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WO2010123575A1 - Etoiles bien définies avec branches segmentées - Google Patents

Etoiles bien définies avec branches segmentées Download PDF

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Publication number
WO2010123575A1
WO2010123575A1 PCT/US2010/001210 US2010001210W WO2010123575A1 WO 2010123575 A1 WO2010123575 A1 WO 2010123575A1 US 2010001210 W US2010001210 W US 2010001210W WO 2010123575 A1 WO2010123575 A1 WO 2010123575A1
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Prior art keywords
star
arms
segment
segments
polymer
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PCT/US2010/001210
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English (en)
Inventor
Wojciech Jakubowski
Patrick Mccarthy
Nicolay Tsarevsky
James Spawswick
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Atrp Solutions Inc
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Priority to PCT/US2010/001210 priority Critical patent/WO2010123575A1/fr
Publication of WO2010123575A1 publication Critical patent/WO2010123575A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/20—Polymers characterized by their physical structure
    • C08J2300/206—Star polymers

Definitions

  • the present invention relates to the preparation and use of well defined star macromolecules wherein the composition of the arms selected to induce self assembly when the multi-arm segmented star macromolecules are dispersed in a liquid.
  • Compositions comprising the self assemblable star macromolecules are suitable for use as rheology modifiers in a number of applications including cosmetic and personal care compositions.
  • This invention generally relates to well defined star macromolecules that self assemble in solution to provide a certain level of control over viscosity and consistency factors in many aqueous or oil based systems where control over the rheology is a concern.
  • Applications include; water- and solvent-based coating compositions, paints, inks, antifoaming agents, antifreeze substances, corrosion inhibitors, detergents, oil-well drilling-fluid rheology modifiers, additives to improve water flooding during enhanced oil recovery, dental impression materials, cosmetic and personal care applications including hair styling, hair conditioners, shampoos, bath preparations, cosmetic creams, gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, sunscreens, shaving preparations, and fabric softeners, with the rheology modifier providing characteristics of high gel strength, highly shear thinning, forms versatile low viscosity soluble concentrations, and synergistic interactions with added agents to
  • compositions of each segment of the star thickening agents disclosed herein can be modified to provide high performance and value in applications such as those discussed above.
  • Cosmetic and personal care compositions such as hair styling sprays, mousses, gels and shampoos, frequently contain resins, gums and adhesive polymers to provide a variety of benefits, for example, film-forming ability, thickening, sensory properties and hair shaping and setting.
  • Polymers designed for use in such compositions generally focus on linear or graft copolymers which contain various monomers in an alternating, random or block configuration.
  • the disclosed self assembling star molecules can provide similar or improved properties at lower concentrations; less than 10 wt% preferably less than 5 wt% and more preferably less than lwt% of the final product.
  • the thickeners used in cosmetic and body care preparations have to meet stringent requirements. First and foremost, they have to show high compatibility with other agents in the formulations and also if possible biodegradability so that many substances have to be ruled out from the outset for use in cosmetics. In addition, they should be universally useable in aqueous, emulsoidal, alcoholic and oil-containing bases, be readily incorporated into the formulations and lead to a rheology which enables the product to be easily applied so that the final preparations can be removed from containers and distributed under clean and simple conditions.
  • Thickeners that are macromolecularly designed to provide the desired properties would be expected to be compatible with many other auxiliaries present in the formulations, more particularly with salts and surfactants.
  • the thickener itself and the other auxiliaries should also lend themselves to ready incorporation into the formulation.
  • the thickened preparations are also expected to show stable rheology and an unchanging physical and chemical quality even in the event of long-term storage and changes in pH and temperature.
  • the thickeners should be inexpensive to produce without causing significant environmental pollution.
  • one problem addressed by the present invention was to provide cosmetic formulations which, after addition of only small quantities of a thickener, would be easy to apply and would leave the skin with a pleasant feeling.
  • the formulations would be easy to distribute on the skin and in the hair without leaving a feeling of stickiness behind. They would have improved physical and chemical stability and would be highly compatible with the skin and scalp.
  • the viscosity and consistency factors would be unaffected by additions of ions and other auxiliaries or by changes in pH and temperature.
