Star macromolecules for personal and home care.

(54) Title: STAR MACROMOLECULES FOR PERSONAL AND HOME CARE.

(54) Title: STAR MACROMOLECULES FOR PERSONAL AND HOME CARE.

(57) Summary

A polymer composition is provided consisting of star macromolecules. Each star macromolecule has a nucleus and five or more arms, where the number of arms within the star macromolecule varies across the composition of star macromolecules. The arms in the star are covalently linked to the core of the star, each arm containing one or more (co) polymer segments; and at least one arm and / or at least one segment has a different solubility than at least one other arm or another segment, respectively, in a reference liquid of interest.

(57) Abstract

A polymer composition comprising star macromolecules is provided. Each star macromolecule has a core and five or more arms, wherein the number of arms within a star macromolecule varies across the composition of star molecules. The arms on a star are covalently attached to the core of the star; each arm comprises one or more (co) polymer segments; and at least one arm and / or at least one segment exhibits a different solubility from at least one other arm or one other segment, respectively, in a reference liquid of interest.

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IMPIC ^ 'I. I - I, &lt;

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PATENT TITLE No. 347644

Owner (s): ATRP SOLUTIONS, INC.

Address: 855 William Pitt Way, Pittsburgh, Pennsylvania, 15238, USA

Denomination: STAR MACROMOLECULES FOR PERSONAL AND HOME CARE.

Classification: CIP: C08G81 / 00; C08F285 / 00; C08F287 / 00

CPC: C08F299 / 0492; A61K8 / 72; A61K8 / 90; A61K8 / 8147; C08F265 / 04;

C08G83 / 003

Inventor (s): WOJCIECH JAKUBOWSKI; PATRICK MCCARTHY; NICOLAY TSAREVSKY;

JAMES SPANSWICK

REQUEST

Number: International filing date:

MX / a / 2014/006714 October 26, 2011

Divisional Patent Number: 322801

PRIORITY ......

Country: Date: Number:

US October 27, 2010 12 / 926,143

Validity: Twenty years .............

Expiration Date: October 26, 2031: ......

Issue Date: May 8, 2017

The reference patent is granted based on articles 1^or, 2^or fraction V, 6th fraction III. and 59 of the Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent is valid for twenty years, non-extendable, counted from the filing date of the application and will be subject to the payment of the fee to keep the rights in force.

Whoever signs this title does so on the basis established by articles 6 ° fraCHótíés ín and 7 ° bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 06/27/1991. Amended on 08/02 / 1994, 10/25/1996, 12/26/1999. 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 05/06/2009,06/01/20118 / 06/2010, 06/28/2010, 01/27/2012 and 04/09/2012); items 1^or, 3 'section V subsection a), 4th and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999 amended on 07/01 (2002, 07/15/2004 07/28 / 2004 and 7/09/2007); articles 1^or, 3°, 4^or, 5^or Section V subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1 »3 'and 5 ° subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of Regional Offices. ^ Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007). ..... = ,, f '......

This official letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Payment and Electronic Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

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THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

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Tax 1695 || MX / 2017/38299 | MX / a / 2014/006714 | PCT patent title | 1220 | RRGO | Page (s)

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IMPI 'N'TnVTOMttlCANO ^Ot THE INDUSTRY PRQMEDAD_to(

STAR MACROMOLECULES FOR PERSONAL AND BODY CARE

HOME

CROSS REFERENCE WITH RELATED REQUESTS

This application claims the priority benefit of US Patent Application No. 12 / 926,143, filed on October 27, 2010, which is another continuation in part of US Application No. 12/799, 411, filed on April 23, 2010, which by itself claims priority from US Provisional Patent Application No. 61 / 214,397, filed April 23, 2009. All of the aforementioned applications are incorporated herein in their entirety by reference.

FIELD OF THE INVENTION

The present invention relates to multi-arm star macromolecules that are used as rheology modifiers, including use in cosmetic, personal care and home compositions.

BACKGROUND OF THE PREVIOUS TECHNIQUE

Most of the personal care products' on the market contain many types of polymers that vary in structure, chemistry, and source of raw materials (synthetic or natural) that are combined to

IMPI

INSTITUTO MEXICANO DE! A PROPERTY INDUSTRIAL

<img file="MX347644B_D0004.tif" />

provide products with many different desired functions. A class of polymer additives is chosen to alter or modify the rheological properties of the product that are very important in attracting consumers. Often times, additives that provide sufficient viscosity are needed, especially for those formulations where the viscosity without the additives is close to that of the pure solvent (water). However, increasing the viscosity alone is not sufficient, and in reality, modifiers must be selected to provide certain desired rheological properties for the formulation depending on its nature, mode of delivery, type of flow, and aesthetic appeal of the formulation. the final application. Low molecular weight surfactants are commonly used to modify rheological properties but they have to be used in large concentrations. Resulting in a relatively high cost, and an adverse impact on the environment (eg, water pollution).

Thickeners used in cosmetic and body care preparations have to meet stringent requirements. First of all, they have to show high compatibility and also - if possible - 25 biodegradability so that many substances have

IMPI

ΓΝίΤΓΓυΤΟ MEXICAN OF INDUSTRIAL PROPERTY to be regulated from the beginning to be used in cosmetics. In addition, they should be able to be used universally in aqueous, emulsoidal, alcoholic and oil-containing bases, which can be easily processed and directed to a rheology that allows the product to be easily applied so that the preparations can be removed and distributed in clean conditions. and simple.

Thickeners that are of the molecular level designed to provide the desired properties would be expected to be compatible with many other auxiliaries, more particularly salts and surfactants. The thickener itself and the other auxiliaries should also allow themselves to be easily incorporated into the formulation. Thickened preparations are also expected to show stable rheology and unchanged physical and chemical quality even in the case of long-term storage and changes in pH and temperature. Finally, the 20 thickeners should not be expensive to produce without causing significant environmental contamination.

In view of this complex profile of requirements, it is clear why, even now, there is still a demand for 25 new thickeners in the cosmetic field.

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IMPI Mexican institute • E LA FROF1EDAD INDUSTRIAL

COMPENDIUM OF THE INVENTION

Accordingly, in one aspect the invention provides a polymeric composition containing star macromolecules, each star macromolecule having a nucleus and five or more arms, wherein the number of arms within a star macromolecule varies throughout the composition of star molecules. ; and the arms on a star are covalently attached to the core of the star; each arm contains one or more copolymer segments; and at least one arm and / or at least one segment exhibits a different solubility from at least one different arm or another different segment, respectively, in a reference liquid of interest.

Use of the polymeric composition in personal care products and home care products is also provided.

In one aspect of the invention, there is a process for forming a mikto star macromolecule consisting of:

i) creating a reaction mixture containing a plurality of first polymeric segments having an ATRP functional end group and a plurality of second monomers, wherein at least a portion of the first polymeric segments are formed by polymerizing a

<img file="MX347644B_D0006.tif" />

IMPI

INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL plurality of first monomers, non-limiting examples of first monomers include hydrophobic monomers;

ii) forming a second polymer segment that extends from the first polymer segment by activating the ATRP functional end group in the first polymer segment to initiate polymerization of a portion of the second monomers, to form a plurality of block copolymer arms;

iii) during the polymerization of the second monomers, introducing a plurality of second monomer initiators having an ATRP functional end group into the reaction mixture;

iv) activating the ATRP functional end group on the second monomer initiator to initiate polymerization of a second portion of the second monomer to form a plurality of homopolymeric arms; and

v) crosslinking at least a portion of the block copolymer arms and at least a portion of the homopolymer arms to form at least one mikto star macromolecule.

In one aspect of the invention, there is a gel-forming star macromolecule when dissolved in water at a concentration of at least 0.2% by weight and formed:

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INSTITUTO MEXICAN (1

DF THE INDUSTRIAL PROPERTY

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i) creating a reaction mixture containing 'a * plurality of first polymeric segments having a terminal group with ATRP functionality and a plurality of second monomers, wherein at least a portion of the first polymeric segments are formed polymer by lifting a plurality of first monomers;

ii) forming a second polymer segment that extends from the first polymer segment by activating the ATRP functional end group in the first polymer segment to initiate polymerization of a portion of the second monomers, to form a plurality of block copolymer arms;

iii) during the polymerization of the second monomers, introducing a plurality of second monomer initiators having an ATRP functional end group into the reaction mixture;

iv) activating the ATRP functional end group on the second monomer initiator to initiate polymerization of a second portion of the second monomer to form a plurality of homopolymeric arms; and

v) crosslinking at least a portion of the block copolymer arms and at least a portion of the homopolymer arms;

where:

IMPI

INSTITUTO MEXICANO DE LAFRUFIEDAL) INDUSTRIAL

<img file="MX347644B_D0008.tif" />

a) the gel has a dynamic viscosity of at least

20,000 c P; and

b) the star macromolecule has a molecular weight of

150,000 g / mol and 600,000 g / mol.

In one aspect of the invention, there is a star macromolecule polymer composition containing one or more star macromolecules prepared by an improved, efficient, first-arm, living / controlled, radical polymerization method wherein the one or more star macromolecules are represented. by Formula X:

Formula X [(PI) qi- (P2X | 21r^Core- ((P3) q »] r where:

Core represents a cross-linked polymer segment;

PI represents a hydrophobic homopolymeric segment consisting of repeating units of monomeric residues of polymerized hydrophobic monomers;

P2 represents a homopolymeric segment consisting of repeating units of monomeric residues of polymerized hydrophilic monomers;

P3 represents a hydrophilic homopolymeric segment consisting of repeating units of monomeric residues of polymerized hydrophilic monomers;

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MEXICAN IWSTnVTO OF INDUSTRIAL PROMBDAD

<img file="MX347644B_D0009.tif" />

ql represents the number of repeated units in has an index between 1 and 50;

q2 represents the number of repeated units in P2 and has an index between 30 and 500;

q3 represents the number of repeated units in P3 and has an index between 30 and 500;

r represents the number of homopolymeric arms covalently attached to the Core;

t represents the number of copolymer arms covalently attached to the Core; and wherein the rat molar ratio is in the range of between 20: 1 and 2: 1.

In one aspect of the invention, there is a star macromolecule having a molecular weight of between 150,000 g / mol and 600,000 g / mol forming a clear homogeneous gel when dissolved in water in a concentration of at least 0.2% by weight wherein the gel has:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced breaking rate of at least 60%;

iii) a pH-induced failure rate of at least 80%;

iv) a shear thinning index of at least 10; me

<img file="MX347644B_D0010.tif" />

v) an emulsion index&gt; 12 hours.

In one aspect of the invention, there is a clear homogeneous gel, containing a star macromolecule having a molecular weight of between 150,000 g / mol and 600,000 g / mol, which has the following properties:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced breakage rate of at least 60%&gt;;

iii) a pH-induced breakdown rate of at least 80%&gt;;

iv) a shear thinning index of at least 10; me

v) an emulsion index&gt; 12 hours;

wherein the clear homogeneous gel is formed when the star macromolecule is dissolved in water in a concentration of at least 0.2% by weight.

In one aspect of the invention, there is an emulsifier-free emulsion containing: a water soluble star macromolecule having:

i) molecular weight of at least 150,000 g / mol; and ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4% by weight.

