WO2009115428A1

WO2009115428A1 - Cationic polymer emulsifiers

Info

Publication number: WO2009115428A1
Application number: PCT/EP2009/052753
Authority: WO
Inventors: Bingham Scott Jaynes; Xian-Zhi Zhou
Original assignee: Basf Se
Priority date: 2008-03-20
Filing date: 2009-03-10
Publication date: 2009-09-24

Abstract

Stable emulsions are obtained via the incorporation of a hydrophobically modified copolymer comprised of diallyldimethylammonium chloride (DADMAC) and diallylamine (DAA) and an optional third monomer. The polymeric emulsifying agent is an effective emulsifier at very low concentration and can be used as a part of, or in the preparation of personal care formulations.

Description

Cationic polymer emulsifiers

Stable emulsions containing an oil component and an aqueous component, e.g. oil-in-water and water in oil emulsions, are obtained via the incorporation of a hydrophobically modified copolymer comprised of diallyldimethylammonium chloride (DADMAC) and diallylamine (DAA) and an optional third monomer. The polymeric emulsifying agent is an effective emul- sifier at very low concentration and also provides conditioning and sensory benefits for lotions, conditioners, body washes and other personal care formulations.

Polymeric emulsifiers offer enhanced stability over traditional emulsifiers as a result of their strong adsorption to interfaces, the formation of steric or electrostatic barriers between drop- lets, and their tendency to thicken formulations as they emulsify. Commercial polymeric emulsifiers currently available include cross-linked polyacrylates, natural based materials, such as proteins, starches or gums, homopolymers, such as polyvinylalcohol and PVP, block copolymers including EO-PO copolymers, and a limited number of grafted copolymers. Of these materials very few are cationic in nature. It has been found that the use of hydrophobi- cally modified diallyldimethlyammonium chloride/diallylamine (DADMAC/DAA) copolymers as polymeric emulsifiers results in good emulsifying properties and good skin feel in several prototype emulsions. Good conditioning properties on hair have also been found. As a result, these materials represent a new class of multifunctional polymeric emulsifiers for both skin and hair care formulations. Cationic polymers have been used in home and personal care, water treatment, papermak- ing, mineral processing, petroleum recovery, fabrics, and pharmaceuticals. Among the most important cationic polymers are the quaternary ammonium polymers of diallyldialkyl ammonium compounds. Polymers of diallyldimethyl ammonium chloride (DADMAC) are well known in the home and personal care industry as polyquaternium 6, and are used in skin and hair care applications. The use of homo- and copolymers of diallyldimethylammonium salts in hair care applications and other personal care formulations has been disclosed in several U.S. Patents.

U.S. Pat. Appl. No. 11/595, 152 discloses cationic copolymers of diallyldimethylammonium chloride (DADMAC) and diallylamine (DAA), which are useful in home and personal care formulations. For example, these polymers provide excellent hair conditioning properties, e.g. excellent feel with less static fly away, without excess tackiness.

The copolymers as disclosed in U.S. Pat. Appl. No. 11/595, 152 also contribute useful properties to skin care products, and a variety of other personal care formulations are found therein. A number of these formulations may be oil-in water emulsions and U.S. Pat. Appl. No. 11/595, 152 discloses, along with the copolymers, the presence of from 1.0-30.0.0% by weight base on the formulation of added emulsifiers in such formulations.

Emulsifiers are not always necessary in view of the fact that the hydrophobically modified di- allyldimethylammonium chloride (DADMAC)/ diallylamine (DAA) copolymers themselves are effective emulsifying agents and can be used at low levels to prepare stable emulsions, such as oil-in water emulsions.

U.S. Pat. Spec. Nos. 3,700,623 and 3,833,531 disclose acid stabilized poly(diallylamine)- epihalohydrin resins. To prevent gelling, the resin solutions are stabilized by adding enough water-soluble acid, e.g. HCI, to adjust the pH to about 2. The acid-stabilized poly(diallyl- amine)-epichlorohydrin resins are reactivated prior to use by addition of a base, e.g. NaOH, to adjust pH to above 7.

U.S. Pat. Spec Nos. 4,354,006, 4,419,498 and 4,419,500 teach a process for making poly(DAA-ECH) polymers by reacting a diallylamine (DAA) polymer first with an allyl halide and then with hypohalous acid to convert the allyl substituents to halohydrin moieties.

JP 6, 108,382 discloses the preparation of poly(diallylamine)-epihalohydrin polymers by first preparing a diallylamine-epihalohydrin halo salt monomer by reacting diallylamine with an epihalohydrin (preferably epichlorohydrin) and then neutralizing with a halo acid (preferably HCI) followed by polymerization using a radical initiator. U.S. Patent Spec. No. 5, 147,411 discloses a method to prepare the DAA-ECH monomers (3-halo-2-hydroxypropyl)diallylamine and (2,3-epoxypropyl)diallylamine, and their quaternary ammonium salts.

U.S. Patent Spec .No. 4,341,887 discloses the conversion of the reaction product of diallylamine and epichlorohydrin (3-chloro-2-hydroxypropyl)diallylamine (a DAA-ECH monomer) to N,N-diallyl-3-hydroxy-azetidinium chloride (DAA-ECH azetidinium monomer) by heating in the presence of water. Removal of the solvent water by distillation or freeze drying causes the DAA-ECH azetidinium monomer to reconvert to the linear, non-quaternary N-3-chloro-2- hydroxypropyl-N,N-diallylamine which on standing dimerizes to 2,5-bis(diallylami- nomethyl)-p-dioxane. Polymers and copolymers of the DAA-ECH azetidinium monomer are prepared by free radical polymerization and are useful for demulsification, flocculation and floatation in water treatment.

U. S. Pat. Spec. No. 6,323,306 discloses a method to prepare certain water-soluble cationic polymers by reacting an amino-functionalized DADMAC polymer with a difunctional reactive cross linker. The reactive cross linkers include epihalohydrin and other polyfunctional com- pounds that can be used to cross-link the diallylamine polymers. The patent is limited to a DAA content of less than 5.0% to prevent formation of undesirable insoluble products which can be caused by excessive cross linking due to use of the difunctional reactive cross linker.

According to U.S. Pat. Appl. No. 11/595, 152 functionalized cationic polymers are prepared by reacting a linear or branched and optionally cross linked, amino-functional, cationic base polymer of the formula

, where R is hydrogen or d-C₄ alkyl, R₁ and

R₂ are, independently of each other, alkyl, hydroxyalkyl, carboxyalkyl, carboxamidoalkyl, or alkoxyalkyl groups having from 1 to 18 C-atoms, M_c represents a residue from an optional monomer (C), such as (meth)acrylamide or (meth)acrylate, n, m and p are the mol fractions of the repeating units in the corresponding brackets, respectively, of the cationic reactant of formula (I), m + n + p = 1 , and Y^" represents an anion, with at least one functional compound which can react with at least a part of the amino functional groups in the base polymer.

It has been found that polymers of U.S. Pat. Appl. No. 11/595, 152 are hydrophobically modified during the above reaction are surprisingly effective in preparing and stabilizing emulsions, such as O/W emulsions, even when used in low concentrations.