  • agents that are included in the term "auxiliaries” include; surfactants, oils, fats and waxes, emulsifiers, silicone compounds, UV protectors, antioxidants, various water soluble substances, biogenic agents, deodorants, odor absorbers, antiperspirants, and germ and enzyme inhibitors. Such agents are disclosed in US patents 6,663,855 and US 7,318,929 herein incorporated by reference to provide definitions for those terms.
  • the basic concept behind the various CRP procedures is the reversible activation of a dormant species to form the propagating radical. A dynamic and rapid equilibrium between the dormant and the active species minimizes the probability of bimolecular radical termination reactions and provides an equal opportunity for propagation to all polymer (or dormant) chains.
  • Scheme 1 shows how they can be classified based on the mechanism of reversible activation: (a) stable free radical polymerization (SFRP, Scheme Ia), (b) degenerative chain transfer polymerization (DT, Scheme Ib), and (c) atom transfer radical polymerization (ATRP, Scheme Ic).
  • SFRP stable free radical polymerization
  • DT degenerative chain transfer polymerization
  • ATRP atom transfer radical polymerization
  • ATRP as an exemplary controlled radical polymerization process but the strategy disclosed for the preparation of star macromolecules with segmented arms and no remaining transfer/capping agent can be applied to any of the above polymerization processes.
  • This ability to use different CRP's to form specific arm segments in the star macromolecule allows one to increase the range of monomers that can be incorporated into the star arms.
  • a degenerative transfer process including procedures "e”, "f ' or "g”, can be used if one wishes to polymerize vinyl acetate from a multi-functional low molecular weight initiator which after hydrolysis forms stars with a polyvinyl alcohol inner shell, when segmented arms are formed.
  • the procedure employed for the preparation of the arms is known as initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) or a related procedure names activators regenerated by electron transfer (ARGET) as discussed by two of the current inventors.
  • IIR continuous activator regeneration
  • ARGET activators regenerated by electron transfer
  • the ICAR ATRP approach a low concentration of catalyst complex is employed to provide controlled growth of each arm from a well defined multifunctional core initiator and the excess higher oxidation state transition metal complex formed by a low incidence of radical/radical termination reactions is reduced to the activator state by reaction with radicals formed by controlled degradation of an added standard free radical initiator.
  • the concentration of the initially added transition metal complex can be less than 500 ppm, preferably less than 100 ppm.
  • Star Macromolecules Star polymers are nano-scale materials with a globular shape. They can optionally possess multiple segmented arms and a high-density of peripheral functionality. The spherical shape and dense structure of this type of polymer are expected to provide a suite of properties and functions different from that of linear polymers. Indeed the preparation of functional ized star polymers with uniformed size and multiple arms with site specific functionalities is presently the subject of extensive academic and industrial interest due to their unique structure and potential applications in cosmetics, drug delivery systems, coatings, membranes and lithography.
  • core-first which is accomplished by growing arms from a multifunctional initiator
  • the "core-first” method is exemplified by the use of a multifunctional initiator in a living polymerization process most often employing living ionic polymerization systems. This approach is also called the “grafting from” approach where the arms of the star are grown from a preformed functional ized core molecule or particle, see US Patents, 5,763,548 and 6,627,314 for examples of core first synthesis of star molecules using the ATRP procedure.
  • the "arm-first” strategy can be further sub-categorized according to the procedure employed for star formation.
  • One method is chain extension of a linear arm precursor with a multivinyl cross-linking agent, and the other is coupling linear polymer chains to a multifunctional linking agent, or "grafting-onto" a multifunctional core.
  • the development of living/controlled radical polymerization has revitalized the field of star polymer synthesis, especially for functional star polymers and various star polymers with many arms have been synthesized, mostly using these two “arm-first” methods.
  • Controlled Radical Polymerization process known as ATRP; disclosed in U.S. Patents 5,763,546; 5,807,937; 5,789,487; 5,945,491; 6,1 11 ,022; 6,121,371 ; 6,124,41 1 : 6,162,882: 6,407,187; 6,512,060; 6,538,091; 6,541,580; 6,759,491; and 7,332,550; and in U.S. Patent Applications 10/887,029; and 1 1/990,836 and discussed in numerous publications listed elsewhere with Matyjaszewski as co-author, which are hereby incorporated into this application.