<img file="MX347644B_D0011.tif" />

IMPI ιμ &lt;ΤΤΤΜΤΟ MlXlCANO ^{, N} DEUrtomoA? INDUSTRIAL

In one aspect of the invention, there is an emulsion containing: a water soluble star macromolecule having: i) a molecular weight of at least 150,000 g / mol; and ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4% by weight.

In one aspect of the invention, there is a clear homogeneous gel-forming thickening agent when dissolved in water at a concentration of at least 0.2% by weight, wherein the gel has:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced breakage rate of at least 60%&gt;;

iii) a pH-induced breakdown rate of at least 80%&gt;;

iv) a shear thinning index of at least 10; me

v) an emulsion index greater than 12 hours.

In one aspect of the invention, the star macromolecule, emulsifier, gel, emulsifier-free emulsion, emulsion, and / or thickening agent, including those formed by the one-pot process, ATRP, CRP, and / or combinations of one or more of these processes are

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL RUBBING

<img file="MX347644B_D0012.tif" />

can be used to provide some level of control over viscosity and consistency factors in many aqueous and oil-based systems including, for example, solvent and water-based coating compositions, paints, inks, antifoam agents, antifreeze substances, inhibitors corrosion, detergents, rheology modifiers of oil well drilling fluids, additives to enhance flush flooding during oil-enhanced recovery, dental impression materials, cosmetic and personal care applications including hair styling, hair sprays, mousses, hair gels, hair conditioners, shampoos, bath preparations, cosmetic creams, cosmetic gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin cloths, sunscreens, shaving preparations, and fabric softeners.

In one aspect of the invention, there is a macromolecule, which contains: a plurality of arms containing at least two types of arms, wherein a first type of arm extends beyond a second type of arm and the first type of arm has a hydrophobic segment at its end

<img file="MX347644B_D0013.tif" />

IMPI

MEXICAN INSTITUTE

OF Distant industrial mUPltTY, where at least one porca ^ a - ^ ie ± ^ S ^ gTf®Yrfo hydrophobic can be extended beyond the length of the second type of arm either by segment size or monomeric segments ( which can vary in length of monomeric residue, degree of polymerization, and / or both) whereby the hydrophobic segment is attached. Recognizing that the length of an arm or segment and the limitation extends beyond it can be theoretical, meaning that as long as it is not measured empirically, it is understood that it extends further and / or has a longer length in relation to the length of the second type arm if the degree of polymerization is greater for monomeric residues of the same type or of the same theoretical length.

In one aspect of the invention, there is a star macromolecule, which contains: a plurality of arms having at least two types of arms, wherein the degree of polymerization of a first type of arm is greater than the degree of polymerization of a second arm type, and wherein the first arm type has a distal end portion that is hydrophobic. In another aspect of the invention, this star macromolecule can be formed by first forming or obtaining the hydrophobic portion and then forming the remaining portion of the first type of

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

<img file="MX347644B_D0014.tif" />

arm from the end of the hydrophobic portion and the second arm type in a one-pot synthesis where the polymerization of the second portion of the first arm type is started prior to the initialization of the second arm type but there is at least some point where the portions, eg, sizable portions, of the first type of arm and second type of arm are being polymerically extended at the same time.

In one aspect of the invention, there is an oil soluble star macromolecule, containing: a plurality of different arms containing at least two types of arms, wherein a first type of arm extends beyond a second type of arm and the first type of arm has a hydrophilic segment at its distal end.

In one aspect of the invention, there is an oil-soluble star macromolecule 20, containing: a plurality of arms containing at least two types of arms, wherein the degree of polymerization of a first type of arm is greater than the degree of polymerization of a second type of arm, and wherein the first type of arm 25 has a hydrophilic segment at its distal end.

IMPI

X5TTTVTO MEXICAN

OF THE INDUSTRIAL FXOFIEDAD

<img file="MX347644B_D0015.tif" />

In one aspect of the invention, there is a star macromolecule, which contains: a plurality of arms having at least two types of arms, wherein the degree of polymerization of a first type of arm is greater than the degree of polymerization of a second type of arm, and wherein the first type of arm has a distal end portion that is hydrophobic and the proximal portion of the first type of arm and second type of arm are the same with the only difference between the first type of arm and the second type of arm. being that the first type of arm has a hydrophobic portion at its distal end. In another aspect of the invention, this star macromolecule can be formed by first obtaining or forming the hydrophobic portion and then forming the remaining portion of the first type of arm from the end of the hydrophobic portion and the second type of arm at the same time in a synthesis. in a single container.

In one aspect of the invention, the star macromolecules can have an HLM index greater than 0 .85, for example greater than 0.87 or 0.9 or 0.93 or 0.95 or 0.97 or 0.98.

In one aspect of the invention, the star macromolecules may have a calculated HLM index greater than

IMPI ικπτυτο mmicano di la nopiUMT INDUSTRIA !.

0.85, for example greater than 0.87 or 0.9 -e - Ό-.93 g 0.05 or 0.97 or 0.98 and a viscosity greater than 60,000 cP at a pH between 7 to 10.5 and a molecular weight of between 200,000 g / mol and 550,000 g / mol and a shear thinning index of at least 10 and, optionally, a salt-induced rupture index of at least 60%.

BRIEF DESCRIPTION OF THE DRAWINGS

The characteristics and advantages of the present invention can be better understood with reference to the accompanying Figures, in which:

Figure 1: shows the structure of a segmented homologous arm star macromolecule and two different types of mikto arm star macromolecule.

Figure 2: GPC (Gel Permeation Chromatography) curve for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary star macromolecule (PSt-b-PAA).

Figure 3: GPC curves for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary star macromolecule (PSt-b-PAA) and GPC curve

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL I KeMEDAD

<img file="MX347644B_D0016.tif" />

for the block copolymer formed after chain extension with tBA in step 2 of the synthesis.

Figure 4: GPC curves of the PSt-b-tBA block copolymer and the star macromolecule formed after the core formation reaction is step 3 of the formation of an exemplary star macromolecule (PSt-b-PAA).

Figure 5: Image showing the thickening properties of the star macromolecule (PSt-b-PAA).

Figure 6: Viscosity of the aqueous solution of the star macromolecule (PSt-b-PAA) against the shear rate.

Figure 7: Viscosity of the star macromolecule aqueous solution (PSt-b-PAA) against concentration.

Figure 8: Viscosity of a solution in water / Windex (1: 1) (PSt-b-PAA) versus speed of aqueous solution and one of macromolecule star shear.

Figure 9: Viscosity of an aqueous solution and a solution in water / Windex (1: 1) of Carbopol EDT 2020 against shear rate.

<img file="MX347644B_D0017.tif" />

IMPI

HJTfTUTO MEXICANO DE LA NtCPIEDAD INDUSTUIAl

Figure 10: GPC curves for the preparation¹ TféT 'pTecursor for a PAA star. Solid line PtBA M_n = 18,900 PDI = 1.14; Dotted Star Line (PtBA)_x with M_n,_app112,600 PDI = 1.36

Figure 11: Viscosity of the aqueous solution of the star macromolecule (PSt-b-PAA) and star macromolecule (PAA) against shear rate.

Figure 12: Images demonstrating the emulsification properties of the star macromolecule (PSt-bPAA).

Figure 13: Synthesis of the star macromolecule [(PSt-bPtBA) / (PtBA)] using the first arm method.

Figure 14: GPC curves for Cig-PtBA arm star macromolecule, Solid line Cig-PtBA arm with M_n = 19,200 PDI = 1.16; dotted line star macromolecule (CigPtBA) x M_n, app = 95,600 PDI = 1.48.

Figure 15. GPC curves for macromolecule star arm Ci2 ~ PtBA, Solid line arm Cig-PtBA M_n = 17,500 PDI = 1.22; Dotted line (Ci₂-PtBA)_x M_n,_app 113,900 PDI = 1.53.

Figure 16: is a graph comparing the viscosity of Advantomer and Carbopol ETD 2020 in different% by weight of the thickening agent.

Figure 17: is a graph comparing the viscosity of Advantomer and Carbopol ETD 2020 at different shear rates.

Figure 18: is a graph comparing the viscosity of Advantomer and Carbopol ETD 2020 in different% by weight of NaCl.

Figure 19: is a graph that compares the viscosity of

Advantomer and Carbopol ETD 2020 with different pH.

Figure 20: is a graph that compares the viscosity of

Advantomer and Carbopol ETD 2020 in different% by weight of H₂0₂.

Figure 21: is a graph comparing the viscosity of

Advantomer and Carbopol ETD 2020 at different temperatures.

Figure 22: is a graph comparing the viscosity of Advantomer and Carbopol ETD 2020 in different% by weight of

NaCl.

<img file="MX347644B_D0018.tif" />

Figure 23: GPC curves for the reaction product resulting from step 2 of Example 9.

Figure 24: GPC curves of the reaction product resulting from step 3 of example 9.

DETAILED DESCRIPTION OF THE INVENTION

The term solubility or soluble is understood to mean that when a component is mixed in a solvent and tested, in STP in a 1 cm test tube, it has a transmittance index of light, at a wavelength at or around the length minimum wave

UV / Vis for mixing, of at least 40%, for example, at least 50%, 70%, 85% or at least 95%.

The term clear when used to describe a homogeneous gel or homogeneous solution is understood to mean that when the qel or solution is tested, at STP in a 1 cm test tube, it has a transmittance index of light, at a wavelength in or about a minimum UV / Vis wavelength for the gel or solution, of at least 40%, eg, at least 50%, 70%, 85%, or at least 95%.

The term "water soluble monomer" is understood to mean that a monomer that has at least

IMPI

MKICANC INSTITUTE OF INDUmUAL PROPERTY

<img file="MX347644B_D0019.tif" />

about 10% by weight water solubility in STP. For example, a water soluble monomer can have at least 15% by weight, 20% by weight, 25% by weight, or at least 30% by weight solubility in water in STP.

The term "water insoluble monomer" is understood to mean that a monomer that has less solubility in water than a water soluble monomer, for example less than about 5% by weight), such as may be less than 1% by weight or 0.5% by weight water solubility in STP.

The term "water-soluble star macromolecule" is understood to mean a star macromolecule that is soluble in water, with pH adjusted if necessary to a pH no higher than 8 with sodium hydroxide, in a concentration of at least 5g / L, for example , between 8g / L to 100g / L, which can be at least 10g / L, 12g / L, 15g / L, or at least 20g / L. For example, a water-soluble star macromolecule that has an aqueous solubility of at least 10g / L may include introducing at least 10 of the star macromolecule into approximately 1 L of water, neutralizing the mixture, if necessary, adjusting the pH. of the resulting mixture to approximately pH 8 (e.g., with the addition of base, such as sodium hydroxide), and stirring vigorously at a

IMPI

INSTITUTO MEXICANO OF ΙΛ FROFIÍDAD INDUSTRIAL

<img file="MX347644B_D0020.tif" />

temperature no higher than 100 ° C for no more than approximately 60 minutes, to obtain the dissolution of the star macromolecule, and testing the solubility in STP.

The term oil-soluble star macromolecule is understood to mean a star macromolecule that is soluble in mineral oil at a concentration of at least 5 g / L, for example, between 8 g / L to 100 g / L, as can be, at least 10 g / L, 12 g / L, 15 g / L, or at least 20 g / L of mineral oil. For example, an oil-soluble star macromolecule having an oil solubility of at least 10 g / L may include introducing at least 10 g of the star macromolecule into about 1 L of mineral oil, and vigorously stirring at a temperature not suitable. greater than 100 ° C for no more than about 60 minutes, to obtain the dissolution of the star macromolecule, and test the solubility in STP.