The invention relates to a stable emulsion of an oil component and an aqueous component comprising as emulsifier a co-polymer, diallyldimethylammonium chloride (DADMAC), diallylamine (DAA) and an optional third monomer unit which copolymer has been hydrophobically modified at the nitrogen of the diallyl amine by reaction of grafting with a functionalizing agent and a method for forming the stable emulsion oil-in-water emulsion. More than one copolymer may be used.

For example, the copolymers contain as repeating units the following moieties:

B' B or R₁ R_n

B' B

Wherein, w, m and p are the mol fractions of the corresponding repeating units incorporated into the copolymer wherein n is from about 20.0% to about 99.0%, m is from about 0.0% to about 40.0%, w is from about 0.1.0% to about 40.0%, p is 0.0% to about 40.0%, and m + w + n + p = 100.0%;

Mc represents a residue from an optional ethylenically unsaturated monomer;

Ri and R₂ are, independently of each other, alkyl, hydroxyalkyl, carboxyalkyl, carboxamidoal- kyl, or alkoxyalkyl having from 1 to 18 C-atoms;

R₃ is hydrogen or Ci-i₈alkyl; each Y^" independently represents an anion;

Fg is selected from the group consisting of

Wherein F₉' is H, C i-₃o alkyl or a group

— O-R

\ / I \ I

.Si-O H- Si-O + Si-R I \ \ h \

-N-R

wherein R is hydrogen, Ci_-3oalkyl, Ci_-3operfluoroalkyl, 1 to 1500 ethoxy units, 1 to 1500 pro- poxy units, 1 to 1500 mixed ethoxy-propoxy units and r is a number from 1 to 100 and wherein the polymer may be substituted by one or more than one group F₉. The molecular weight of the copolymer may vary, for example, an average molecular weight is in the range of one 1.0 x 10 - 5.0 x 10⁶ atomic mass units.

The stable emulsion comprises as emulsifier from about 0.05% to about 30.0% by weight, based on the total weight of the co-polymer.

The stable emulsion may be, for example, a water-in-oil emulsion or an oil-in-water emulsion. In one embodiment the stable emulsion which is a stable oil-in-water emulsion comprising the copolymers described above.

For example, in the above formulae describing the co-polymer used as emulsifier

Mc represents a residue selected from the group consisting of acrylamide, methacrylamide, alkyl or dialkyl acrylamide or methacrylamide, acrylate, methacrylate, acrylic acid and methacrylic acid monomer;

R₁ and R₂ are, independently of each other,

R₃ is H or Ci_-4alkyl;

Y^" is selected from the group consisting of chloride, bromide, iodide, fluoride, sulphate, phosphate, nitrate, acetate and tetrafluoroborate anions; and

OH Fg is selected from the group consisting of and , wherein F₉' is H,

Ci_-30alkyl or a group — O-R

-N — R

wherein R is hydrogen or

For example, Y^" is selected from the group consisting of chloride, bromide and iodide anions; and F₉' is H, Ci-₂₄ alkyl or a group

— O-R

-N — R

For example, F₉' is group — \ ^R .

The copolymer is effective at very low concentrations as well as at higher concentrations. For example, the invention provides a stable emulsion, such as stable oil-in-water emulsion, wherein the copolymer is present in a concentration of from about 0.1.0% to about 30.0%, for example from about 0.1 % to about 20.0%, for example from about 0.1% to about 2.0% or from about 0.05% to about 2.0% by weight based on the total weight of the emulsion.

According to a preferred embodiment, M_c is the residue of a vinyl monomer selected from the group consisting of acrylamides, methacrylamides, acrylates, methacrylates, acrylic acid, methacrylic acid, vinyl sulphonic monomers, vinyl phosphonic monomers, vinyl pyrrolidones, vinyl alcohol and vinyl acetate.

The amount of oil component in the emulsion can vary, for example a stable oil-in-water emulsion comprising the present copolymers wherein the oil phase is from about 1.0% to about 60.0%, for example from about 1.0% to about 40.0%, for example, from about 1.0% to about 30.0% by weight based on the total weight of the emulsion.

The coefficients n, m, p and w relate to the proportional amount of each repeating unit in the polymer. While a very broad range of values for each coefficient may be envisioned, the following ranges are typical: n = about 20.0% - 99.0%, for example about 40.0%- 98.0%, preferably about 50.0% - 95.0%, for example about 60.0% - 95.0%; m = about 0.0% - 40.0%, for example about 0.1.0%- 30.0%, preferably about 0.1 -20.0%, for example about 0.1- 15.0%; w = about 0.1 % - 40.0%, for example about 0.1%- 30.0%, preferably about 0.1 -20.0%, for example about 1.0- 15.0%, p = 0.0% to about 40.0%, preferably less than 20.0%.

Given that w represents the amount of repeating unit B which is modified during the function- alization or grafting reaction, its upper limit is the amount of B present prior to functionaliza- tion or grafting and m represents that amount of B which remains after the starting polymer is functionalized. Thus, m can be 0.0% or close to 0.0% if the functionalization or grafting reaction is run under conditions leading to total derivatization. The term "about 0.0%" is used because, in reality, even when attempting 100.0% derivatization, there are trace amount of starting moiety remaining. In the event that p may actually be 0.0% this represents the amount of optional monomer used in preparing co-polymer which is then derivatized into the present emulsifiers.

Any amount of derivatization of the diallyl amine moiety B can occur to produce the present emulsifiers depending on the final application. Some finite amount is required.

It should of course be understood that the above formulae are idealized - in the actual poly- mers the various groups may be linked in any order so that, for example, both block and random copolymers are within the scope of the above formulae.

A further embodiment of the invention relates to a method for preparing a stable emulsion of an oil component and an aqueous component, for example, a water-in-oil or an oil-in-water, for example, a stable oil-in water emulsion, which method comprises incorporating via stan- dard means into the components of the emulsion from about 0.05% to about 30.0% by weight based on the total weight of the emulsion at least one of the above copolymers. Any manner of copolymer addition may be used and the copolymer may be incorporated first into either the water phase or oil phase prior to combination of the two phases, or the copolymer may be added to a combination of the two phases. The copolymers, that is the polymeric emulsifying agents of the invention, are prepared according to the procedures of U.S. Pat. Appl. No. 11/595, 152. For example: Preparation of the amino-functionalized base polymer

Any quaternary ammonium cationic monomer may be used as monomer precursor to moiety A. The cationic monomers useful in the practice of this invention include diallyldialkyl ammonium compounds, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, and 3-acrylamido-3- methyl butyl trimethyl ammonium chloride. The preferred cationic monomers for monomer A are diallyldialkyl ammonium compounds which may be represented by the formula A'

where R₃ and R₄ are, independently of each other, hydrogen or a Ci-C₄alkyl group, Ri and R₂ are, independently of each other, an alkyl, hydroxy-C₂-C₄alkyl, carboxyCi-C₄alkyl, or car- boxyamidoalkyl or alkoxyalkyl group having from 1 to 18 C-atoms, for example methyl, and Y^" represents an anion. R₃ and R₄ are preferably hydrogen.