  • the disclosed ATRP procedures describe the preparation of polymers displaying control over the polymer molecular weight, molecular weight distribution, composition, architecture, functionality and the preparation of molecular composites and tethered polymeric structures comprising radically (co)polymerizable monomers, and the preparation of composite macromolecular structures under mild reaction conditions.
  • ATRP generally requires an alkyl halide, or pseudo- halide, as an initiator (R-X) and a transition metal complex (e.g., Cu, Ru, Os, Mo, Fe, etc.) as a catalyst.
  • ATRP involves homolytic cleavage of an R-X bond by a partially soluble (WO 96/30421) transition metal complex in a lower oxidation state, such as Cu(I)-X/L (with a rate constant k a ), followed by propagation (with a rate constant k p ) and reversible deactivation of the propagating chain radical (R * ) (with a rate constant ⁇ 3 ) by the higher oxidation state catalyst complex, Cu(II)-X 2 /L where L is a ligand that solubilizes the transition metal and adjusts the activity of the formed catalyst complex.
  • the reaction progresses by repetitive transfer of halogen, or pseudo-halogen atoms, to and from the transition metal complex, as shown in Scheme Ic.
  • ATRP is such a useful procedure and can incorporate polymer segments prepared by other polymerization procedures it has been employed for the preparation of linear polysiloxane block copolymers for use in topical cosmetic and personal care compositions as disclosed in US Patent 6,365,672. ATRP has also been employed for synthesis of graft polymers, comprising hydrophobic and hydrophilic segments, for cosmetic applications US Patent 5,986,015.
  • the polymeric backbone has a weight average molecular weight of from about 500 grams/mole to about 200,000 grams/mole, wherein the polymeric backbone and the plurality of polymeric side chains form hydrophilic and hydrophobic graft polymers having a weight average molecular weight of from about 16,000 grams/mole to about 10,000,000 grams/mole.
  • Figure 1 Presents the kinetic data from ICAR ATRP of hydroxyethyl acrylate from a monofunctional initiator, Et 2 BrMM.
  • Figure 2 Evolution of molecular weights and polydispersity with monomer conversion in the ICAR ATRP of HEA (containing inhibitor) initiated by Et 2 BrMM.
  • Figure 3 Presents A) the kinetic data, and B) evolution of molecular weight and polydispersity with conversion, in the ICAR ATRP of hydroxyethyl acrylate in protic media conducted from multifunctional core initiators to form 3-arm; 4-arm and 6-arm stars using tri-, terra-, and hexa-functional initiators.
  • Figure 4 Viscosity measurements of 1.5 wt% of the star macromolecules in a shampoo.
  • polymer is used to refer to a chemical compound that comprises linked monomers, and that may or may not be linear; the term “(co)polymer” includes homo polymers and copolymers.
  • “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.
  • the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.
  • narrow molecular weight distribution or “narrow polydispersity” are used herein to mean a molecular weight distribution or polydispersity of less than 2.0 preferably less than 1.5.
  • multi-arm star indicates that a star shaped macromolecule with three or more arms linked at the core of the star is formed.
  • the core of the star molecule can optionally comprise degradable functionality.
  • Well defined multiarm stars with segmented arms are the preferred topology for the present invention as they can adopt a globular shape wherein each arm can chain extend in a selected targeted solvent to attain a highly swollen structure or highly chain extended structure.
  • the present disclosed star macromolecules comprise inner shell segments that are stable in the presence of salts and over a range of pH, and in one embodiment do not contain control agents, in addition to being more efficient as they can be employed at lower concentration in the formulations.
  • composition of the stars of the present invention can be selected so that one or more segments in the star macromolecules can interact with other components of a cosmetic product to provide the final physical properties desired for the final product.
  • the terminal segments on one or more of the tethered arms can comprise a polymer composition that is compatible with added agents, to provide an additional degree of self assembly thereby providing an additional level of control over thickening properties.