The term hydrophilic is understood to mean, in relation to a material, such as a polymeric arm, or a polymeric segment of a polymeric arm, that the material is soluble in water and contains 25 hydrophilic segments that have an HLB index equal to or

<img file="MX347644B_D0021.tif" />

IMPI

INSTITUTO MEXICANO • ΐ THE TNDl'STMjAL PROPERTY greater than 8, for example, an HLB index equal to 16-20, or equal to or greater than 18, 19 or 19.5. In certain embodiments, the hydrophilic segment may contain at least 75 mol% of water soluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol%, 90 mol%, 95 mol%, or al minus 97 mol% water soluble monomer residues.

The term hydrophobic is understood to mean, in relation to a material, such as a polymeric arm, or a polymeric segment of a polymeric arm, that the material is insoluble in water and contains hydrophobic segments with an HLB index less than 8, for For example, an HLB index less than 7. In certain embodiments, the hydrophobic segment may contain at least 75 mol% water insoluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol%, 90 mol%, 95 mol%, or at least minus 97 mol% water insoluble monomer residues.

The term "monomer residues" or "monomeric residues" is understood to mean the residue that results from the polymerization of the corresponding monomer. For example, a polymer derived from the polymerization of an acrylic acid monomer (or

INSTITUTO MEXICANO DE LA MOHODAl; INOUST »IAl derivatives of these, such as acid-protected acrylic acid derivatives including but not limited to methyl or t-butyl ester of acrylic acid), will provide polymeric segments, identified as 5 PAA, containing repeating units of monomeric residues. of acrylic acid, ie, -CH (COzH) CH2-.

For example, a polymer derived from the polymerization of styrene monomers will provide polymeric segments, identified as PS, containing repeating units of styrene monomeric residues, i.e.,

-CH (C₆H₅) CH₂~. For example, a polymer derived from the polymerization of monomeric divinylbenzene monomers will provide polymeric segments containing repeating units of monomeric divinylbenzene residues, i.e., -CH₂CH (C₆H₅) CHCH₂~ .

The term "emulsifier" is understood to mean a component that contains an appreciable weight percentage of an amphiphilic compound having a molecular weight of less than 5,000 MW. Emulsifiers are generally linear organic compounds that contain hydrophobic portions (tails) and hydrophilic portions (heads), both, that is, they are amphiphilic. Examples of emulsifiers include but are not limited to:

alkyl benzenesulfonates, alkanesulfonates, sulfonates

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HWTTWTO MCUCANO miamohcdap iKWsnuAi

<img file="MX347644B_D0022.tif" />

olefin, alkyl ether sulfonates, ethe ¹ aulf unuteoo dt »glycerol, alpha methyl ester sulphonates, sulfo fatty acids, alkyl sulphates, fatty alcohol ether sulphates, glycerol ether sulphates, mixed hydroxyether sulphates, monoglyceride (ether) sulphates, amide (ether) sulphates of fatty acids, mono- succinate fatty acids , mono- and dialkylsulfosuccinamates, sulfotriglycerides, carboxylic acid ethers and salts thereof, fatty acid isethionates, fatty acid sarcosinates, taurid fatty acids of fatty acids, acyl lactylates, acyl tartrates, acyl glutamates, acyl aspartates, oligoglucoside alkyl sulfates, protein condensates, fatty acids (particularly wheat-based plant products) and alkyl phosphates (ether), alkylbetaines, alkylamidobetaines, aminopropionates, aminoglucinates, imidazoliniobetaines and sulfobetaines.

The term "emulsifier-free" is understood to mean a composition or mixture wherein the formulation is considerably devoid of any emulsifier, for example less than 0.1% by weight of emulsifier, relative to the total composition, or less than 0.05% by weight of emulsifier, in relation to the total composition, or less than 0.01% in

<img file="MX347644B_D0023.tif" />

emulsifier weight, relative to the total composition, or a formulation where there is no emulsifier.

The term STP is understood to mean normal temperature and pressure conditions for experimental measurements, where the normal temperature is a temperature of 25 ° C and the normal pressure is a pressure of 1 atm.

Structure of the polymer composition

The multi-armed star macromolecules are shown schematically in Figure 1.

In one embodiment, the arms in a star macromolecule consist of two or more copolymer segments selected to modify the rheology of the reference liquid of interest. The structure of the star macromolecule is represented by the following formula [F- (MI)_pi- (M2) _p2] _n~ C θη where

i. [F- (Ml) pi- (M2)_p2] represents an arm consisting of a segmented (co) polymer chain wherein each (co) polymer segment, ii. - (ME)_pl- and (M2)_p2 are compositionally distinct, contiguous copolymer segments where each segment contains one or more homo gradient monomers,

IMPI

ΓΝΓΠΤυΤΟ MEXICANO DF LA FROFIEDAC INDUSTRIAL

<img file="MX347644B_D0024.tif" />

random, or block (co) polymer structure and where pl and p2 represent the degree of polymerization of each copolymer segment, iii. F- represents an optionally functional group or mixture of functional groups present at the end of the arm chain, iv. (Ml) pi is not soluble or not completely soluble in the reference liquid of interest,

v. (M2) p₂ it is soluble or most of it is soluble in the reference liquid of interest, vi. and C represents the crosslinked core of the star macromolecule consisting of the crosslinker (Mx), crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2), and vii. n represents the average number of arms covalently attached to the nucleus of the star macromolecule.

In another embodiment, the structure of the star macromolecule can be represented by the following formula, [F- (MI) _pl- (M2) _p2] _n-C- [(M3) _p3-F]_m where

i. [F- (MI) pi- (M2) p₂ ] represents an arm consisting of a segmented (co) polymer chain, ii. (Ml) pi- and (M2)_P2 are compositionally distinct, contiguous copolymer segments where each segment contains one or more homo gradient monomers,

INSTITUTO MEXICANO DE LA MOHEDAL INDUSTRIA!

random, or block (co) polymer structure and where pl and p2 represent the degree of polymerization of each copolymer segment, iii. F- represents an optionally functional group or mixture of functional groups present at the end of the arm chain, iv. (Ml) pi is not soluble or not completely soluble in the reference liquid of interest,

v. (M2)_P2 is soluble or most soluble in the reference liquid of interest, vi. and C represents the crosslinked core of the star macromolecule consisting of the crosslinker (Mx), crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2), and vii. n represents the average number of arms covalently attached to the nucleus of the star macromolecule viii. (M3)_P3 is a copolymer segment consisting of one or more monomers with homo, (co) polymer, random, gradient or block structure with a degree of polymerization p3 and ix. M is the number of (M3)_p3 of copolymer arms covalently attached to the core,

x. (M3)_P3 is soluble or mostly soluble in the reference liquid of interest and

<img file="MX347644B_D0025.tif" />

IMPI

MEXICAN INSTnVTO

Ot THE m »MÍDAl&gt; rwSTXIAL xi. M2 and M3 can consist of the same or different (co) monomers.

In another embodiment, the polymeric composition consists of star macromolecules in which the structure of a star can be represented by the following formula, [F- (Ml)_pl]_s-C- [(M3)_p3-F]_m where

i. [F- (MI)_pi ~ (M2) _p2] represents an arm consisting of a segmented (co) polymer chain, ii. (Ml) pi- is a (co) polymer segment where each segment contains one or more monomers with homo, (co) polymer, random, gradient or block structure with a degree of polymerization pl, iii. F- represents an optionally functional group or mixture of functional groups present at the end of the arm chain, iv. (Ml) pi is not soluble or is not completely soluble in the reference liquid of interest, v. C represents the crosslinked core of the star macromolecule which contains crosslinker (Mx), crosslinker 20 (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and ( M2), and I saw. (M3)_P3 is a (co) polymer segment consisting of one or more monomers with a homo, (co) polymer, random, gradient or block structure with a degree of polymerization p3 and

IMPI

INSTITUTO MEXICANO • E LA PROPERTY

-INDUSTRIAL

<img file="MX347644B_D0026.tif" />

vii. (M3)_P3 It is soluble or mostly soluble in the reference liquid of interest and viii. m is the number of arms of (co) polymer (M3)_P3 covalently attached to the Nucleus, and ix. s is the average number of (co) polymer (Ml) pi arms covalently attached to the Core.

In one embodiment, the polymer composition, the number of arms in any particular star varies across the population of star macromolecules in each composition, due to the synthetic process used for the synthesis of the composition. This process is called the first arm method and is described in detail later here. Due to the variation in the number of arms in star macromolecules, the number of arms n, m and m is referred to as an average number of arms.

Star macromolecules with a single peak on the curve

GPC with a polydispersity index (PDI) above

1.0 and below 2.5 are preferred.

As used herein, the term "reference liquid of interest" means the liquid to which the polymer composition will be added. Suitable examples of reference liquids include, but are not limited to,

<img file="MX347644B_D0027.tif" />

<img file="MX347644B_D0028.tif" />

INSTITUTC · MEXICANO DE TA INDUSTRIAL PROPERTY water, oil or a mixture of these or water with additives that include but are not limited to; 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. Those agents are described in US Patents 6,663,855 and US 7,318,929 and are incorporated herein by reference to provide definitions for those terms.

The arms of a star can have the same composition or be different (eg the star macromolecule with formula (1) versus (2) or (3), these stars are shown in Figure 1). The difference may be in composition or molecular weight or both (eg different monomer units MI, M2, M3 and / or different degrees of polymerization pl, p2, p3).

The term (co) polymer is defined as a polymer derived from two (or more) monomeric species (monomer units)

The most preferred specific monomer units as building blocks of MI, M2, M3 and My include

<img file="MX347644B_D0029.tif" />

IΜ ΡI INSTITUTO MEXICANO DE LA PROPIEDAf

INDI ISTWlAI those selected from acryl acid, co ”prophegl ^ ~ y protect, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, alpha butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, glyceryl monoethacrylate, glycidyl methacrylate, acrylate. glycidyl, acrylamide, methacrylamide, ethacrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, Netyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-butyl acrylamide, acrylamide butyl acrylamide , N-di-nbutyl, N, N-diethylacrylamide, N-octyl acrylamide, N-octadecyl acrylamide, N, N-diethylacrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide of N-dodecyl,

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL PRCHEDAD

<img file="MX347644B_D0030.tif" />

N, N-dimethylaminoethyl acrylamide, quaternized N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl methacrylamide, quaternized N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminoethyl acrylate, aminoethyl-acrylate, N-dimethyl-acrylate Quaternized N, N-dimethyl aminoethyl, quaternized N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, maleic acid, maleic anhydride and its half esters, fumaric acid, itaconic acid, itaconic anhydride and itaconic anhydride semi esters, crotonic acid, angelic acid, diallyldimethylammonium chloride, vinyl pyrrolidone, vinylimidazole, methylvinylether, methylvinylketone, maleimide, vinylpyridine, vinylpyridine N-oxide, vinylfuran, sulfonation of styrene and its salts, allyl alcohol, allyl citrate, allyl tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam, vinyl acetamide, vinyl formamide, and mixtures of these.

Even more preferred monomer units as a constituent part of MI, M2, M3 and My are those

IMPI

MEXICAN INSTITUTE

OF THE MOHEDA!