Examples of cationic monomers include diallyldimethyl ammonium chloride (DADMAC), di- allyldimethyl ammonium bromide, diallyldimethyl ammonium sulphates, diallyldimethyl am- monium phosphates, dimethallyl dimethyl ammonium chloride, diethylallyl dimethyl ammonium chloride, diallyl di(beta-hydroxyethyl ammonium chloride and diallyl di(beta-ethoxyethyl) ammonium chloride. For example, the cationic monomer DADMAC is preferably used because of its commercial importance.

Suitable compounds for the monomer precursor to moiety B and B' include diallylamines. In one embodiment the diallylamine represented by the formula B"

where R, R₃ and R₄ are, independently of each other, hydrogen or Ci-C₄alkyl. R, R₃ and R₄ are preferably hydrogen.

Examples of diallylamine monomers of formula B include diallylamine (DAA), 2,2'-dimethyl diallylamine, 2,2'-diethyl diallylamine, 2,2'-diisoprpyl diallylamine, 2,2'-dipropyl diallylamine, 2,2'-diisobutyl diallylamine, N-methyl diallylamine (MDAA), N-ethyl diallylamine, 2,2'-dime- thyl-N-methyl diallylamine, 2,2'-diethyl-N-methyl diallylamine, 2,2'-diisopropyl-N-methyl dial- lylamine, 2,2'-dipropyl-N-methyl diallylamine, 2,2'-dimethyl-N-ethyl diallylamine, and 2,2'-diethyl-N-ethyl diallylamine, for example, DAA and MDAA.

Suitable compounds for monomer precursor for C are olefin monomers that are other than monomer A or monomer B". Examples of such olefin monomers include acrylamide, methacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N,N-dimethyl aminopropyl acrylamide and their salts, acrylic acid, methacrylic acid, vinyl sulphonic acid and their salts, vinyl pyrrolidone, hydroxyethylacrylate, vinyl amines, vinyl formamide, vinyl alcohol, vinyl caprolactam, vinyl derivatives of dimethyl siloxane, aminosiloxanes, vinyl fluorocarbons, hy- droxyalkyl acrylates, 2-hydroxypropyl-acrylate, and 2-hydroxybutyl-acrylate, aminoalkyl acrylates, such as N,N-dimethyl aminoethyl methacrylate, N,N-dimethyl aminoethyl acrylate, diethylaminoethyl acrylate and 7-amino-3,7-dimethyloctyl acrylate, and their salts including their alkyl and benzyl quaternized salts, and the like.

The copolymerization of monomers A', B" and, optionally, precursor monomer for C to form the cationic polymer which is subsequently functionalized can be carried out by aqueous solution polymerization, water-in-oil inverse emulsion polymerization or dispersion polymerization using a suitable free radical initiator.

(B) Functionalizing or grafting the polymer.

An amino-group containing polymer (I) prepared for example as described above, is func- tionalized or modified by reacting it with at least one reactive functional compound (grafting agent and/or cross linking agent) (II). Compounds with groups that can react with the amino- functional groups polymer (I) include epoxy compounds, haloalkyl compounds, isocyanate compounds and compounds containing activated olefin double bonds, such as acrylates and acrylamides. Suitable reactive compounds for grafting or cross linking in non-aqueous sys- terns also include acid halides and anhydrides.

In one embodiment of the invention, the functional reactive compound or grafting agent (II) is

an epoxy or halohydrin compound to give the functional group F₉ as

Examples of monofunctional epoxy compounds suitable for grafting include glycidyl compounds, for example: mono-(2,3-epoxy)propylether-terminated polydimethylsiloxanes, 3-gly- cidoxypropyltrimethoxysilane, 1-oxy-2,2,6,6,-tetramethyl-4-glycidyloxypiperidine, glycidyl iso- propyl ether, glycidyl isobutyl ether, glycidyl heptyl ether, glycidyl 2-methylphenyl ether, glycidyl hexadecyl ether, glycidyl hexadecafluorononyl ether, glycidyl 4-nonylphenyl ether, 1 ,2- epoxydodecane, 1 ,2-epoxyoctadecane, 1 ,2-epoxy-3-phenoxy propane, glycidyltrimethylam- monium chloride, glycidyl 3-nitrobenzenesulphonate, and the like.

Examples of polyfunctional epoxy compounds include, ethylene glycol diglycidyl either (EGDE), diglycidyl ether, 1 ,2,3,4-diepoxybutane, 1 ,2,5,6-diepoxyhexane, poly(propylene gly- col) diglycidyl ether (PPGDE), 1 ,4-butanediol diglycidyl ether, 3-bis(glycidyloxy)methyl-1 ,2- propanediol, bisphenol A diglycidyl ether (BADGE), poly(phenyl glycidyl ether-co-formalde- hyde), glycerol propoxylate tri-glycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, triglycidyl isocyanurate and the like.

Certain epoxy compounds in halohydrin form can also be used as reactive compounds for functionalizing the amino cationic base polymer. Examples of these include 3-chloro-2-hydro- xypropyl-dimethyldodecylammonium chloride and 3-chloro-2-hydroxypropyl-dimet.hyloct.ade- cylammonium chloride (Quab^® 342 and QUAB 426, DEGUSSA).

Haloalkyl compounds can also be used as reactive compounds for functionalizing the base amino cationic polymer. Examples of mono-functional haloalkyl compounds suitable for graf- ting include chloroethane, bromoethane, 1-chloropropane, 1-chlorobutane, chloroacetic acid and its salts, dichloride-substituted cyanuric chloride and the like. Thus, in the functionnalized cationic polymer F₉ will be the residue of a haloalkyl compound to give the functional group

The haloalkyl compound may also be a monovalent, perfluorinated, alkyl or alkenyl, linear, branched or cyclic organic radical having three to twenty fully fluorinated C-atoms, which organic radical is optionally interrupted by divalent oxygen or sulphur atoms, and having a terminal iodine group. The perfluoroalkyl moiety may be a single perfluoroalkyl group, for example perfluorobutyl or perfluorohexyl, or a mixture of such groups, for example a mixture of

^C4^F9^"' ^C6^F13^"' ^C8^F17^"' ⁰IO¹V' ^C12^F2₅ ^{" and}

Perfluoroalkylethyl iodides and perfluoroalkyl iodides C_nF_2n+I-I with n = 4 to 14 are commercially available as described in U.S. Pat. Appl. No. 11/595, 152.

In one embodiment the functionalized cationic polymers of this invention may be synthesized by first reacting allyl glycidyl ether or an allyl halide with a primary or secondary amine on the cationic base polymer to introduce at least one allyloxy group, then adding an R_F-iodide to the resulting allyloxy radical, followed by partial or complete dehydrohalogenation. This is analogous to the reaction sequence as disclosed in U.S. Pat. Spec. No. 6, 706,923. The addition of the perfluoroalkyl iodide to the allyloxy group may be carried out using methods and conditions similar to those disclosed for the addition of a perfluoroalkyl iodide to allyl alcohol in U.S. Pat. Spec. No. 5,585,517.