  • This embodiment is exemplified below by incorporation of an aliphatic chain end to provide a thickening agent compatible with hydrophobic functional groups present in added commercially available surfactants.
  • surfactants include anionic, nonionic, cationic, zwiterionic and amphoteric surfactants.
  • anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkylether sulfonates, glycerol ether sulfonates, .alpha.-methyl ester sulfonates, sulfofatty acids, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carb
  • anionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution although they preferably have a narrow-range homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partly oxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow-range homolog distribution.
  • Typical examples of cationic surfactants are quaternary ammonium compounds, for example dimethyl distearyl ammonium chloride, and esterquats, more particularly quaternized fatty acid trialkanolamine ester salts.
  • Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are all known compounds.
  • surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, .alpha.-olefin sulfonates, ether carboxylic acids, fatty acid glucamides, alkylamidobetaines, amphoacetals and/or protein fatty acid condensates, preferably based on wheat proteins.
  • the composition of the shell can be selected to provide desired degree of interaction between the shell and surfactant(s).
  • the rheology of the formulations remains unchanged even after prolonged storage and despite changes in temperature.
  • the formulations are highly compatible with the skin and scalp.
  • the small quantities of polymers lead to a pleasant, non-sticky feeling on the skin so that hair fibers are also prevented from sticking together.
  • the preparations show high physical and chemical stability, even when the composition contains high salt concentrations.
  • the present invention will be initially exemplified by the preparation of a multi-arm star macromolecule wherein the number of arms in the star macromolecule is between 3 and 25, preferably between 3 and 15, with segments selected to induce self assembly wherein the self assemblable star macromolecules are suitable for use as thickening agents or rheology modifiers in cosmetic and personal care compositions at low concentrations of the solid in the thickened solution, less than 5 wt%, preferably less than 2 wt%.
  • an exemplary new thickening agent is a multiarm star copolymer wherein one or more segments in the arms of the star macromolecule are prepared by controlled radical polymerization (CRP) using a well defined multifunctional low molecular weight soluble molecule as initiator for the CRP.
  • CRP controlled radical polymerization
  • the inner segments of the arms i.e. those segments tethered close to the core and optionally the core, are hydrophilic, and other, outer shell segments are hydrophobic.
  • the phylicity of the inner and outer segments in the arms of the star can be reversed.
  • the inner segments of the arms comprise non-ionizable hydrophilic segments selected to make the star macromolecules compatible with solutions further comprising dissolved/dispersed salts thereby providing rheology modifiers that are additionally stable over a range of pH, from 1 to 14.
  • Scheme 3 shows a purely exemplary series of multifunctional initiators that were used to provide stars with 3, 4 or six arms in the following examples section.
  • These specific multifunctional initiators were prepared by esterification of commercially available alcohols with an acid further comprising a radically transferable atom or group, in this instance bromine.
  • esterification of any hydroxyl-molecule can be utilized to form a multifunctional initiator e.g. in one embodiment of the invention the multifunctional core of the star can comprise natural biodegradable polysaccharides.
  • Tri-arm initiator Tetra-arm initiator Hexa-arm initiator
  • the initiator on the right, the hexa-arm initiator can be considered an example of two initiators with the topology and composition of the initiator on the left, the tri-arm initiator, linked by an ether functionality. Indeed this could be considered as an exemplary precursor of a "dendritic" core structure.
  • a simple procedure for the preparation of a "dendritic" core comprising initiating functionality by the controlled polymerization of AB* monomers was disclosed in WO 1997/018247 and an improvement regarding appropriate selection of ligand and catalyst to increase reaction rate and modify the topology of the core in WO 1998/040415. Therefore in one embodiment of the invention the multifunctional initiator forming the core of the star, C in formula (I) is prepared using an AB* inimer.
  • Such AB* monomers can also be employed to increase the number of arms in a star macromolecule formed from a multi-f ⁇ nctional initiator with a low number of initiating sites.
  • an AB* monomer is added to an ongoing polymerization of the first arms the unsaturated functionality is incorporated into the growing arm and the attached initiator functionality of the AB* monomer forms a three point branching point in the arm by initiating polymerization of mono-vinyl monomers present in the system and results in an increase in the number of tethered chains as the polymerization progresses.