INDUSTRIAL

<img file="MX347644B_D0031.tif" />

selected from methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate 2-ethylhexyl, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, acrylamide-buttylacrylamide, acrylamide-butylacrylate acid , N-sec-butylacrylamide, N, N-dimethylacrylamide, N, N-dibutylacrylamide, N, N-dihydroxyethylacrylamide 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, 4-butyloxycarbonylacrylamide acrylate, 4-butyloxycarbonylacrylamide acrylate, acrylatebutyl acrylate cyclohexyl, dodecyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, iso-butyl acrylate, 3-methoxybutyl acrylate, 3-methoxypropyl acrylate, methyl acrylate, N-butyl acrylamide, N, N-dibutyl acrylamide, ethyl acrylate, ethyl methoxyacrylate, hydroxyethyl acrylate, diethylene glycol ethyl acrylate, styrene (optionally substituted with one or more C1-C12 straight or branched chain alkyl groups), alphamethylstyrene, t- butylstyrene, p-methylstyrene and mixtures of these.

<img file="MX347644B_D0032.tif" />

IMPI

INSTFTVTO MEXICANA

OF THE PKOP1EDA1 INMUSTXIAI

The monomer units within the arms can be connected with CC covalent bonds. This is believed to make them hard to degrade so that the star macromolecule can perform as an efficient thickening agent in a harsh environment (very high / low pH or in the presence of strong oxidizing agents).

When C represents the cross-linked core of the star macromolecule, it can consist of cross-linker (Mx), cross-linker (Mx) and monomer (My), cross-linker (Mx) and (M2), or a mixture of (Mx), (My) and ( M2).

Suitable cross-linkers (Mx) encompass all compounds which are capable, under polymerization conditions, of causing cross-linking. These include but are not limited to (meth) acrylates with difunctionality, trifunctionality, tetrafunctionality, styrenes with difunctionality, trifunctionality and tetrafunctionality and other crosslinkers with multifunctionality or poly-functionality.

Some examples of crosslinking agents may include but are not limited to 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene, 1,2-ethandiol di (meth) acrylate, 1,3 di (meth) acrylate -propandiol,

<img file="MX347644B_D0033.tif" />

1,4-butandiol di (meth) acrylate, 1,5hexandiol di (meth) acrylate, divinylbenzene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, di (meth ) triethylene glycol acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and allyl (meth) acrylate, glycerol di (meth) acrylate, tri (meth) acrylate trimethylolpropane, pentaerythritol tetra (meth) acrylate, allyl methacrylate, allyl acrylate.

The terms 'most soluble', 'not completely soluble', and 'not soluble' are used to describe the extent to which a composition is capable of dissolving in a reference liquid of interest.

The term 'most soluble' is used to describe a composition that is capable of being completely dissolved except for a slight haze in the reference liguide of interest. The term 'not completely soluble' is used to describe a composition that disperses with a cloudiness in the reference liquid of interest. The term 'not soluble' is used to describe a composition that does not disperse and remains as a solid in the liquid of

<img file="MX347644B_D0034.tif" />

IMPI Mexican institute DE LA PROPERTY INDIISTIIAI reference of interest. A list of solvents and non-solvents for polymers can be found in Polymer Handbook, 4th Ed. Edited by Brandrup J .; Immergut, Edmund H .; Grulke, Eric A .; Abe, Akihiro; Bloch, Daniel R., John Wiley &amp; Sons: 2005.

Multi-arm star macromolecules are the preferred topology for an embodiment of the present invention since they can adopt a globular shape where the inner segment, (M2)_p2 of each arm covalently attached to the core, you can chain extend in a selected solvent to obtain a highly swellable stable structure. The dispersing medium can be water, oil or a mixture of these. The degree of polymerization p2 of the segment (M2) can be higher than the pl of the segment (MI) to obtain a highly swellable stable structure. A star macromolecule with p2&gt; (3 x pl) is more preferred.

In one embodiment, a star macromolecule described with formula (2) and shown in Figure IB, containing a fraction of segmented (co) polymer arms [F- (Mi) _pi ~ (M2)_p2], the average number of arms, n, must be greater than two per star, preferably greater than three, and may contain one

IMPI

INSTITUTO Mexicano DE LA PMOHSDAD INDUSTRIA * molar fraction between 0.5 and 100% of the arms in the average star macromolecule. The nam ratio is more preferably between 100 and 0.1.

In one embodiment, in a star macromolecule described with formula (3) and shown in Figure 1C that contains a fraction of arms [F— (Ml)_pi] the average number of arms, o, must be greater than two per star, preferably greater than three, and may contain a mole fraction between 0.5 and 100% of the arms in the average star macromolecule. The oam ratio is more preferably between 100 and 0.1.

One embodiment of the present invention can be exemplified by a multi-arm star macromolecule wherein the average number of arms in the star macromolecule is between 5 and 500, preferably between 10 and 250.

In one embodiment, the star macromolecule has a nucleus that contains additional functionalities and / or expanded free volume. The 'expanded free volume' of the core is defined as the core with lower crosslink density. The free volume in the core is generated when during the crosslinking process

<img file="MX347644B_D0035.tif" />

INDUSTRIAL uses the Mx crosslinker with M2 or My monomer. If M2 or My are monomers with functional groups, these groups will be incorporated into the nucleus.

In one embodiment, the star macromolecule can be stored and the small molecules released at controlled rates. The 'small molecules' are flagrances, UV absorbers, vitamins, minerals, colorants, pigments, solvents, surfactants, metal ions, salts, oils, or drugs. These small molecules can be stored within the core of the star macromolecule and released later. Each small molecule has some affinity for the nucleus, it is soluble in the nucleus environment. The higher affinity of the small molecule for the nucleus will result in the lower release rate of the star macromolecule. Affinity can be increased or decreased through non-covalent forces including hydrogen bonding, electrostatic, hydrophobic, coordination, and metal chelation interactions.

In one embodiment, the star macromolecule exhibits shear-thinning behavior. 'Shear thinning' is defined as an effect where the viscosity decreases by increasing the

<img file="MX347644B_D0036.tif" />

<img file="MX347644B_D0037.tif" />

MUlCANí INSTITUTE. ΟΕΙΑΡβΟΡΙΪΡΛΓ INDUSTRIAL shear stress rate. The measurement of T shear thinning behavior is characterized using a Brookfield type viscometer where viscosities are measured at different shear rates.

In one embodiment, the star macromolecule contains a functional group exhibiting hydrogen bonding, coordinating, hydrophobic, metal chelating, and / or electrostatic forces. F represents a functional group or mixture of functional groups optionally present at the end of the arm chain. Functional groups (F) encompass all compounds capable of interacting through non-covalent forces including hydrogen, electrostatic, hydrophobic, coordination, and metal chelation bonds.

Some examples of end groups F capable of hydrogen bonding include but are not limited to modified bases adenine, tintin, guanine, cytosine, or derivatives thereof, peptides etc. Some examples of end groups capable of electrostatic interactions include but are not limited to carboxylate, phosphate, sulfonate, secondary, tertiary, and quaternary amines. Some examples of groups

<img file="MX347644B_D0038.tif" />

IMPI

Terminal MomuroMixicANo rHDUTHUAl capable of hydrophobic interactions include but are not limited to C1-C30 aliphatic groups, saturated and unsaturated hydrophobic aliphatic benzyl and benzyl groups. Some examples of end groups capable of coordinating interactions include but are not limited to metal ions and / or metal ion ligands. Some examples of end groups capable of metal chelating interactions include derivatives of diethylenetriamine-N, N, N ', N', N-pentaacetic acid (DTA), ethylenedinitriletetraacetic acid (EDTA), or nitriltriacetic acid (NTA).

In one embodiment, the star macromolecule contains a functional group F that is designed to interact with small molecule surfactant micelles. 'Interacts with' is defined as any intermolecular force between two molecules. These intermolecular forces include electrostatic, hydrogen bonding, hydrophobic, spherical, dipolardipolar, pi-pi, or other intermolecular forces.

Surfactants represent a class of molecules with a hydrophobic tail and a hydrophilic head. Some examples of surfactants include but are not limited to linear alkylbenzenesulfonate (LAS) salts, salts of

<img file="MX347644B_D0039.tif" />

alkyl ether sulfates (AEOS), alkylpolyg-buGÓs-ido-s— (ΆΡθΉ * alcohol ethoxylates, fatty acid glucoamides, betaines, alpha-defined sulfonate salts, polysorbates, PEGs, alkylphenolethoxylates, esterquats, imidizole salts, diamido salts of quaternary ammonium, etcetera.

In one embodiment, the arms of the star macromolecule contain a segment of (co) polymer that presents a higher or higher critical solution temperature (UCST or HCST) considering that the star macromolecule is soluble in a liquid at a higher temperature, say above 44 ° C, then at the lower use temperature the polymer segments of the outer shell become insoluble and self-assemble to form a shear-sensitive gel or in another embodiment of the invention the outer shell of the arms of the star macromolecule contains a segment of ( co) polymer exhibiting a lower critical solution temperature (LCST), say 5 ° C, Considering that the star macromolecule is soluble in a liquid at a lower temperature then at the temperature of use the polymer segments of the outer shell become insoluble and self-assemble to form a shear-sensitive gel. In the case of an LCST it is planned that a

<img file="MX347644B_D0040.tif" />

<img file="MX347644B_D0041.tif" />

INSTITUTO MEXICANO DE LA MONEDAD INDUSTRIAL copolymer segment with an LCST below 10 ° C, preferably below 5 ° C would be optimal. A non-limiting example would be a copolymerization of BuMA and DMAEMA and the preparation of copolymers with engineered LCST. A copolymer with 10% BuMA has an LCST close to 0 ° C and less BuMA or a less hydrophobic monomer such as MMA would be used to increase the LCST to ~ 5 ° C. In fact the Tg of the star segment can be selected to allow dissolution of the star in aqueous media at room temperature.

In one embodiment, a star macromolecule further consists of a personal care and cosmetic formulation and / or product. Personal care and cosmetic products include but are not limited to a shampoo, conditioner, hair lotion, toner, hair spray, hair mousse, hair gel, hair coloring, moisturizer, bronzer, color cosmetics, body lotions, hand cream, baby skin care products, face cream, lipstick, mask, blush, eyeliner, baby shampoo, baby moisturizers, baby lotion, body wash, soap, shaving products, deodorants, bath cream, body soap, serum, cream, solid, gel, lubricant, jelly,

INSTITUTO MEXICANO DE LA rtOTIHM INDUSTÍIAI balm, toothpaste, whitening gel, disposable towels, disposable cloths or ointment.

In one embodiment, a star macromolecule also consists of a formulation and / or home care product. Home care products include but are not limited to a surface cleaner, window cleaner, laundry detergent, bathroom cleaner, fabric cleaner, fabric softener, dish detergent, cleaning bar, stain remover bar, spray cleaners , dispersible formulations, lubricant, disposable towels or disposable cloths.

The polymer chains containing the arms are preferably provided with a molecular mass greater than or equal to 500 which can range up to 2,000,000. These numbers correspond to pi, p2, p3 in the range of 5 to 20,000, preferably in the range of 8 to 2,000.