In another embodiment perfluoroalkylethyl iodides may also be added to a cationic base polymer backbone by first forming a perfluoroalkylethylene intermediate, which then adds to the amine groups on the polymer backbone as described in U.S. Pat. Spec. No. 6,365,676.

The group F₉ may also be attached by reacting at least one compound containing an activated olefin double bond, wherein said compound is, for example, an acrylate or acrylamide

compound, to give the functional group Fg as the F₉

groups are the same or different.

Anhydride compounds can also graft to base polymers containing primary or secondary amino groups. Examples of suitable anhydride compounds for reactant (II) include phthalic, maleic, succinic, pyromellitic and tetrahydrophthalic anhydrides, 2-dodecen-1-yl succinic anhydride and the like. In one embodiment the anhydride compound is 2-dodecen-1-yl succinic anhydride.

The grafting reaction can be carried out in an aqueous medium or in the same reaction medium, e.g. water-in-oil emulsion, as is used for preparing the base polymer in step (A). The reaction is, for example, carried out in aqueous medium at a pH of from about 7 to about 1 1 , for example, from 7.5 to 9.5, and at a temperature from about 0.0 to about 100.0⁰C, for ex- ample, from 20.0 to 80.0 C. The solids concentration of the base polymer in the reaction medium prior to reaction can be, by weight, from 1.0% to about 60.0%, preferably from 10.0% to 25.0% for a solution of the base polymer, and preferably from 20 to 50.0% for an emulsion or dispersion of the base polymer.

The amount of copolymer amine which is functionalized or grafted is determined by the reac- tion conditions and stoichiometry. When preparing a copolymer with more than one

F_g-groups, the different functionalizing or grafting agents can be added either at the same time in a single step or in separate steps.

In one embodiment the reactive compound is a hydrophobic reactant (II) which dissolves, at least in part, in the aqueous phase and is grafted onto the functional portion of the polymer backbone to form a polymer having both cationic and hydrophobic groups. When the hydrophobic reactant (II) is added to the polymer in an amount higher than its water solubility, the excess amount can form a second phase in the form of fine droplets if adequate agitation is provided. At the high reaction pH (> 8), the amine groups in the cationic base polymer are not protonated and may form hydrophobic domains to absorb hydrophobic reactant (II) for grafting. The hydrophobic domains of the polymer will grow as the hydrophobic grafting progresses, accelerating transfer of hydrophobic reactant (II) to the reaction sites. The fine drop- lets of hydrophobic reactant (II) will eventually disappear after they are all transferred to the hydrophobic domain of the base polymer (I) for grafting.

Reactants with a functional group reactive to the amino groups in the base cationic polymer but also very reactive with water are preferably grafted in a non-aqueous solvent. In one embodiment the cationic base polymer is prepared in an aqueous solution. The aqueous solu- tion of base polymer can then be dried to remove water and redissolved in a non-aqueous solvent for reacting with water-sensitive reactive compounds, such as acid halides and anhydrides. Alternatively, a non-aqueous solvent can be added to the solution of the aqueous base polymer and the water removed by azeotropic distillation.

Examples of water-sensitive reactive compounds preferred for non-aqueous grafting include but are not limited to acid halides, anhydrides and isocyanates. Since the reaction of an iso- cyanate with a primary or secondary amino group is much faster than with water, isocyanate compounds can also be reacted in an aqueous medium.

Another embodiment of the present invention is polyDADMAC copolymers with grafted antioxidant or UV absorbent functionality, such as those shown in U.S. Pat. Appl. No. 11/595, 152.

The molecular weight of the polymers of the present invention is not critical. It can range from 1.0 x 10³ to 5.0 x 10⁶, for example 1.0 x 10⁴ to 5.0 x 10⁶, and especially 2.0 x 10⁴ to 2.0 x 10⁶ atomic mass units, which can be a number or weight average molecular weight and can be determined by any commonly available method, such as light scattering, gel permeation chromatography, size exclusion chromatography, etc.

The polymers, prior to emulsion formation, can be present in various physical forms, i.e. solutions, dispersions, suspensions, granules, powders, beads, blocks, etc. In the case of liquid forms, such as solutions, dispersions, suspensions, etc., the liquid phase can be aqueous and/or non-aqueous, such as a dispersion in soybean oil, an ester or mineral oil. Preferred hydrocarbons as the non-aqueous solvent or dispersion medium include, naphthol spirits, Escaid®1 10 (Exxon), LPA 170 (Condea Vista) and Conosol® 200 (Penreco), which are aro- matics/paraffins/naphthalenes mixtures.

As stated above, the present emulsions are prepared by incorporating the copolymers via any standard technique to the emulsion components. In an oil and water emulsion of the invention, for example in a stable oil-in-water emulsion, the oil phase (oil component) can be chosen form any of the commonly used substances, for example:

Fatty alcohols including: Guerbet alcohols based on fatty alcohols having from 6 to 18, pref- erably from 8 to 10 C-atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoates of Ci₂-Ci₅ alcohols, acetylated lanolin alcohol, etc.

Esters of fatty acids including: Esters of linear C₆-C₂₄ fatty acids with linear C₃-C₂₄alcohols, esters of branched C₆-Ci₃carboxylic acids with linear C₆-C₂₄fatty alcohols, esters of linear C₆- C₂₄fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C₆-C₂₂ fatty alcohols, especially dioctyl maleates, esters of linear and/or branched fatty acids with polyhydric alcohols, for example propylene glycol, dimer diol or trimer triol, and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethyl- hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmit- oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimeriza- tion of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, ara- chidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxo-syn- thesis and as monomer fractions in the dimerization of unsaturated fatty alcohols).

Examples of such ester oils include isopropyl myristate, isopropyl palmitate, isopropyl stea- rate, isopropyl isostearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyl- laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl hept- anoate, diisostearyl maleate, octyl hydroxystearate, etc.

Further oil components that can be used include dicarboxylic acid esters, such as di(2-ethyl- hexyl)-2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and also diol esters,, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelar- gonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C₆-C₂₄fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C₂-Ci₂dicarboxylic acids with linear or branched alcohols having from 1 to 22 C-atoms or polyols having from 2 to 10 C-atoms and from 2 to 6 hydroxy groups can also be used.

Natural or synthetic triglycerides including glyceryl esters and derivatives include:

Di- or tri-glycerides based on C₆-Ci₈ fatty acids, modified by reaction with other alcohols, such as caprylic/capric triglyceride, wheat germ glycerides, etc., fatty acid esters of polyglyc- erol, such as polyglyceryl-n, such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc., or castor oil, vegetable oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, maca- damia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc. can also be used.

Waxes include: Esters of long-chain acids and alcohols as well as compounds having wax- like properties, e.g. carnauba wax (Copernicia Cerifera), bees wax (white or yellow), lanolin wax, candellila wax (Euphorbia Cerifera), ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax, etc., also, hydrophilic waxes as cete- aryl alcohol or partial glycerides.