  • the AB* monomer can comprise a degradable link between the unsaturated vinyl group and the initiator group. Therefore in one embodiment of the invention for an ATRP "grafting from” reaction the core multifunctional initiator “C” comprises three or more initiating functionalities which are used to prepare a polymer or segmented copolymer, (S l) p i-(S2) p2 , the "star" structure of which can be illustrated, in a general way, by the following formulae, (I) or (II):
  • C represents a polyfunctional future star centre or core, with a functionality of "n", n being an integer greater than or equal to 3, preferably between 3 and 25, and ⁇ C ⁇ L - represents the situation when several, two or more, (L) polyfunctional C centers are linked together to provide a central core initiator with an increased number of initiating moieties;
  • [(Sl) p i-(S2) p2 ] represents a polymeric chain, also known as an "arm" of the star, composed of different polymerized monomers wherein segment Sl comprises an inner arm segment comprising one or more monomer units and S2 comprises a second, outer arm oligo-polymer segment on each branch, [(Sl) p i-(S2) p2 ], being identical or different and being covalently grafted from the centre C; n and n' being the initial number of initiating functionalities on the polyfunctional center or core which is greater than or equal to 3, preferably of between 3 and 25; pi being the degree of polymerization of monomers comprising segment Sl which is greater than or equal to 2, preferably of between 10 and 20,000; p2 being the degree of polymerization of monomers comprising segment S2 which is greater than or equal to 1 , preferably of between 1 and 1 ,000.
  • the polymer chains are preferably provided in the form of blocks with a molecular mass of the arms are greater than or equal to 500 but which can range up to 2,000,000. However any specific segment in the copolymer can comprise a molar mass as low as 50.
  • the atom transfer radical trapping procedure discussed in detail below can also be employed using initiators of structure formula (1) where n is 3 or more to couple two or more initiator molecules to provide initiators of structure formula (2).
  • the hydrophobic outer shell segments, - (S2) p2 in the above formulae can comprise one or more units wherein a segment or substituent is a "fatty phase" that can comprise conventional volatile or non-volatile oils, gums and/or waxes of animal, vegetable, mineral or synthetic origin, alone or as mixtures, in particular: linear, branched or cyclic, volatile or non-volatile, molecules and can include silicone oils which are optionally organomodified; gums which are liquid at room temperature; mineral oils, such as liquid paraffin and liquid petrolatum; oils of animal origin, such as perhydrosqualene or lanolin; oils of vegetable origin, such as liquid triglycerides, for example sunflower, maize, soybean, jojoba, gourd, grape seed, sesame, hazelnut, apricot, macadamia, avocado, sweet almond or castor oils, triglycerides of caprylic/capric acids, olive oil, groundnut oil
  • a segment or substituent is a "
  • the inner shell or core of the star comprises water soluble non-ionizable monomer units.
  • the term "monomer units" indicates that a first monomer has been polymerized and the resulting polymer comprises the polymerized monomer units distributed along the polymer backbone.
  • Suitable radically copolymerizable monomers are listed in incorporated references and those particularly suited for the present star macromolecules targeting thickening agents stable in ionic systems include 2-hydroxylethyl (meth)acrylates, hydroxypropyl (meth)acrylates, glycidyl (meth)acrylates, PEO-oligo (meth)acrylates, (meth)acrylamides, allyl alcohol and vinyl pyrrolidone.
  • the hydrophilic segment is grown from the multifunctional core initiator or macroinitiator molecule the radically transferable atom or group on the periphery of the first formed multi-armed star is converted into an oleophobic segment in a novel atom transfer radical trapping reaction.
  • Lauryl peroxide is used as an exemplary agent in scheme 4.
  • the radical formed by activating the dormant polymer chain end by the transition metal complex preferentially reacts with a lower molecular weight radical formed by decomposition of the added radical source to tether the radical to the ⁇ -terminus of the polymer chain.
  • the halogen chain ends of the first exemplary P(HEA) star polymers can be replaced in the presence of an excess of a radical source.