In one example, star macromolecules containing segmented copolymer arms are intended for use in aqueous media. Stars contain a cross-linked nucleus, and arms consisting of copolymers

<img file="MX347644B_D0042.tif" />

IMPI rNsTffirro Mexican

OF THE PR CMEfJAl 'ingustuiai soluble in water (M2)_P2 and a hydrophobic (co) polymer (Ml)_pl. Thus in a non-limiting example the stars contain a cross-linked core, and arms consisting of water-soluble (co) polymer (e.g. poly (acrylic acid), poly (2-hydroxyethyl acrylate), poly (N- isopropylacrylamide), poly (ethylene glycol) methacrylate, quaternized poly (dimethylamino ethyl methacrylate, etc.) and a hydrophobic (co) polymer (eg polystyrene or substituted polystyrenes, poly ((me) alkyl acrylate), etc. ,) or a hydrocarbon-based segment. Suitable hydrocarbon-based segments may contain low molecular weight α-olefin. Lower molecular weight α-olefins are commercially available and higher molecular weight species can be prepared by polymerization of ethylene or ethylene propylene mixtures. [Kaneyoshi, H .; Inoue, Y .; Matyjaszewski, K. Macromolecules 2005, 38, 5425-5435.]

In one embodiment, the polymer compositions can self-assemble in solution to provide some level of control over viscosity and consistency factors in many aqueous and oil-based systems where control over rheology is an issue. Applications include; coating compositions

<img file="MX347644B_D0043.tif" />

MEXICAN INSTITUTE

CE LA MOf-IIDAD INDI 'STKIAI based on water and solvents, paints, inks, antifoaming agents, antifreeze substances, corrosion inhibitors, detergents, rheology modifiers of oil well drilling fluids, additives to improve the flooding by discharge of water 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 cloths, sunscreens, shaving preparations, and fabric softeners, providing the rheology modifier the high strength characteristics of the gel, the shear thinning characteristics, forms low viscosity soluble concentrations, versatile, and synergistic interactions with added agents to adjust its rheology profile to optimize properties such as sedimentation, flow and leveling, bending, splashing, etc.

A non-limiting field of applications that can exemplify the usefulness of star macromolecules

IMPI

Mexican INJTTTUTQ DE LA FRQHEDAL! Np »KT * IAL

<img file="MX347644B_D0044.tif" />

Described are cosmetic and personal care compositions such as hair styling sprays, mousses, gels and shampoos, often containing adhesive resins, gums and polymers to provide a variety of benefits, for example ability to form films, thickeners , detection properties and hair shaping and fixation. The polymers designed for rheological control, such as thickening agents, in those compositions generally focus on linear or graft copolymers containing various monomers in an alternating, random or block configuration.

Suitable hydrophobic monomers that can be used to form an arm or arm segment, such as a polymeric arm segment, of a star macromolecule may include, but are not limited to, methyl acrylate, ethyl acrylate, acrylate n-butyl, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl methacrylate; iso-butyl methacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; n-butyl ethacrylate; iso47 ethacrylate

<img file="MX347644B_D0045.tif" />

IMPI rMTfTUTO MEXICANO DE LA PROPERTY INDUSTRIA!

butyl; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxypropyl acrylate; Hydroxypropyl Methacrylate; Glycidyl Methacrylate; glycidyl acrylate, acrylamides, styrene; styrene optionally substituted with one or more C1-C12 straight or branched chain alkyl groups; or alkyl acrylate. For example, the hydrophobic monomer can contain styrene; alpha-methylstyrene; t-butylstyrene; p-methylstyrene; methyl methacrylate; or t-butyl acrylate. For example, the hydrophobic monomer can contain styrene. In certain embodiments, the hydrophobic monomer can contain a protected functional group.

Hydrophilic monomers that can be used to form an arm or arm segment, such as a polymeric arm segment, of a star macromolecule may include, but are not limited to, protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, a-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl methacrylate;

<img file="MX347644B_D0046.tif" />

iso-butyl methacrylate; 3e t-butyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; n-butyl ethacrylate; iso-butyl ethacrylate; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate; Hydroxypropyl Methacrylate; glyceryl monoacrylate; glyceryl monoethacrylate; Glycidyl Methacrylate; glycidyl acrylate; acrylamide; methacrylamide; ethacrylamide; N-methyl acrylamide; Ν, Ν-dimethyl acrylamide; N, N-dimethyl methacrylamide; N-ethyl acrylamide; N-isopropyl acrylamide; N-butyl acrylamide; Nt-butyl acrylamide; N, N-di-n-butyl acrylamide; N, N-diethylacrylamide; N-octyl acrylamide; N-octadecyl acrylamide; N, N-diethylacrylamide; N-phenyl acrylamide; N-methyl methacrylamide; N-ethyl methacrylamide; N-dodecyl methacrylamide; N, N-dimethylaminoethyl acrylamide; quaternized N, N-dimethylaminoethyl acrylamide; N, N-dimethylaminoethyl methacrylamide; quaternized N, N-dimethylaminoethyl methacrylamide; N, N-dimethylamin oethyl acrylate; N, N-dimethylaminoethyl methacrylate; quaternized N, N-dimethylaminoethyl acrylate; quaternized N, N-dimethylaminoethyl methacrylate; 2-hydroxyethyl acrylate; methacrylate

ΙΝΤΠΤυΤΟ MÍXICANI r&gt; t the precedent to IND'TSTRIAL

2-hydroxyethyl; 2-hydroxyethyl ethacrylate; glyceryl acrylate; 2-methoxyethyl acrylate; 2-methoxyethyl methacrylate; 2-methoxyethyl ethacrylate; 2-ethoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2-ethoxyethyl ethacrylate; maleic acid; maleic anhydride and its half esters; fumaric acid; itaconic acid; itaconic anhydride and its half esters; crotonic acid; angelic acid; diallyldimethylammonium chloride; vinylpyrrolidone vinylimidazole; methyl vinyl ether; methyl vinyl ketone; maleimide; vinylpyridine; Vinylpyridine N-oxide; vinylfuran; sulfonation of styrene and its salts; allyl alcohol; allyl citrate; allyl tartrate; vinyl acetate; vinyl alcohol; caprolactamvinyl; vinyl acetamide; or vinyl formamide. For example, the hydroph ilic monomer can contain protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, α-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl acrylate; methyl methacrylate; methyl ethacrylate; ethyl acrylate; ethyl methacrylate; ethyl ethacrylate; n-butyl acrylate; n-butyl methacrylate; n-butyl ethacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate; 250 ethacrylate

<img file="MX347644B_D0047.tif" />

IMPI

ΠΤΓΓΤΠΓΓΟ MtXlCANÍ. ' M LA FROPIEDAÍ INDU5THI «ethylhexyl; N-octyl acrylamide; · 'DUMTaro cte "2-methoxyethyl; 2-hydroxyethyl acrylate; N, N-dimethylaminoethyl acrylate; N, N-dimethylaminoethyl methacrylate; acrylic acid; methacrylic acid; Nt-butylacrylamide; N-sec-butylacrylamide; N, N-dimethylacrylamide; N, Ndibutylacrylamide; N, N-dihydroxyethylacrylamide; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; benzyl acrylate; 4-Butoxycarbonylphenyl acrylate; butyl acrylate; 4-cyanobutyl acrylate; cyclohexyl acrylate; dodecyl acrylate; 2-ethylhexyl acrylate; heptyl acrylate; iso-butyl acrylate; 3-methoxybutyl acrylate; 3-methoxypropyl acrylate; methyl acrylate; N-butyl acrylamide; N, N-dibutyl acrylamide; ethyl acrylate; methoxyethyl acrylate; hydroxyethyl acrylate; or diethylene glycol ethyl acrylate. For example, the hydrophilic monomer may contain both protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, iso-butyl acrylate, t-butyl acrylate, acrylate. 2-ethylhexyl, decyl acrylate, octyl acrylate; 2-hydroxyethyl acrylate; Nisopropylacrylamide; ethylene glycol methacrylate; (polyethylene glycol) methacrylate; or quaternized dimethylaminoethyl methacrylate. For example, the monomer

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nwrnrrv Mexican Dt THE FRORFDAf INDUSTRY!

Hydrophilic acid may contain 'att 1 ileum,' methacrylic acid, 2-hydroxyethyl acrylate, acrylamide, vinyl pyrrolidone, vinyl pyridine, styrene sulfonation, PEG methacrylate, 25 (dimethylamino) ethyl methacrylate, 2 (trimethylamino) methacrylate ) ethyl, 2-acrylamido-2-methylpropanesulfonic acid. For example, the hydrophilic monomer can contain acrylic acid.

Suitable monomers that can be used to form a core of a star macromolecule may include, but are not limited to, a monomer with multifunctionality, for example, a monomer with hexafunctionality, a monomer with pentafunctionality, a monomer with tetrafunctionality, a monomer with trifunctionality, or a monomer with difunctionality. For example, a crosslinker can be a hydrophobic monomer or a hydrophilic monomer, such as a hydrophobic monomer with multifunctionality or a hydrophilic monomer with multifunctionality, for example, a hydrophobic monomer with difunctionality or a hydrophilic monomer with difunctionality. For example, the crosslinker can be a hydrophobic crosslinker, including, but not limited to, 1,2-divinylbenzene; 1,325 divinylbenzene; 1,4-divinylbenzene; di (meth) acrylate

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<img file="MX347644B_D0050.tif" />

1,2-etiol; 1,3-propanediol di (meth) acrylate; 1,4-butanediol di (meth) acrylate; 1,5-hexanediol di (meth) acrylate; divinylbenzene; ethylene glycol di (meth) acrylate; di (ethylene glycol) diacrylate (DEGlyDA); propylene glycol di (meth) acrylate; butylene glycol di (meth) acrylate; triethylene glycol di (meth) acrylate; polyethylene glycol di (meth) acrylate; polypropylene glycol di (meth) acrylate; polybutylene glycol di (meth) acrylate; allyl (meth) acrylate; glycerol di (meth) acrylate; trimethylolpropane tri (meth) acrylate; pentaerythritol tetra (meth) acrylate; allyl methacrylate; or allyl acrylate. For example, the crosslinker can be di (ethylene glycol) diacrylate (DEGlyDA) or divinylbenzene. For example, the crosslinker can be divinylbenzene.

Star macromolecules may include, but are not limited to, a mikto star macromolecule, a water soluble star macromolecule, a gel-forming star macromolecule, emulsifier / thickening agent star macromolecules, or combinations thereof. In certain embodiments, the star macromolecule can have a molecular weight greater than 100,000 g / mol, for example, between 100,000 g / mol and 2,000,000 g / mol, such as between 125,000 g / mol and 1,750,000 g / mol; between 150,000 g / mol and 1,750,000 g / mol; between 200,000 g / mol and

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1,500,000 g / mol; between 225,000 g / mol and 23U, UU'O g / moi; between 125,000 g / mol and 1,000,000 g / mol; between 125,000 g / mol and 900,000 g / mol; between 125,000 g / mol and 800,000 g / mol; between 125,000 g / mol and 700,000 g / mol; between 150,000 g / mol and 650,000 g / mol; between 200,000 g / mol and 600,000 g / mol; between 225,000 g / mol and 650,000 g / mol; between 250,000 g / mol and 550,000 g / mol; between 350,000 g / mol and 500,000 g / mol; between 300,000 g / mol and 500,000 g / mol; or between 350,000 g / mol and 750,000 g / mol.