Pearlescent waxes include: Alkylene glycol esters, especially ethylene glycol distearate, fatty acid alkanolamides, especially coco fatty acid diethanolamide, partial glycerides, especially stearic acid monoglyceride, esters of polyvalent, unsubstituted or hydroxy-substituted carbo- xylic acids with fatty alcohols having from 6 to 22 C-atoms, especially long-chained esters of tartaric acid, fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 C-atoms, especially laurone and distearyl ether, fatty acids,, such as stearic acid, hydroxystearic acid or behenic acid, ring- opening products of olefin epoxides having from 12 to 22 C-atoms with fatty alcohols having from 12 to 22 C-atoms and/or polyols having from 2 to 15 C-atoms and from 2 to 10 hydroxy groups, and mixtures thereof.

Hydrocarbon oils include: Mineral oil (light or heavy), petrolatum (yellow or white), micro- crystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes, and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from the plant and animal kingdoms.

Silicones or siloxanes (organosubstituted polysiloxanes) include: Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form, linear polysiloxanes: dimethicones, dimethi- conol, cyclic silicone fluids: cyclopentasiloxanes, phenyltrimethicones. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. Fluorinated or perfluorinated oils include: Perfluorhexane, dimethylcyclohexane, ethylcyclo- pentane, and polyperfluoromethylisopropyl ether.

The emulsions of the present invention are very useful in personal care compositions, such as hair and skin care compositions. These compositions will generally comprise at least one cosmetically-functional agent used in an amount effective to impart desired cosmetic proper- ties to the personal care composition.

The term "cosmetically-functional agent", as used herein, means any material, compound or composition applied to the hair or skin for a cosmetic effect. Exemplary cosmetically-functional agents include but are not limited to emollients, humectants, lubricants, UV-light absorbers, sunless tanning agents, e.g. DHA, antioxidants, free radical scavengers, preserva- tives, pigments, dye lakes, dyes, other colorants, aesthetic enhancers, such as polysiloxanes and their various derivatives, rheology modifiers, natural polymers and their various derivatives and copolymers, e.g. starch, cellulosic polymers, gluccans, and their derivatives), perfumes and fragrances, film formers (water proofing agents), antiseptics, antifungal, antimicrobial and other medicaments, solvents, surfactants, natural or synthetic polymers, other conditioning agents and hair fixatives. Such cosmetically-functional agents also include mineral oils, glycerol, beeswax, lanolin, acetylated lanolin, stearic acid, palmitic acid, cetyl alcohol, sodium salts of olefin sulphonates, various proteins and derivatives, polymeric sugars, conditioning agents, such as polyquaterniums and hair fixatives, such as polyvinyl pyrroli- done) and the copolymers of vinyl pyrrolidone with other monomers, and polyvinyl forma- mide.

The cosmetically-functional agent may be present in the personal care composition in an amount of from 0.01 to 60.0% by weight based on the total weight of the personal care composition. In one embodiment the present invention is directed to a personal care composition comprising,

A) The present oil-in water emulsion;

B) At least one cosmetically-functional agent; and C) At least one cosmetically tolerable adjuvant.

Personal care compositions include a very wide range of products including for example, cosmetic formulations for hair treatment, for example hair washes in the form of shampoos, hair conditioners, hair-care products, for example pre-treatment products, hair tonics, hair styling creams and gels, pomades, hair rinses, deep conditioning treatments, intensive hair care treatments, hair setting products, for example waving agents for perms (hot wave, mild wave, cold wave), hair straightening or relaxing products, liquid hair fixatives, hair foams, hair sprays, bleaching agents, bleaching shampoos, creams, bleaching pastes or oils, temporary, semi-temporary or permanent hair dyes, products containing self-oxidizing dyes or natural hair dyes, such as henna or chamomile, and mascaras. They also include rinse off and leave on skin care products, for example softening, moisturizing and anti-wrinkle creams, lotions and gels, light-protective preparations, such as sun tan lotions, creams and oils, sun blocks and pretanning and sunless tanning preparations, therapeutic compositions, such as anti-acne and anti-psoriasis creams, gels and pastes, as well as skin colouring products, such as facial make-up in the form of lipsticks, lip gloss, eye sha- dow, liquid make-up, day creams or powders, and facial lotions, creams etc.

The present emulsions are useful, for example, as part of, or in the preparation of skin products, including cleansers creams, lotions etc. Other emulsifiers may be present in personal care compositions comprising the polymeric emulsifying agents of the present invention, but in general, these are not preferred. In one embodiment, the only emulsifiers present are the copolymers of the present invention.

The personal care formulations of the present invention may also include other common components as described in of U.S. Pat. Appl. No. 11/595, 152, such as surfactants, adjuvants and additives.

The choice of surface-active compound (surfactant) and the amount present in personal care formulations according to the invention will depend on the intended use of the composition. In personal care compositions, different surfactant systems may be chosen, as is well known to the skilled formulator. For example, body washes may incorporate significant amounts of anionic surfactants, moisturizers may incorporate significant amounts of cationic surfactants. The total amount of surfactant present will also depend on the intended end use and may be as high as 60.0% by weight. Preferably, the compositions will comprise at least 2.0% by weight of surfactant, e.g. 2.0-60.0%, preferably 15.0-40.0%, and most preferably 25.0-35.0% as further adjuvants and additives, mild surfactants, super-fatting agents, consistency regu- lators, thickeners, polymers, stabilizers, biologically active ingredients, deodorizing active ingredients, anti-dandruff agents, film formers, swelling agents, UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, solubilizers, perfume oils, colorants, bacteria-inhibiting agents and the like.

The adjuvants and additives may optionally be present in the personal care composition in an amount of, for example, from 0.1 to 25.0% by weight based on the total weight of the personal care composition.

Super-fatting agents: Substances suitable for use as super-fatting agents include, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultane- ously acting as foam stabilizers.

Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds. Other adjuvants: It is furthermore possible for the personal care composition to contain, as adjuvants, antifoams, such as silicones, structurants, such as maleic acid, solubilizers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, fluorocarbons, N₂O, dimethyl ether, CO₂, N₂ or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulphonic acid, or oxidizing agents, such as hydrogen peroxide, potassium bromate or sodium bromate. For skin care there comes into consideration insect repellents. The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments can be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.

PLENARY EXAMPLES

Synthesis of diallyldimethylammonium chloride-co-diallyl copolymer (DADMAC/DAA copolymer)

In a 1 I reactor, diallyldimethylammonium chloride (65.0 wt.0%, 260.0 g), diallylamine (97.0%, 17.2 g) and sodium EDTA (0.23 g in 2 g water) is added. To the mixture HCI aqueous solution (19.1 g cone. HCI (37.0 wt.0%) in 26.7 g water) is added. The solution is heated to 92°C and initiator ammonium persulphate (3.3 g in 18.5 g water) is added at rate of 0.05 ml/min. During the polymerization water is added if the solution viscosity is too high. After addition of the initiator the solution is stirred for an additional 1 hr. Sodium metabisulphite (6.0 g in 24.0 g water) is added at 0.5 ml/min. The solution is stirred for another hour and water is added to bring the solid content to about 40.0 wt.0%. Molecular weight is measured by GPC: M_w: 269 kg/mol. Synthesis of DADMAC/DAA/AA copolymer

In a 1 I reactor, DADMAC (65.0 wt.0%, 260.Og), diallylamine (97.0%, 16.0 g), acrylic acid (99.0%, 22.0 g) and sodium EDTA (0.23 g in 2.0 g water) are added. To the mixture HCI aqueous solution is added to adjust the pH to 5. The solution is heated to 92°C and initiator ammonium persulphate (3.3 g in 18.5 g water) is added at rate of 0.05 ml/min. During the polymerization water is added if the solution viscosity is too high. After addition of the initiator the solution is stirred for an additional 1 hr. Sodium metabisulphite (6.0 g in 24.0 g water) is then added at 0.5 ml/min. The solution is stirred for another hour and water is added to bring the solid content to about 40.0 wt.0%. Molecular weight measured by GPC: M_w: 11 1 kg/mol.