  • An excess of low molecular weight radical source is employed to increase the fraction of cross coupling between the star-macro-radicals and low molecular weight radicals formed by decomposition of the radical source in the presence of small amount of a Cu(II) complex.
  • the radical source provides radicals that both reduce the complex (similar to ICAR) and couple with the radicals generated via activation of the dormant polymer or arm chain ends by the generated Cu(I) activator.
  • This atom transfer radical trapping procedure can be considered a generally applicable procedure for removal of a halogen, or any radically transferable atom or group from a polymer chain end using continuous regeneration of the ATRP activator and cross- coupling. Furthermore it can be applied to any of the polymers prepared by any of the CRP procedures described in Scheme 2 when suitable procedures for chain end activation is conducted in the presence of an excess of low molecular weight radicals further comprising the desired oligo-polymer segment or to attach a suitable functional group that can be used in a second step to attach the selected segment.
  • this process is conducted on the ⁇ -terminus of each arm of the multifunctional star macromolecule formed by controlled polymerization of a hydrophilic arm from a multifunctional compact core molecule as illustrated in Scheme 4 and in greater detail in scheme 4, for the decomposition of lauryl peroxide.
  • a hexa- functional initiator is employed the formed star macromolecule with six segmented arms can be represented by the figure shown in Scheme 4.
  • Such a star macromolecule can be used as a thickening agent and possesses the additional desired property of being insensitive to added salts is provided by the inner hydrophilic core of the star which additionally comprises non-ionizable monomer units.
  • the "fatty phase” can be incorporated by conducting a normal activation procedure in the presence of a saturated ⁇ -olefin that does not contain an activating substituent next to the olefin bond and once it has added to the chain end the dormant species cannot be reactivated.
  • a saturated ⁇ -olefin that does not contain an activating substituent next to the olefin bond and once it has added to the chain end the dormant species cannot be reactivated.
  • Such olefins with low molecular weight are commercially available. Higher molecular weight species can be prepared by telomerization of ethylene or ethylene propylene mixtures. [Kaneyoshi, H.; Inoue, Y.; Matyjaszewski, K. Macromolecules 2005, 38, 5425-5435.]
  • the "fatty phase” can be incorporated by conducting a normal activation procedure in the presence of a few monomer units comprising a substituent that comprises hydrophobic properties, such as lauryl (meth)acrylate or styrene based monomer units with a sufficiently long alkyl-group in the para-position.
  • the transferable control agent can be removed by the novel procedures disclosed herein or by employing the atom transfer radical addition or atom transfer coupling procedures disclosed in WO 98/040415.
  • the example detailed in scheme 4 shows formation of the lower molecular weight radical by decomposition of a peroxide, lauryl peroxide.
  • a similar reaction can involve the decomposition of an azo compound such as AIBN.
  • AIBN can be used to generate a radical (R * ) that can be employed to attached a nitrile group to the terminus of each of the first formed star arms that can be subsequently employed in subsequent azide-alkyne "click" reactions to attach oligomers with complementary functionality to the first formed star after removal of the control agent [WO 2005087818] in a second functionalization reaction that tethers the desired outer shell segments, -(S2) p2 to the arms of the first formed star polymer.
  • peripheral hydrophobic arm segments interact with hydrophobic segments in adjacent star molecules to self-assemble into a three dimensional array when dispersed in aqueous media or optionally interact with surfactant molecules that form micelles in the dispersion medium self-assemble into a shear sensitive three dimensional physically crosslinked network array.
  • the non- ionizable inner shell, (Sl) was formed by a controlled radical polymerization of 2- hydroxyethyl acrylate.
  • the hydrophobic outer shell (S2) on the formed star can comprise oleophylic segments selected to interact with added surfactants to provide a self organized macromolecular gel thereby modifying the rheology of the solution.
  • Surfactants that can interact with the outer shell of the first segmented star macromolecule include anionic, nonionic, cationic zwitterionic and amphoteric surfactants.
  • the phobicity of the inner arm segments and the outer shell segments can be reversed providing a star macromolecule with a hydrophobic core and a hydrophilic shell that can be employed as a thickening agent for oil based formulations.