Star macromolecules can have a polydispersity index (PDI) less than 2.5, for example, a PDI less than 2.0, such as less than 1.7. For example, a star macromolecule can have a POI between 1.0 and 2.5, such as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1; between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; or between 1.15 and 1.55.

Suitable star macromolecules may have arms that are of the same type or a different type and are homopolymeric, copolymeric, contain multiple block segments, random segments,

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<img file="MX347644B_D0054.tif" />

gradients and / or non-particular segments. In certain embodiments, the star macromolecule may have, for example, one or more types of arms, such as two or more, three or more, four or more, or five or more types of arms. Suitable types of arms may include, but are not limited to, homopolymer arms, copolymer arms, such as random copolymer arms or block copolymer arms, or combinations of these. For example, a star macromolecule can have homopolymeric arms and copolymeric arms, such as block copolymeric arms. Suitable types of arms can also include, but are not limited to, hydrophilic arms, hydrophobic arms, or amphiphilic arms. In certain embodiments, a star macromolecule arm can have hydrophilic polymeric segments containing hydrophilic monomeric residues, hydrophobic polymeric segments containing hydrophobic monomeric residues, amphiphilic polymeric segments containing amphiphilic monomeric residues, or combinations of these. For example, in certain embodiments, a star macromolecule can have homopolymeric arms and copolymeric arms, such as hydrophilic homopolymeric arms and copolymeric arms containing hydrophilic polymeric segments and hydrophobic polymeric segments.

Suitable star macromolecules may also have arms that are covalently linked to the core of the star macromolecule. In certain embodiments, the arms of a star macromolecule can be covalently linked to the core of the star macromolecule through cross-linking, such as cross-linking with a cross-linker, for example, a hydrophobic cross-linker with difunctionality or a hydrophilic cross-linker with difunctionality. . For example, the arms of a star macromolecule, such as homopolymeric arms and block copolymeric arms of a mikto star macromolecule, can be covalently linked together to form a nucleus by crosslinking one end of the arms with a crosslinker. , such as with a hydrophobic crosslinker with difunctionality or a hydrophilic crosslinker with difunctionality.

Star macromolecules can also have arms of various lengths and / or degree of polymerization. In certain embodiments, for example, a star macromolecule may have homopolymeric arms and arms

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ΓΗςΤΓΤΉΟ MEXICAN ΠΕ THE INDUSTRIAL FRCPIEnAD block copolymers, where the homopolymeric arms are of a shorter length and / or a lower degree of polymerization in relation to the block copolymeric arms. In certain embodiments, for example, a star macromolecule may have homopolymeric arms and block copolymeric arms, where the block copolymeric arms are of a greater length and / or a higher degree of polymerization relative to the homopolymeric arms. In certain embodiments, a star macromolecule may have hydrophilic homopolymeric arms and block copolymeric arms, which contain hydrophobic polymeric segments distant from the core of the star and hydrophilic polymeric segments that are close to the core of the star, wherein a distant portion of the segments The hydrophilic polymeric arms of the polymeric arm extend beyond a distal portion of the hydrophilic homopolymeric arms. For example, a star macromolecule may have hydrophilic homopolymeric arms that contain polymerized hydrophilic monomeric residues and block copolymeric arms that contain hydrophobic polymeric segments distant from the star core and hydrophilic polymeric segments that are close to the star's core, where the segments

<img file="MX347644B_D0057.tif" />

Distant hydrophobic polymeric PtOMEDAK fNnoSTWMt IMPI tNSTm ΠΌ MEXICAN extend beyond most of the distant portion, relative to the core, of the hydrophilic homopolymeric arms, and / or where a distant portion of the proximal hydrophilic polymeric segments of the polymeric arm extend beyond the most distant portion, relative to the core, of the hydrophilic homopolymeric arms. In certain embodiments, a star macromolecule may have hydrophilic homopolymeric arms and block copolymeric arms, which contain hydrophobic polymeric segments distant from the star core and hydrophilic polymeric segments that are close to the star core, where the degree of polymerization of the hydrophilic polymeric segments of the polymeric arm is greater than, for example, 20% greater than, such as between 30% and 300% greater than, between 40% and 250%, between 50% and 200%, or between 75% and or 250% greater than, the degree of polymerization of the hydrophilic homopolymeric arms, such that a distant portion of the hydrophilic polymeric segments of the polymeric arm extends beyond a distant portion of hydrophilic homopolymeric arms.

In certain embodiments, a star macromolecule may have hydrophilic homopolymeric arms that contain

INSTITUTO MEXICANO nor the noriDAl · lNn &lt;t $ TWIAL polymerized hydrophilic monomeric residues and block copolymeric arms containing hydrophobic polymeric segments distant from the core of the star and hydrophilic polymeric segments close to the 5 core of the star, where the polymerized hydrophilic monomeric residues of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm can be derived from the same hydrophilic monomers, and they can have the same or different degree of polymerization, for example, a degree of polymerization of between 50 and 500 monomeric residues, such as between 50 and 400 monomeric residues; between 50 and 300 monomeric residues; between 50 and 200 monomeric residues; between 100 and 250 monomeric residues; between 15,125 and 175 monomeric residues; or between 150 and 300 monomeric residues. For example, a star macromolecule may have hydrophilic homopolymeric arms containing polymerized hydrophilic monomeric residues and block copolymeric arms containing hydrophobic polymeric segments distant from the star's core and hydrophilic polymeric segments close to the star's core, wherein the polymerized hydrophilic monomeric residues of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm can be derived from

<img file="MX347644B_D0058.tif" />

the same hydrophilic monomers, and can have the same degree of polymerization, and wherein the hydrophobic polymeric segments of the copolymeric arm can have a degree of polymerization of between 1 and 60 monomeric residues, such as between 1 and 50 monomeric residues; between 1 and 45 monomeric residues; between 5 and 40 monomeric residues; between 8 and 35 monomeric residues; between 10 and 30 monomeric residues; between 12 and 25 monomeric residues; between 14 and 20 monomeric residues; between 15 and 30 monomeric residues; or between 5 and 20 monomeric residues.

Star macromolecules can have a wide range of total number of arms, for example, a star macromolecule can have more than 15 arms. For example, a suitable star macromolecule can have between 15 and 100 arms, such as between 15 and 90 arms; between 15 and 80 arms; between 15 and 70 arms; between 15 and 60 arms; between 15 and 50 arms; between 20 and 50 arms; between 25 and 45 arms; between 25 and 35 arms; between 30 and 45 arms; or between 30 and 50 arms.

Suitable star macromolecules may have more than one type arm, such as two or more different arm types, where in a molar ratio of the types of

<img file="MX347644B_D0059.tif" />

Different arm can be between 20: 1 and 1: 1. For example, a star macromolecule that contains two different types of arms, such as a homopolymeric arm, for example, a hydrophilic homopolymeric arm, and a copolymeric arm, for example, a copolymeric arm that contains hydrophilic polymeric segments and hydrophobic polymeric segments, it can have a molar ratio of the two different types of arms between 20: 1 and 2: 1, such as between 15: 1 and 2: 1; between 10: 1 and 2: 1; between 9: 1 and 2: 1; between 8: 1 and 2: 1; between 7: 1 and 2: 1; between 6: 1 and 2: 1; between 5: 1 and 2: 1; between 4: 1 and 2: 1; between 3: 1 and 2: 1; between 2: 1 and 1: 1; between 8: 1 and 3: 1; between 7: 1 and 2: 1; or between 5: 1 and 3: 1.

Suitable star macromolecules may include, but are not limited to, those containing arms with a molecular weight greater than 10,000 g / mole. For example, a star macromolecule can contain arms that have a molecular weight of between 10,000 g / mol and 200,000 g / mol, such as between 10,000 g / mol and 175,000 g / mol; between 10,000 g / mol and 150,000 g / mol; between 10,000 g / mol and 125,000 g / mol; between 10,000 g / mol and 100,000 g / mol; between 10,000 g / mol and 90,000 g / mol; between 10,000 g / mol and 80,000 g / mol; between 10,000 g / mol and 70,000 g / mol; between 60,000 g / mol and 50,000 g / mol; between 10,000 g / mol and 40,000 g / mol;

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between 10,000 g / mol and 30,000 g / mol; between 10,000 g / mol and 20,000 g / mol; between 20,000 g / mol and 175,000 g / mol; between 20,000 g / mol and 100,000 g / mol; between 20,000 g / mol and 75,000 g / mol; between 20,000 g / mol and 50,000 g / mol; between 15,000 g / mol and 45,000 g / mol; or between 15,000 g / mol and 30,000 g / mol.

The proper arms of a star macromolecule can; include, but are not limited to, arms that have an HLB index of at least 17 (where the HLB index is calculated by the formula set forth in the test procedures). For example, suitable arms of a star macromolecule may have an HLB index greater than 17.25, as may be greater than 18.5; at least 19;

between 17.5 and 20; between 17.5 and 19.5; between 18 and 20; between 18.5 and 20; between 19 and 20; between 19.5 and 20; between 18 and 19.5; between 18.5 and 19.75; between 18.2 and 19.2; or between 18.75 and 19.5.

Suitable hydrophobic polymeric segments of a copolymeric arm of a star macromolecule may include, but are not limited to, hydrophobic polymeric segments having an HLB index of less than 8. For example, suitable hydrophobic polymeric segments may have an HLB index of less than 7 , how can it be

IMPI • Mexican MSTtnrro

OF LA RIOW.DAD industrial

<img file="MX347644B_D0061.tif" />

less than 6; Less than 5; less than 4; less than 3; less than

2; or about 1.

Suitable arms of a star macromolecule can include, but are not limited to, arms having a polydispersity index (PDI) of less than 2.5. For example, suitable arms of a star macromolecule may have a PDI index of less than 2.25, such as less than 2.0; less than 1.7; between 1.0 and 2.5, such as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1; between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; or between 1.15 and 1.55.

Suitable nuclei of a star macromolecule may be formed of or derived from, but are not limited to, cross-linking of a plurality of arms and a cross-linker. For example, a core may be formed by or derived from crosslinking a plurality of homopolymeric arms and a plurality of copolymeric arms with a crosslinker, such as a monomer crosslinker with multifunctionality, for example, a hydrophobic crosslinker monomer with difunctionality. In certain embodiments, the nucleus can

<img file="MX347644B_D0062.tif" />

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From THE industrial FROHSTY, it is formed or derived from the crosslinking of a plurality of hydrophilic homopolymeric arms and a plurality of copolymeric arms, containing block hydrophilic polymeric segments and block hydrophobic polymeric segments, with a crosslinker, such as a monomer crosslinker. hydrophobic with difunctionality, for example divinylbenzene, wherein the molar ratio of the homopolymer arms to the copolymer arms can be between 20: 1 to 2: 1.

Suitable star macromolecules may include, but are not limited to, those that contain a core having a molecular weight of greater than 3,000 g / mole. For example, a star macromolecule can have a nucleus with a molecular weight of between 3,000 g / mol and 50,000 g / mol, such as between 3,000 g / mol and 45,000 g / mol; between 3,000 g / mol and 40,000 g / mol; between 3,000 g / mol and 30,000 g / mol; between 3,000 g / mol and 20,000 g / mol; between 3,000 g / mol and 15,000 g / mol; between 5,000 g / mol and 40,000 g / mol; between 6,000 g / mol and 30,000 g / mol; between 7,000 g / mol and 25,000 g / mol; between 8,000 g / mol and 20,000 g / mol; between 5,000 g / mol and 15,000 g / mol; between 7,000 g / mol and 12,000 g / mol; between 5,000 g / mol and 9,000 g / mol; between 8,000 g / mol and 10,000 g / mol; or between 9,000 g / mol and 15,000 g / mol.

