 g of TMPTA (0.0001 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. While maintaining the temperature at 55.6 ° C, a mixture of 7.7 g of DMAEMA (0.049 mol) and 1.16 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.3184 grams of sodium persulfate and 41.38 grams of water. Initiator B was prepared using 3.90 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 12 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 113.6 g of ethyl acrylate (1.134 mol), 11.53 g of cetyl 20 EO itaconate associative monomer (0.009 mol) and 0.6187 g of TMPTA (0.002 mol) were used at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 69.1 grams of DMAEMA (0.44 mol) and 10.48 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 108 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7879 grams of sodium persulfate and 23.96 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.4% solids at pH 8.33.

Example 38 - 90/10 core/shell (wt%); shell containing 2.8 mol% crosslinker; shell containing more DMAEMA
A 1 liter reaction vessel was charged with 658.86 grams of water and heated to 65.6 ° C and the surface was filled with nitrogen. The surface was continuously flushed with nitrogen for one hour and then moved to the surface. Next, 10.58 grams of Polystep® TD 507 and 8.33 grams of 5% sodium hydroxide were added to the reactor.

A monomer mixture of 96.2 grams of ethyl acrylate (0.96 mol) and 11.54 grams of cetyl 20 EO itaconate-associated monomer (0.009 mol) was added to the reactor at 20 ml/min using a subsurface feed. While maintaining the temperature at 55.6 ° C, a mixture of 96.5 g of DMAEMA (0.614 mol) and 14.63 g of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. Next, the initiator solutions A and B were simultaneously added over 120 minutes. Initiator A was prepared using 1.32 grams of sodium persulfate and 41.36 grams of water. Initiator B was prepared using 3.91 grams of 41% sodium bisulfite and 37.33 grams of water. The reactor temperature was maintained below 60 °C during the initiator solution feed. The initiator solution was fed over 108 minutes, the initiator solutions A and B were stopped and the reaction mixture was held at 55.6 ° C for 30 minutes. Next, 10.7 g of ethyl acrylate (0.107 mol), 1.28 g of cetyl 20 EO itaconate associative monomer (0.001 mol) and 1.4519 g of TMPTA (0.005 mol) were added at 20 ml/min using a subsurface feed. The monomer mixture is added to the reactor. Next, a mixture of 10.7 grams of DMAEMA (0.068 mol) and 1.63 grams of propylene glycol was added to the reactor at 20 ml/min using a subsurface feed. In the next 12 minutes, the initiator solutions A and B were recovered and continued to be fed. The temperature was maintained below 60 °C during the feeding of the initiator solution. At the end of the feeding of the initiator solution, the reaction temperature was raised to 60 °C. Next, a solution of 0.7912 grams of sodium persulfate and 24.14 grams of water was added to the reactor over 60 minutes. At the end of this feed, the temperature was raised to 76.7 ° C and held at 76.7 ° C for 60 minutes. Next, the reactor was cooled to room temperature and the reaction product was filtered through a 210 micron filter. The final product was an opaque white emulsion containing 21.4% solids at pH 8.34.

Example 39 - Evaluation of Viscosity and Cleanliness, 2 wt% of Living Polymer In a 250 ml beaker, 4 g of the active polymer from Examples 23-38, respectively, was diluted with 196 g of water. These solutions were mixed for 5 minutes at 400 rpm using a Giffy mixer. Next, the solutions were neutralized using 2 grams of 70 wt% glycolic acid. The final pH of the resulting solution is between 3 and 3.5. The viscosity was measured using a Brookfield DV-I+ viscometer at 25 °C using a spindle 4 at 10 rpm. Next, the clarity of the solution was measured using HACH 2100AN turbidity measurement. The results are set forth in Table 12.
Table 12

Claims (16)