  • a fraction of AB* monomer units equal to the number of initial initiating sites can be added to form a branch in the growing polymer chain thereby increasing the number of active chain ends for conversion to oleophilic units. This procedure increases the number of outer arm segments without increasing congestion at the core of the star.
  • EtOH ethanol In one non-limiting example for the environmentally benign procedure for the preparation of a star shaped macromolecule designed to act as a rheology modifier an ICAR ATRP of HEA was studied in order to prepare well-defined star copolymers, which could be used for further functionalization reactions.
  • HEA The antioxidant present in HEA was removed and then 20 mL, (22.12 g, 0.190 mol), HEA and EtOH (20 mL) were added to a 100 mL round bottomed flask, and a magnetic stir bar was added to mix the reagents. Separately, a stock solution containing CuBr 2 (0.0088 g, 3.94xlO "5 mol), TPMA (0.01 15 g, 3.94x10 * mol) and AIBN (0.0156 g, 9.5OxIO "5 mol) in DMF (10 mL) was prepared.
  • the flask was capped with a rubber septum and was then cooled in an ice bath (to minimize solvent evaporation). The liquid was purged with nitrogen for 1 h and the polymerization was then carried out at 65 0 C.
  • the stock solution (5 mL, corresponding to 1.97xlO "5 mol Of CuBr 2 and TPMA, and 4.75x10 5 mol of AIBN) was then added to the mixture of monomer and solvent, followed by addition of the trifunctional ATRP initiator (0.5402 g, 9.525XlO "4 mol).
  • the flask was capped with a rubber septum and then cooled in an ice bath (to minimize solvent evaporation) while the liquid was purged with nitrogen for 1 h.
  • the polymerization was then carried out at 65 0 C.
  • the reaction was carried out at conditions identical to the ones described above but the tetrafunctional 2-bromosiobutyrate initiator was used (0.6973 g, 9.525XlO "4 mol).
  • the initiator did not fully dissolve in the cold mixture of monomer and EtOH but did dissolve completely within 4-5 minutes after heating the mixture to 65 0 C.
  • the reaction was carried out under conditions identical to those described above but the hexafunctional 2-bromosiobutyrate was used at a lower concentration (1/10) than in reaction (nvt-08-007-55, i.e., 0.1094 g, 9.525xlO "5 mol).
  • the amount of catalyst added to the reaction was the same as in the above reactions but the amount of AIBN was decreased three-fold.
  • the reaction was carried out at 65 0 C for 30 h.
  • some arm-arm coupling can be accepted, indeed selected, as this chemically linked structure mimics the self-assembled physical network we envision the stars to adopt when acting as efficient rheology modifies.
  • the halogen chain ends on each PHEA arm of the star polymers can be replaced in an atom transfer coupling reaction in the presence of a large excess of a radical source.
  • This disclosed procedure increases the fraction of cross coupling between the high molecular weight slow diffusing macro-radicals and low molecular weight radicals, in the presence of small amount of a Cu(II) complex.
  • the radical source provides radicals that both reduce the stable higher oxidation state transition metal complex (similar to ICAR) and couple with the radicals generated via activation of the dormant polymer chain ends on each arm of the star by the generated Cu(I) activator (Scheme 4).
  • the reaction can be used for a variety of modifications, including removal of halogen atoms from the polymer chain ends when halogen is undesirable, but is employed herein to tether oleophobic segment(s) to the termini of the arms.
  • hexafunctional PHEA star copolymers were coupled with the radicals generated in the decomposition of lauryl peroxide (Scheme 4) thereby providing a star copolymer with a PHEA core and a peripheral shell comprising tethered saturated Ci i alkyl chains.
  • EXAMPLE 5 Synthesis of a thickening agent from a six-arm star polymer with polyHEA arms and hydrocarbon chain ends
  • 5 g of lauryl peroxide, 0.0212 g OfCuBr 2 , and 0.0276 g of TPMA were mixed with 15 mL of DMF. The heterogeneous mixture was purged for 1 h with nitrogen and was then heated to 65 0 C for 16 h. The polymer was precipitated in ether and washed well with the solvent. It had very different solubility compared to the starting polyHEA. It dissolved in shampoos but not in water, whereas the behavior of polyHEA is the opposite.