General synthesis of hydrophobically modified polyDADMAC Aqueous NaOH-solution (5.0 wt.0%) is added to DADMAC copolymer solution (40.0 wt.%) to adjust the pH to 9.5. The mixture is heated to 70⁰C. To the solution QUAB-agents (40.0 wt.0% active, 90.0 mol% with respect to the DAA content) are added. During the reaction water is added if the solution viscosity is too high. The mixture is then stirred for 10 hrs.

Preparation of emulsions The polymer is first dissolved in the aqueous phase. The resulting solution is combined with the oil phase (80:20 v/v) and mixed with a Heidolph mechanical stirrer for 2 min at 1000 rpm. Emulsion stability is visually evaluated over time for separation. Co-polymerization of diallyldimethylammonium chloride (DADMAC), diallylamine (DAA) and the optional third hydrophilic monomer results in a DADMAC copolymer with a DAA weight percentage in the range of 0.0-40.0%. The secondary amines of the DAA in the copolymer are subsequently chemically modified by a variety of grafting chemistry. Grafting of 3-chloro- 2-hydroxypropyl-alkyl-dimethyl-ammonium chloride (QUAB) to the secondary amines of the DAA results in a hydrophobically modified cationic polymer with various degrees of hydrophobic content as shown in Figure 1. A wide range of additional monomers can be included in the DADMAC/DAA without interfering with the reactivity of the DAA component. Examples of terpolymers that are subsequently grafted include DADMAC/DAA/acrylamide and DADMAC/DAA/acrylic acid.

I = 60-100 wt %; m = 0-40 wt%; n = 0-20 wt% R= COOH, CONH₂

Q _R, _ _{|au ry| steary}|

Figure 1 : Structure of hydrophobically modified DADMAC copolymer

Three hydrophobically modified copolymers that are evaluated for emulsifying properties are shown in Table 1 , along with weight percentage of DADMAC, DAA, and third monomer (where applicable), and type of hydrophobic graft.

Table 1 : Hvdrophobically Modified Copolymers Evaluated for Emulsifying Properties

Hydrophobic modification with lauryl or stearyl groups results in materials that provide good emulsification of oil/water mixtures at low polymer concentrations of 0.25-1.0%. Two other commercially available polymeric acrylate emulsifiers are included as comparison, Pemulen® TR- 1 and lnutec®SP1. The results of emulsification trials of 20.0% oil phase in water using three different oils are shown in Table 2. Results indicate that Polymer B is particularly effective at emulsifying oil in water mixtures. Both Polymer B and Pemulen provide stability for >2 weeks, as long as the samples are observed. It should be noted that Pemulen is not cationic, but is chosen as a general comparison because it is a well known hydrophobically modified polymer.

Additional formulations are prepared containing glycerol as shown in Table 3 and are emulsified using Polymer B. These lotion prototypes also demonstrated excellent stability over the test period. Initial investigations of the skin feel of these formulations indicate that the polymer delivers a highly lubricious and durable modification to the skin in comparison to the Pemulen containing system.

Table 2: Emulsification Properties of Oil/Water mixtures with Three Different Oils at 20.0% (v/v) in Deionized Water

a⁾ PEMULEN mixture neutralized with 1.13g 4.0% NaOH solutions Table 3: Emulsification Properties of Lotion Prototypes Containing Glycerol

¹⁾20.0% i-propyl myristate, 5.0% glycerol, 75.0% water

²⁾ 10.0% i-propyl myristate, 15.0% glycerol, 5.0% mineral oil, 75.0% water In hair care applications, the highly cationic nature of these polymers results in high affinity to the hair cuticle similar to pDADMAC homopolymer (PQ-6). Thus, these materials provide conditioning and protection benefits to the hair in both leave on and rinse off applications.

The evaluation of the present copolymers in various water/oil systems reveals that the material is an effective emulsifier at very low concentration. Stable emulsions are formed at 0.5% polymer addition in 20.0% oil systems containing either isopropyl myristate, mineral oil or

ISOPAR M. Glycerol containing systems are also stabilized. In addition, the cationic nature of the polymer in combination with the large hydrophobes provide lubricious and silky skin feel when used in prototype lotion formulations and provided conditioning properties on hair.

Working Examples

EXAMPLE 1

Synthesis of pDADMAC/DAA copolymer

A 1 -liter reactor equipped with a condenser, a thermometer, a nitrogen inlet and an overhead agitator is charged with 260.0 g of 66.0% DADMAC monomer, 34.5 g of diallylamine (DAA), 35.0 g of HCI solution, 6.0 g of deionized water, and 0.4 g of 20.0% Na₄EDTA solution. The polymerization mixture is purged with nitrogen and heated with agitation to a temperature of 8O⁰C. An aqueous solution containing 2.1 g of ammonium persulphate (APS) is slowly fed to the reaction mixture over 190 minutes. The reaction temperature is allowed to increase to above 90 C and then maintained at 90 to 100⁰C during the APS feed period. After the APS feed, the reaction temperature is held at 95⁰C for about 30 minutes. Then an aqueous solu- tion containing 6.0 g of sodium metabisulphite (MBS) is added over 30 minutes. The reaction mixture is held at 95⁰C for another 30 minutes to complete the polymerization (above 99.0% conversion). The polymer solution is then diluted with sufficient water to about 35.0% solids by weight and cooled to room temperature. The final product has a Brookfield viscosity of 9100 cps at 25 ⁰C (using a Brookfield LV4 spindle at 30 rpms) and 33 .0% polymer solids.

EXAMPLE 2

Following the same procedure as Example 1 the following polymers (in Table 1 below) are synthesized. The final product viscosities are measured at 25 ⁰C using a Brookfield viscometer using a Brookfield LVT #3 spindle at 12 rpms. The viscosity results are shown in Table 1 below.