An acid-swellable rheology modifier comprising a core-shell polymer comprising a core polymer and a shell comprising at least one shell copolymer layer, wherein the core polymer and the at least one shell copolymerize The layers are each polymerized from a monomer mixture 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) one or more associative monomers, as appropriate, and At least one of the shell copolymer layers is at least partially crosslinked and comprises a crosslinker having a molar percentage greater than the molar percentage of the crosslinker in the core polymer. The acid swellable rheology modifier of claim 1, wherein the core polymer and the at least one shell polymer each contain less than 10 mol% of an anionic monomer. The acid swellable rheology modifier of claim 1 wherein the core polymer comprises 0 mole percent crosslinker. The acid swellable rheology modifier of claim 1, wherein the core polymer contains more than 0 mole percent crosslinker. The acid-swellable rheology modifier of any one of claims 1 to 4, wherein the core comprises more than 40% by weight of the core-shell polymer. The acid-swellable rheology modifier of any one of claims 1 to 5, wherein the core polymer comprises an associative monomer. The acid-swellable rheology modifier of any one of claims 1 to 6, wherein the at least one shell copolymer layer comprises an associative monomer. The acid-swellable rheology modifier according to any one of claims 1 to 7, wherein at least one of the cationic ethylenically unsaturated monosystems is selected from the group consisting of: (meth)acrylic acid N, N-di Alkylaminoalkyl ester, N-alkylaminoalkyl (meth)acrylate, N,N-dialkylaminoalkyl(meth)acrylamide and N-alkylaminoalkyl (A) Acrylamide, wherein the alkyl groups are independently a C _{1 - 22} linear, branched or cyclic moiety; an aromatic amine-containing monomer such as vinylpyridine; an alkenylamine-containing monomer, wherein such ethylenically unsaturated group C _{1 - 22} straight-chain, branched or cyclic moiety, such as vinylamine or allylamine; and acyclic ethylenically unsaturated carboxylic or as acetamide Amides, such as vinyl Formamide, vinyl acetamide; and mixtures of any of the foregoing. The acid-swellable rheology modifier of any one of claims 1 to 8, wherein at least one of the cationic ethylenically unsaturated monosystems is selected from the group consisting of N,N-dimethyl methacrylate Aminoethyl ester, tert-butylaminoethyl methacrylate, N,N-dimethylaminopropylmethacrylamide, 3-(dimethylamino)propyl methacrylate, A 2-(Dimethylamino)propan-2-yl acrylate, 3-(dimethylamino)-2,2-dimethylpropyl methacrylate, 2-(dimethyl) methacrylate Amino)-2-methylpropyl ester and 4-(dimethylamino)butyl methacrylate, and mixtures of any of the foregoing. The acid swellable rheology modifier of any one of claims 1 to 9, wherein the one or more hydrophobic ethylenically unsaturated monosystems are selected from the group consisting of C ₁ -acrylic acid and methacrylic acid C ₃₂ alkyl ester; C ₄ -C ₃₂ alkyl decylamine of acrylic acid and methacrylic acid; benzyl (meth) acrylate, phenyl (meth) acrylate, ethoxylated (meth) acrylate Ester, ethoxylated phenyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and 10-hydroxy decyl (meth) acrylate, styrene, α-methyl styrene, vinyl toluene, Tert-butyl styrene, isopropyl styrene and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl heptanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl decanoate , vinyl phthalate, 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, and combinations thereof. The acid swellable rheology modifier of any one of claims 1 to 10, wherein the one or more nonionic ethylenically unsaturated monosystems are selected from the group consisting of acrylamide, methacrylium oxime Amine, NC ₁ -C ₃ alkyl (meth) acrylamide, N, NC ₁ -C ₃ dialkyl (meth) acrylamide, C ₁ to C ₄ hydroxyalkyl (meth) acrylate, ethylene Mymorpholine, vinylpyrrolidone, vinyl propionate, vinyl butyrate, (poly) C ₁ -C ₄ alkoxylated (meth) acrylate such as poly(ethylene glycol) _n (methyl) Acrylate and poly(propylene glycol) _n (meth) acrylate, wherein n = 1 to 100, preferably 3 to 50, and most preferably 5 to 20; ethoxylated C ₁ -C ₄ alkyl, a C ₁ -C ₄ alkaryl or aryl monomer such as methoxypolyethylene glycol (meth) acrylate, allyl glycidyl ether, allyl alcohol, and glycerol (meth) acrylate; combination. The acid-swellable rheology modifier of any one of claims 1 to 11, which further comprises a spray-dried adjuvant. The acid-swellable rheology modifier of any one of claims 1 to 12, which is in the form of an emulsion. The acid-swellable rheology modifier of any one of claims 1 to 12, which is in the form of a dry powder. An aqueous composition comprising the acid swellable rheology modifier of any one of claims 1 to 14. The aqueous composition of claim 15, wherein the composition is selected from the group consisting of a personal care formulation, a health care formulation, an agricultural formulation, a paint formulation, a paint formulation, a garment, and a fabric care formulation. Cleansing formulations for household and household cleaning, as well as industrial and institutional cleaning formulations, as well as formulations for use in the electronic components industry, and for formulations in the construction industry.