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<img file="MX347644B_D0063.tif" />

Suitable star macromolecules can be used to form a homogeneous gel, clear when dissolved in water at a concentration of at least 0.05% by weight at a pH of about 7.5 in STP. For example, a star macromolecule can form a homogeneous gel, clear when dissolved in water at a concentration of between 0.05% by weight and 3% by weight, such as between 0.1% by weight and 2.5% by weight; between 0.1% by weight and 2% by weight; between 0.2% by weight and 2.0% by weight; between 0.2% by weight and 1.5% by weight; between 0.2% by weight and 1.0% by weight; between 0.2% by weight and 2.5% by weight; between 0.3% by weight and 2.5% by weight; between 0.4% by weight and 2.0% by weight; between 0.5% by weight and 2.0% by weight; between 0.6% by weight and 2.0% by weight; between 0.7% by weight and 1.5% by weight; between 0.8% by weight and 1.2% by weight; between 0.9% by weight and 1.1% by weight; between 0.5% by weight and 2.5% by weight; between 0.75% by weight and 1.5% by weight; or between 0.8% by weight and 1.6% by weight.

Star macromolecules, according to the pH Efficiency Range Test Procedure described hereinafter, can be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4% by weight can have a viscosity of at least 20,000 cP, at a pH of between about 4 and about 12,

<img file="MX347644B_D0064.tif" />

IMPI twrmuTO mexicanl; OF INDUSTRIAL PRICE

<td></td><td colspan="2">for example, in a</td><td>pH</td><td colspan="2">between approximately</td><td>5 and</td>

<td></td><td>approximately</td><td> 11.5</td><td colspan="2">how can it be to a</td><td>pH of</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 11;</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 10.5;</td><td>between</td>

<td> 5</td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 10;</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 9.5;</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 9;</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 8.5;</td><td>between</td>

<td></td><td>approximately</td><td> 5</td><td>and</td><td>approximately</td><td> 8;</td><td>between</td>

<td> 10</td><td>approximately</td><td> 6</td><td>and</td><td>approximately</td><td> 11;</td><td>between</td>

<td></td><td>approximately</td><td> 5.5</td><td>and</td><td>approximately</td><td> 10;</td><td>between</td>

<td></td><td>approximately</td><td> 6</td><td>and</td><td>approximately</td><td> 9;</td><td>between</td>

<td></td><td>approximately</td><td> 6.5</td><td>and</td><td>approximately</td><td> 8.5;</td><td>between</td>

<td></td><td>approximately</td><td> 7</td><td>and</td><td>approximately</td><td> 8;</td><td>between</td>

<td> 15</td><td>approximately</td><td> 7.5</td><td>and</td><td>about 8</td><td>. 5; or</td><td>between</td>

<td></td><td>approximately</td><td>6.5 and</td><td colspan="2">approximately 7.5.</td><td></td><td></td>

In certain embodiments, for example, star macromolecules, according to the pH Efficiency Range Test Procedure 20 described hereinafter, can be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4% by weight it can have a viscosity of at least 20,000 cP at a pH between about 5.5 and about 11. For example, at

<img file="MX347644B_D0065.tif" />

a pH between about 5.5 and about 11 can have a viscosity of at least 30,000 cP, such as at least 40,000 cP; between 20,000 cP and 250,000 cP; between 20,000 cP and 250,000 cP; between 20,000 cP and 225,000 cP; between 20,000 cP and 200,000 cP; between 20,000 cP and 175,000 cP; between 20,000 cP and 150,000 cP; between 20,000 cP and 125,000 cP; between 30,000 cP and 250,000 cP; between 30,000 cP and 200,000 cP; between 40,000 cP and 175,000 cP; or between 40,000 cP and 150,000 cP. For example, a gel at a pH between about 6 and about 11 can have a viscosity of at least 20,000 cP, such as at least 30,000 cP; at least 40,000 cP; between 20,000 cP and 250,000 cP; between 20,000 cP and 250,000 cP; between 20,000 cP and 225,000 cP; between 20,000 cP and 200,000 cP; between 20,000 cP and 175,000 cP; between 20,000 cP and 150,000 cP; between 20,000 cP and 125,000 cP; between 30,000 cP and 250,000 cP; between 30,000 cP and 200,000 cP; between 40,000 cP and 175,000 cP; or between 40,000 cP and 150,000 cP. For example, at a pH between about 7 and about 10.5 it can have a viscosity of at least 60,000 cP, such as at least 70,000 cP; between 60,000 cP and 250,000 cP; between 60,000 cP and 225,000 cP; between 60,000 cP and 200,000 cP; between 60,000 cP and 175,000 cP; between 60,000 cP and 150,000 cP; between 60,000 cP and 125,000 cP; between 60,000 cP and 115,000 cP; between 60,000 cP and 105,000 cP; or between

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IMPI πντπντο MauCANC Ot U nOHlTY DÍDUSTRIAt

60,000 cP and 100,000 cP. For example, 'at' a 'pH between about 7.5 and about 9.0 may have a viscosity of at least 95,000 cP, such as at least 100,000 cP; between 95,000 cP and 250,000 cP; between 95,000 cP and 225,000 cP; between 95,000 cP and 200,000 cP; between 95,000 cP and 175,000 cP; between 95,000 cP and 150,000 cP; between 95,000 cP and 125,000 cP; between 95,000 cP and 115,000 cP; or between 95,000 cP and 105,000 cP.

The star macromolecules, according to the Dynamic Viscosity Shear Thinning Test Procedure described hereinafter, can be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4% in weight can have a viscosity less than 5,000 cP at a shear rate of 4 sec '¹, such as a viscosity of less than 4,000 cP. For example, the star macromolecule in a concentration of 0.4% by weight may have a viscosity of less than 5,000 cP at a shear rate of 6 sec '¹, such as a viscosity of less than 4,000 cP or less than 3,000 cP. For example, a gel may have a viscosity of less than 15,000 cP at a shear rate of 0.7 sec '¹, such as a viscosity of less than 14,000 cP or less than 13,000 cP.

Suitable gels may include, but are not limited to, gels having a shear thinning index of at least 5, such as a shear thinning index of at least 6, or between 5 and 15, such as between 5 and 15; between 7 and 12; between 8 and 10; or between 6 and 13.

Suitable star macromolecules, according to the Dynamic Viscosity Shear Thinning Test Procedure described hereinafter, include those that have a shear thinning index of at least 15, such as a thinning index by shear between 15 and 100, such as between 15 and 90; between 20 and 80; between 25 and 70; between 25 and 50; or between 30 and 40.

Suitable star macromolecules, according to the Salt-Induced Breakdown Test Procedure described hereinafter, include those that have a salt-induced breakdown rate of at least 50%, such as an induced breakdown rate. for salts between 65% and 100%, such as between 75% and 100%; between 80% and 95%; between 75% and 90%; between 50% and 85%; between 70% and 95%; or between 60% and 100%.

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Suitable star macromolecules, according to the pH Efficiency Range Test Procedure described hereinafter, include those that have a pH-induced breakdown rate of at least 15%, such as a breakdown rate. induced by pH between 15% and 100%, such as between 25% and 100%; between 30% and 95%; between 40% and 90%; between 50% and 85%; between 70% and 95%; between 80% and 97%; between 90% and 99%; between 95% and 100%; or between 60% and 100%.

Suitable star macromolecules, according to the Dynamic Viscosity Shear Thinning Test Procedure described hereinafter, include those having a dynamic viscosity index, greater than 20,000 cP at 1 rpm, and at a concentration of 0.2% by weight, such as a dynamic viscosity index greater than 24,000 cP; greater than 28,000 cP; or greater than 30,000 cP in a concentration of 0.2% by weight.

Suitable emulsions may include, but are not limited to, emulsions that are free of emulsifiers and where the emulsion is thickened by a star macromolecule. For example, the star macromolecule that may be included in the emulsion free of

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<img file="MX347644B_D0069.tif" />

The emulsifier may be a water soluble star macromolecule, wherein the water soluble star macromolecule emulsifies the emulsifier-free emulsion.

Suitable star macromolecules include star macromolecules having an emulsion index greater than 60 minutes, eg, greater than 3 hours, such as may be greater than 6 hours; greater than 10 hours; greater than 20 hours; greater than 40 hours; or greater than 100 hours.

Suitable star macromolecules, according to formula X, can include star macromolecules wherein Pl, P2 and / or P3 contain hydrophobic monomers, hydrophilic monomers, amphiphilic monomers, or combinations of these. For example, PI contains hydrophobic monomers, P2 contains hydrophilic monomers, and P3 contains hydrophilic monomers. For example, star macromolecules, according to formula X, can include star macromolecules where ql can have an index between 1 and 100, for example between 1 and 60, such as between 1 and 45; between 5 and 40; between 8 and 35; between 10 and 30; between 12 and 25; between 14 and 20; between 15 and 30; or between 5 and 20; and q2 and / or q3 have an index between 50 and 500, for example between 50

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DF THE PROPERTY INN »STR» *. Í and 400, as it can be, between 50 and 300; between 5Ό and 200; between 100 and 250; between 125 and 175; or between 150 and 300. For example, star macromolecules, according to formula X, can include star macromolecules where rot, or the sum of r and t, can be greater than 15, such as between 15 and 100; between 15 and 90; between 15 and 80; between 15 and 70; between 15 and 60; between 15 and 50; between 20 and 50; between 25 and 45; between 25 and 35; between 30 and 45; or between 30 and 50. For example, star macromolecules, according to formula X, can include star macromolecules where the rat molar ratio is in the range of between 20: 1 and 2: 1, such as between 15: 1 and 2: 1. ; between 10: 1 and 2: 1; between 9: 1 and 2: 1; between 8: 1 and 2: 1; between 7: 1 and 2: 1; between 6: 1 and 2: 1; between 5: 1 and 2: 1; between 4: 1 and 2: 1; between 3: 1 and 2: 1; between 2: 1 and 1: 1; between 8: 1 and 3: 1; between 7: 1 and 2: 1; or between 5: 1 and 3: 1. For example, star macromolecules, according to formula X, can include star macromolecules where the core can be derived from crosslinking monomers, such as hydrophobic crosslinking monomers. For example, star macromolecules, according to formula X, can include star macromolecules where the core may contain cross-linking monomeric residues, such as hydrophobic cross-linking monomeric residues. By

<img file="MX347644B_D0071.tif" />

<img file="MX347644B_D0072.tif" />

IWTHUTO MEXICANO DE LA PI0F1EDAO INPUSTKIAt example, star macromolecules, according to formula X, can include star macromolecules where the arm [(Pl) _whati ~ (P2) _q2] _t they can be homopolymeric or copolymeric, such as the block copolymer.