TABLE 4

EXAMPLE 3

A 0.5-liter reactor fitted with a mechanical stirrer, addition funnel and condenser is charged with 228.0 g (0.129 mol secondary amine, NH) of the base polymer from Example 1. The reactor content is adjusted with 6.0 g of 25.0% NaOH-aqueous solution to a pH of 9.0 to 10.0 and heated to 7O⁰C with agitation. After the pH adjustment, 7.6 g (0.0076 mol epoxide) of mono-(2,3-epoxy)propyl ether-terminated polydimethylsiloxane (MCR-E1 1 from Gelest) is added into the reactor. The grafting reaction is maintained at about 7O⁰C, and the viscosity of the reaction solution is monitored with an agitator torque meter. The viscosity of the reactor contents, as is indicated by the torque meter reading, increases with reaction time. The viscosity increase is believed to result from association of grafted hydrophobic siloxane groups and can be an indication of the grafting reaction. While the viscosity shows little further increase with increasing reaction time after about four hours, the reaction mixture is held at 70 C for another 2 hrs. A concentrated HCI solution and deionized water are added to adjust the pH to about 5 and the solids. The resulting polymer product is a homogeneous, yellowish emulsion-looking solution having 20.0 wt.-% of polymer solids (base polymer Ia + grafting agent II) and a Brookfield viscosity of about 1200 cps (using a Brookfield LV3 spindle at 30 rpms at 25 ⁰C). The functionalized cationic polymer contains about 10.0 wt.-% of grafted MCR-E11 , which provides hydrophobic siloxane functionality to the copolymer. EXAMPLE 4

The procedure of Example 3 is followed except that 18.1 g instead 7.6 g of MCR-E11 grafting agent is added. The resulting polymer product is a homogeneous, yellowish emulsion-looking solution with 20.0 wt.-% of polymer solids (base polymer I + grafting agent II) and a Brookfield viscosity of about 1200 cps (using a Brookfield LV3 spindle at 30 rpms at 25⁰C). The copolymer contains about 20.0 wt.-% of grafted MCR-E11 which provides substantial hydrophobic siloxane functionality to the cationic copolymer.

EXAMPLE 5

A 1 -liter reactor fitted with a mechanical stirrer, addition funnel and condenser is charged with 250.0 g of 22.1 wt.-% base polymer from Example 1 (0.096 mol secondary amine, NH). 6.0 g of a 25.0% NaOH solution is added to bring the pH above 9.0. The reactor contents are diluted with 26.2 g of deionized water. 10.0 g of 2-hydroxyethyl acrylate (HEA, 97.0%) is added at a temperature of about 2O⁰C. The reaction is monitored by following the disappear- rance of HEA via liquid chromatography (HPLC). The grafting reaction is terminated after more than 95.0% of the added HEA has reacted. The reaction causes an increase in visco- sity. Deionized water is added from time to time during the reaction to maintain a suitable reaction viscosity for agitation. The resulting product is a clear solution containing 1 1.5 wt.-% of the grafted polymer solids. The polymer solids contain about 15 wt.-% of grafted HEA units which adds hydroxy functionality to the cationic pDADMAC/DAA copolymer.

EXAMPLE 6 1.8 g acrylamide (50.0%) solution is added to 25.0 g of the product from Example 1 after the pH is adjusted to 9.0 with a 25.0% NaOH solution. After thorough mixing the solution is allowed to react at 23 to 26⁰C for about three days. The solution viscosity increases from an initial 7720 cps to 16,320 cps after the reaction. The resulting polymer solution is clear and contains 31.2 wt.-% polymer solids. The obtained cationic copolymer has about 15.0 wt.-% of grafted acrylamide units which adds the functionality of pendant amide groups to the cationic pDADMAC/DAA copolymer. EXAMPLE 7

50.0 g (428 mmol) of methoxypolyethylene glycol 350 (MPEG 350, Dow chemical) is placed into a round-bottomed flask equipped with a stirrer, nitrogen inlet and a thermoregulator and heated with stirring. When the temperature reaches 65⁰C, 1.6 g of boron trifluoride etherate is added to the flask. Then 35.7 g (386 mmol) of epichlorohydrin is added dropwise to the flask over 1 hour. An exothermal reaction is observed with an increase in temperature from 65⁰C to 74⁰C. When the rise in temperature subsides, the reaction mixture is maintained at 65⁰C for three hours with stirring. At this time the consumption of epichlorohydrin is deter- mined to be complete by gas chromatography. Next 30.8 g of a 50.0% NaOH solution is added to the mixture, which is then stirred at 6O⁰C for one hour. Formation of epoxy groups is monitored by gas chromatography and chloride ion titration. The mixture is extracted using diethyl ether to separate the product from water and salts. This intermediate is obtained as a clear amber liquid. EXAMPLES 8-28

50.0 g (20.5 mmol/eq.-wt. based on DAA in sample) of the base polymer B from Example 2 is diluted with 20.0 g of deionized water. The pH is adjusted with 1.2 g of a 50.0% NaOH solution. 1.2 g (6.2 mmol) of 1-oxy-2,2,6,6,-tetramethyl-4-glycidyloxypiperidine (glycidol TEMPO) is added to the solution. After thorough mixing, the reaction mixture is allowed to react at 7O⁰C for 5 hours. After this time the consumption of glycidol TEMPO is determined to be > 99.0% by liquid chromatography. 50.0 g of deionized water is added along with 0.5 g of 50.0% NaOH solution. When the temperature reaches 7O⁰C, 5.5 g (6.2 mmol) of a 38.0% solution of 3-chloro-2-hydroxypropyl-dimethyldodecylammonium chloride (Quab^® 342) and 5 g of 2-propanol are added to the flask. The reaction mixture is maintained at 70-75⁰C for three hours with stirring. During the reaction 20.0 g of deionized water is added to aid in viscosity control. The mixture is then analyzed for the consumption of QUAB 342 using liquid chromatography. Also the hydrolysis of the QUAB 342 to glycol is monitored by titration and using liquid chromatography. The mixture is cooled to room temperature and 1 16.0 g of deionized water and 1.4 g of concentrated HCI is added to adjust the pH. The modified poly- DADMAC copolymer is obtained as a clear viscous yellow mixture of 9.1 wt.-0% solids. The cationic polymer contains about 4.4 wt.-% of grafted glycidol TEMPO which provides antioxidant functionality from the pendant nitroxyl groups and 7.7 wt.-% of the 3-chloro-2-hy- droxypropyl-dimethyldodecylammonium chloride reaction product.

EXAMPLES 29- 49 50.0 g (42 mmol/eq.-wt. based on DAA in sample) of the base polymer A from Example 2,

10.1 g of deionized water and 3.3 g 50.0% NaOH solution are placed into a round-bottomed flask equipped with a stirrer, nitrogen inlet and a thermoregulator and heated. When the temperature reaches 7O⁰C, 30.2 g (33.5 mmol) of a 38.0% solution of 3-chloro-2-hydroxypropyl- dimethyldodecylammonium chloride (QUAB 342) and 8.0 g of 2-propanol are added to the flask. An exotherm is observed with an increase in temperature from 65⁰C to 7O⁰C. When the rise in temperature subsides, the reaction mixture is maintained at 65⁰C for three hours with stirring. During the reaction 6.0 g of deionized water is added to aid in viscosity control. At this time the consumption of QUAB 342 is determined to be > 99.0% by chloride titration. Also the hydrolysis of the QUAB 342 to glycol is monitored by titration and using liquid chromatography. After this time the mixture is cooled to room temperature and 179.0 g of deionized water and 1.5 g of a 2.3% HCI/ water solution is added to adjust the pH. The modified polyDADMAC copolymer is obtained as a clear viscous yellow mixture of 12.8 wt.-% solids. The final product has a Brookfield viscosity of 4900 cps at 25⁰C (using a Brookfield LV3 spindle at 12 rpms) at 12.8 % polymer solids. Table 5 summarizes the properties of the above polymer and others prepared analogously.