  • Example 5b (nvt-08-007-59)
  • 30 g of six-arm star polyHEA, apparent M n (from GPC) 101,000 g mol "1 .
  • 5 g of lauroyl peroxide, 0.0212 g OfCuBr 2 , and 0.0276 g of TPMA were mixed with 15 mL of DMF.
  • the heterogeneous mixture was purged for 2 h with nitrogen and was then heated to 70 0 C for 20 h.
  • the polymer was again precipitated in ether and washed well with ether.
  • Cosmetic and personnel care preparations prepared with star macromolecules of the present invention may contain the star molecules in quantities of 0.01 to 5% by weight, preferably in quantities of 0.05 to 3% by weight and more particularly in quantities of 0.1 to 2% by weight, based on the formulation as a whole.
  • the viscosity of the formulation can be adjusted to an exact value through the choice of the star molecule the composition and molecular weigh of each segment of the arms of the star.
  • Final viscosity can be adjusted by modifying the composition and molecular weight of each arm in the star in addition to the number of arms in the star.
  • the shampoo was a sulfate free shampoo #1 (US-00760-195) provided by Cognis.
  • Figure 4 shows that addition of 1.5 wt% of the six armed star molecule significantly changed the viscosity of the formed solution.
  • the sulfate free shampoo, #1 (US-00760-195) was provided by Cognis. The figure shows that the presence of a hydrophobic "shell" on the star modifies the viscosity of the formulation.
  • the present invention provides a general method for the synthesis of star polymers with pre-determinable molecular weight and narrow molecular weight distribution and preselected site specific functionality.
  • a further embodiment of the present invention provides a method for the synthesis of multi-arm star polymers where the core of the star polymers contains additional functionality.
  • a further embodiment of the present invention provides a method for the synthesis of multi-arm star polymers where the periphery of the star polymers contains additional functionality.
  • the functionality at the periphery of the star comprises molecular recognition functionality wherein the dominating non-covalent bonds responsible for the molecular recognition comprise hydrophobic segments that interact with added agents.
  • An embodiment of the present invention is a general method for the synthesis of star polymers comprising block copolymer arms with high molecular weight and narrow molecular weight distribution wherein the control agent employed in synthesis of the first formed star has been removed.

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Abstract

La présente invention porte sur la préparation et l'utilisation de macromolécules en étoile bien définie dans lesquelles la composition des branches sont choisies pour induire un auto-assemblage lorsque les macromolécules en étoile segmentées à multiples branches sont disposées dans un liquide. Les macromolécules en étoile auto-assemblées modifient la rhéologie du milieu en dispersion. Lorsque l'on cible une utilisation dans des systèmes à base aqueuse, la coque interne des macromolécules en étoile comprend des unités monomères non ionisables. Les compositions comprenant les macromolécules auto-assemblables sont appropriées pour être utilisées en tant que modificateurs de rhéologie dans un certain nombre d'applications comprenant des compositions cosmétiques et de soin personnel.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9856331B2 (en) 2008-12-22 2018-01-02 ATRP Solutions, Inc. Control over reverse addition fragmentation transfer polymerization processes
WO2018067561A1 (fr) * 2016-10-04 2018-04-12 ATRP Solutions, Inc. Combinaison d'une composition tensioactive sulfonée et de macromolécules en étoile

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* Cited by examiner, † Cited by third party
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US9856331B2 (en) 2008-12-22 2018-01-02 ATRP Solutions, Inc. Control over reverse addition fragmentation transfer polymerization processes
WO2018067561A1 (fr) * 2016-10-04 2018-04-12 ATRP Solutions, Inc. Combinaison d'une composition tensioactive sulfonée et de macromolécules en étoile
CN110191901A (zh) * 2016-10-04 2019-08-30 先导聚合物技术股份有限公司 磺化的表面活性剂成分和星形大分子化合物的组合
US11441065B2 (en) 2016-10-04 2022-09-13 Pilot Polymer Technologies, Inc. Combination of a sulfonated surfactant composition and star macromolecules

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