TABLE 5

¹ Based on diallylamine content

² Brookfield LVT #3, Speed 12 rpm

³ Brookfield LVT #4, Speed 12 rpm

⁴ Brookfield RVT-E, Speed 10 rpm 5 Brookfield LVT #2, Speed 12 rpm

⁶ Brookfield LVT A, Speed 12 rpm

QUAB 151 : glycidyltrimethylammonium chloride

QUAB 342: S-chloro^-hydroxypropyl-dimethyldodecylammonium chloride

QUAB 426: S-chloro^-hydroxypropyl-dimethyloctadecylammonium chloride E-Dodecane: 1 ,2-epoxydodecane

E-Hexane: 1 ,2-epoxyhexane

PGE: phenyl glycidyl ether

PSA: 3-chloro-2-hydroxy-1 -propane sulphonic acid, Na-salt

SCA: sodium chloroacetate CA: 2-chloroacetamide

PEG 350: Carbowax 350: polyethylene glycol 350

Dodecenyl SA: 2-dodecen-1-yl succinic anhydride

EXAMPLE 50

40.0 g (1 15.6 mmol) of perfluorobutyl iodide (Dupont), 4.1 g of deionized water and 1.1 g so- dium metabisulphite (26.8 % solution) are placed into a round-bottomed flask equipped with a stirrer, nitrogen inlet and a thermoregulator and heated. When the temperature reaches 6O⁰C, 16.8 g (231.2 mmol) allyl alcohol (Acros) is added to the flask over one hour. An exothermal reaction is observed with an increase in temperature from 6O⁰C to 7O⁰C. When the rise in temperature subsides, the reaction mixture is maintained at 6 ⁰C for three hours with stirring. At this time the consumption of perfluorobutyl iodide is determined to >95.0% by gas chromatography. The excess allyl alcohol is removed by vacuum distillation at 85⁰C. The remaining mixture is cooled and transferred to a separatory funnel. 25.8 g of deionized water and 10Og of diethyl ether is added. The water layer is discarded and the ether layer dried un- der vacuum distillation at 40 ⁰C. The perfluoroalkyl iodide intermediate, is

obtained as a clear orange mixture containing 42.3 % fluorine. EXAMPLES 51 -54

Table 6 summarizes the properties of grafted cationic copolymers prepared analogously to Example 29 with the grafting component of Example 50.

TABLE 6

Based on diallylamine content

Claims

1. An emulsion of an oil component and an aqueous component comprising as the emulsifier from 0.05 % to 30.0 % by weight, based on the total weight of the emulsion, a co-polymer containing as repeating units the following moieties:

and optionally -hc-Jr or

and optionally ^*+^Mc-t

Wherein n, w, m and p are the mol fractions of the corresponding repeating units incorporated into the copolymer, wherein n is from 20.0% to 99.0%, m is from 0.0% to 40.0%, w is from 0.1.0% to 40.0%, p is 0.0% to 40.0%, and m + w + n + p = 100.0%,

Mc represents the residue from an optional ethylenically unsaturated monomer,

R₁ and R₂ are, independently of each other, alkyl, hydroxyalkyl, carboxyalkyl, carbox- amidoalkyl, or alkoxyalkyl having from 1 to 18 C-atoms,

R₃ is hydrogen or Ci-i₈alkyl, each Y^" independently represents an anion, Fg is selected from the group consisting of

Wherein F₉' is H, Ci_-30 alkyl or a group

— O-R

\ / I \ I

.Si-O H- Si-O + Si-R I \ \ /T l

-N-R

-R

wherein R is hydrogen, Ci_-3oalkyl, Ci_-30perfluoroalkyl, 1 to 1500 ethoxy units, 1 to 1500 propoxy units, 1 to 1500 mixed ethoxy-propoxy units and r is a number from 1 to 100 and wherein the polymer may be substituted by one or more than one group F₉.

2. An oil-in-water emulsion according to claim 2, wherein n is from 40.0% to 98.0%, m is from 0.1 % to 30.0%, w is from 0.1% to 30.0%, p is 0.0% to 20.0% and M_c is the residue of a vinyl monomer selected from the group consisting of acrylamides, methacrylamides, acrylates, methacrylates, acrylic acid, methacrylic acid, vinyl sul- phonic monomers, vinyl phosphonic monomers, vinyl pyrrolidones, vinyl alcohol and vinyl acetate.

3. An oil-in-water emulsion according to claim 2, wherein

Mc represents a residue selected from the group consisting of acrylamide, methacrylamide, alkyl or dialkyl acrylamide or methacrylamide, acrylate, methacrylate, acrylic acid and methacrylic acid monomer, Ri and R₂ are, independently of each other, Ci_-4 alkyl, R₃ is H or Ci_-4 alkyl,

Y^" is selected from the group consisting of chloride, bromide, iodide, fluoride, sulphate, phosphate, nitrate, acetate, and tetrafluoroborate anions, and

OH

F_g is selected from the group consisting of and, wherein F₉' is H, Ci_-30 alkyl or a group

— O-R

wherein R is hydrogen or Ci_-24alkyl.

4. An oil-in-water emulsion according to claim 3, wherein Y^" is selected from the group consisting of chloride, bromide and iodide anions; and

F₉' is H, Ci_-24 alkyl or a group

— O-R

\ / I \ I

,,-0-(-Si-O^-Si-R

5. An oil-in-water emulsion according to claim 2, wherein the copolymer is present in a concentration of from 0.1.0% to 30.0% by weight, based on the total weight of the emulsion.

6. An oil-in-water emulsion according to claim 2, wherein the oil phase is from 1.0% to 60.0% by weight, based on the total weight of the emulsion.

7. A method for preparing an emulsion of an oil component and an aqueous component which comprises incorporating into the components of the emulsion from 0.05 % to 30.0% by weight, based on the total weight of the emulsion, a co-polymer containing as repeating units the following moieties:

and optionally ^*+^Mc^"t^β or

and optionally *— ^M^-^— *

Wherein n, w, m and p are the mol fractions of the corresponding repeating units incorporated into the copolymer wherein n is from 20.0% to 99.0%, m is from 0.0% to 40.0%, w is from 0.1.0% to 40.0%, p is 0.0% to 40.0%, and m + w + n + p = 100.0%,

Mc represents a residue from an optional ethylenically unsaturated monomer,

Ri and R₂ are, independently of each other, alkyl, hydroxyalkyl, carboxyalkyl, carbox- amidoalkyl, or alkoxyalkyl having from 1 to 18 C-atoms,

R₃ is hydrogen or C_M8 alkyl, each Y^" independently represents an anion,

Fg is selected from the group consisting of OH

O

Wherein F₉' is H, Ci_-30 alkyl or a group

— O-R

\ / I \ I

.Si-O H- Si-O + Si-R

-N-R

8. A personal care formulation comprising the stable oil-in-water emulsion according to claim 2.

9. A personal care formulation according to claim 8 which is a skin care formulation.