Suitable star macromolecules may include, but are not limited to, star macromolecules formed by crosslinking the arms with a crosslinker, such as crosslinking the homopolymer arms and block copolymer arms with a hydrophobic crosslinker. For example, the homopolymeric arms and the copolymeric arms of a star macromolecule can be covalently attached to the core through crosslinking with a crosslinker. For example, a core of a prepared star macromolecule can be prepared by crosslinking one end of a homopolymeric arm with one end of a copolymeric arm, such as a hydrophilic homopolymeric arm end with a hydrophilic end of a copolymeric arm. For example, the core of a prepared star macromolecule can be formed by crosslinking one end of the ATRP functional end group of a homopolymeric arm with one end of the ATRP functional end group of a copolymeric arm.

<img file="MX347644B_D0073.tif" />

Suitable initiators that can be used to form the star macromolecules described herein may include, but are not limited to, nitroxide initiators, such as stable nitroxide initiators, eg, 2,2,6,6-Tetramethylpiperidine-l -oxyl, sometimes called TEMPO; transition metal complexes, such as cobalt-containing complexes; ATRP initiators, containing halides, such as bromide, chloride, or iodide, and transition metal sources, such as copper, iron, ruthenium transition sources; iodide with RCTP catalysts, such as germanium or tin catalysts; RAFT initiators, such as dithioesters, dithiocarbamates, or xanthates; ITP catalysts, containing iodides; tellurium compounds (eg, TERP); stibine compounds (eg. , SBRP); or bismuth compounds (eg, BIRP). For example, in certain embodiments, an initiator may further contain a monomeric residue, a polymeric segment containing monomeric residues, or a small molecule. For example, in certain embodiments, an initiator can have an ATRP initiator, where the ATRP initiator serves as a terminal functional group. For example, in certain embodiments, an initiator may contain a terminal group with ATRP functionality, which contains a Mexican ητπτντο ATRP initiator, such as halides and transition metal sources.

Suitable materials containing the star macromolecules described herein include, but are not limited to, lotions, such as cosmetic lotions, personal care lotions, body lotions, emulsifier-free body lotions; serums, such as anti aging serums; sun filters, such as SPF 30 sunscreens, SPF 35 sunscreens, SPF 40 sunscreens, SPF 50 sunscreens; creams, such as face creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or gels for personal care; products to be applied to the skin, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin cloths, shaving preparations; fabric softeners;

dental impression materials; or variations of these.

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MEXICAN INSTITUTE OF INDUSTRIAL NOFISDAD

Suitable materials containing an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule described herein, may include, but are not limited to, lotions, such as cosmetic lotions, personal care lotions, lotions. body, emulsifier-free body lotions; serums, such as anti aging serums; sunscreens, as can 30 sunscreens be SPF, sunscreens SPF 35, sunscreens SPF 40, sunscreens SPF 50; creams, such as face creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or personal care gels; products to be applied to the skin, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin cloths, shaving preparations; fabric softeners; dental impression materials; or variations of these.

In one embodiment, examples of suitable lotion formulations include body lotion formulations,

<img file="MX347644B_D0074.tif" />

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OF LAMOPlEOAl.

ΙΜΙΉΙ5ΤΚΙΑΙ containing an enrertyifdrradóre ^ free emulsion; wherein the emulsion is thickened by a star macromolecule described herein, may include, but are not limited to, formulations containing one or more of the following: Ionized water; Di sodium EDTA; 1,3-Butylene Glycol; Glycerin; Allantoin; Urea; TEA 99%; Edible Olive Oil (NF); shea butter; Wickenol 171; squalane; Crodamol CAP; Crodamol STS; Crodacol C; Tween 20; Lipo GMS 470; PEG 100 stearate; Cetyl Palmitate; Crodamol PTIS; Crodafos CES; DC 1401; Ass Grass Oil; Vitamin E Acetate; Panthenol D; HA2 Distinctive; Diocida; or derivatives or combinations thereof.

In one embodiment, examples of suitable lotion formulations include emulsifier-free personal care lotion formulations, which contain an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule described herein, may include, but not are limited to, formulations containing one or more of the following: Ionized water; Di sodium EDTA; 1,3-Butylene Glycol; Glycerin; Allantoin; Urea; TEA 99%; Edible Olive Oil (NF); Wickenol 171; Miritol 318; squalane; Crodamol PTIS; Isododecane; Herb Oil

<img file="MX347644B_D0075.tif" />

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INSTITUTO MEXICANO DE LA PROPERTY INDUSTRIAL del Asno; Vitamin E Acetate; Panthenol D; HA2 Distinctive; Diocida; or derivatives or combinations thereof.

In one embodiment, examples of suitable formulations include - serum formulations, such as anti aging serum formulations, containing an emulsion free of emulsifiers, wherein the emulsion is thickened by a star macromolecule 10 described herein, may include, but are not limited to, formulations containing one or more of the following: Ionized water; Di sodium EDTA; Glycerin; 1,3-Butylene Glycol; Caffeine; Allantoin; Triethanolamine 99%; Crodamol STS; Miritol 318; Wickenol 171; Tween 20;

Crodafos CES; BVOSC; Vitamin E Acetate; Vitamin A Palmitate; Vitamin D3; Gransil IDS; Panthenol D; DC Upregulex; DC Skin Bright MG; Actifilo from Japanese Green Tea G; Actifilo from Grape Seed G; DC Hydroglide; Diocida; or derivatives or combinations thereof.

In one embodiment, suitable formulations include sunscreen formulations, containing an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule described herein, may include, but are not limited to,

INSTITUTO MEXICANO DE LA RRONEÍMP INDUSTRIA!

formulations containing one or more of the following: ionized water; Di sodium EDTA; Glycerin; Triethanolamine 99%; Homomethyl Salicylate; Ethylhexyl Salicylate; Avobenzone; Benzophenone 3; Miritol 318; Lexfeel 7; Octocrylene; Cetyl Alcohol; Cocamine PEG15; Lipo GMS 470; Crodafos CS-20; Vitamin E Acetate; Aloe Vera Leaf Juice; Diocida; or derivatives or combinations thereof.

In one embodiment, examples of suitable formulations include face cream formulations, containing an emulsion free from emulsifiers, wherein the emulsion is thickened by a star macromolecule described herein, may include, but are not limited to, formulations containing one or more of the following: Deionized water; Disodium EDTA; 1,3 Butylene Glycol; Glycerin; Caffeine; Allantoin; Triethanolamine 99%; Miritol 318; Octyl Palmitate; Wickenol 171; Crodaphos CES; Cetyl Alcohol; Pationico SSL; Cetyl Palmitate; Vitamin E Acetate; BVOSC; Lexfeel 7; Lipo GMS 470; Vitamin A / D3 in Corn Oil; DC 1401; Actifilo from Japanese Green Tea G; Actiphyte from Grape Seed G; DC Hydroglide; Diocida; or derivatives or combinations thereof.

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<img file="MX347644B_D0076.tif" />

Synthesis of the Rheology Modifier

Although any conventional method can be used for the synthesis of the multi-arm star macromolecules of the invention, free radical polymerization and living / controlled radical polymerization (CRP) is the most preferred process.

During the past decade CRP has emerged as one of the most robust and powerful techniques for polymer synthesis, combining some of the desirable attributes of conventional free radical polymerization (e.g., the ability to polymerize an interval broad monomers, tolerance of various functionalities in monomers and solvents, compatibility with viable reaction conditions, simple in the industrial setting) with the advantages of living ionic polymerization techniques (e.g., the low polydispersity index polymer preparation (PDI = M_or/ M_n) and homo- and (co) polymers) in block with functional group at the end of the chain. The basic concept behind the various CRP procedures is the reversible activation of a latent species to form the propagating radical. A dynamic and rapid equilibrium between latent and active species minimizes the probability of bimolecular root termination reactions and

<img file="MX347644B_D0077.tif" />

provides an equal opportunity for propagation to all polymer (or latent) chains.

CRP procedures can be classified into three main groups based on the reversible activation mechanism: (a) stable free radical polymerization (SFRP, Scheme la), (b) degenerative chain transfer polymerization (DT, Scheme Ib), and (c) atom transfer radical polymerization (ATRP, Scheme 1c).

(a) Stable free radical polymerization (SFRP)

<img file="MX347644B_D0078.tif" />

(b) Degenerative chain transfer polymerization (DT)

P_n-X ₊

<img file="MX347644B_D0079.tif" />

Initiator ...................

<img file="MX347644B_D0080.tif" />

Pn'X (c) Radical Atom Transfer Polymerization (ATRP)

Ρ_Ί-Χ + Cu (l) -X / L

<img file="MX347644B_D0081.tif" />

p_n* Cu (II) -X₂/ L

<img file="MX347644B_D0082.tif" />

Scheme 1. Three main groups of controlled radical polymerization based on the reversible activation mechanism: (a) radical polymerization

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free stable free (SFRP), (b) degenerative chain transfer polymerization (DT), and (c) atom transfer radical polymerization (ATRP).

As shown in Scheme 1 various protective agents, X, are used for the different CRP procedures and are summarized in Scheme 2. They include stable nitroxides (Scheme 2a), transition metal complexes (Scheme 2b), halides with metal catalysts of transition (Scheme 2c), iodine catalysts (Scheme 2d), sulfur compounds (Scheme 2e), iodine (Scheme 2f), and organometallic compounds (Scheme

2 g)

<img file="MX347644B_D0083.tif" />

(a) Nitroxides (NMP)

X = -ON ~) (TEMPO) etc.

(b) Transition metal complexes

X = -cQ etc.

(c) Halides with transition metals (ATRP)

X = -Br, Cl, 1+ Metal (Cu, Fe, Ru, etc.) (d) Iodide with catalysts (RCTP)

X = -I + Ge, Sn, etc.

(e) Dithioester, dithiocarbamate and xanthate (RAFT)

X = -SC = S

Z (Z = Ph, CH₃, NEt₂, OEt, etc. ) (f) Iodine (ΓΓΡ)

X- -i (g) Tellurium, stibine and bismuth compounds (TERP, SBRP and BIRP)

X = -RR '(R - Te, Sb, or Bi, R' = CH₃, etc. )

Scheme 2. Examples of protective agent X.

Star polymers are nano-scale materials with a globular shape. As shown in Figure 1, stars formed by the first arm process, described in detail below, may have a lattice core and optionally may possess multiple segmented arms of similar composition. The stars can be designed as homo arm stars

<img file="MX347644B_D0084.tif" />

or mikto arm stars. The figure represents a homo-star arm with block copolymer arms. Mikto arm stars have arms with different composition or different molecular weight; Figure IB and 1C.

Homo-arm stars and mikto-arm stars can optionally have high-density peripheral functionality.

The synthesis of the star polymers of the invention can be carried out by means of living polymerization techniques through one of three strategies: 1) first nucleus that is carried out by growing the arms of an initiator with multifunctionality; 2) Engaging involves joining the preformed arms on a core with multifunctionality and the 3) first arm method that involves crosslinking the preformed linear arm precursors using a divinyl compound.

Although all of the above controlled polymerization procedures are suitable for the preparation of one embodiment of the self-assembled star macromolecules described. Other modalities are also exemplified, for example, the preparation of self-assembly of multi-arm stars with narrow MWD, on the contrary the prior art used ATRP. The

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I heard LA MC * at&gt; Al

INDUSTRIAL

<img file="MX347644B_D0085.tif" />

reason for the use of the Controlled Radical Polymerization (CRP) process known as ATRP; described in US Patents 5,763,546; 5,807,937; 5,789,487; 5,945,491; 6,111,022; 6,121,371; 6,124,411: 6,162,882: and US Patent Applications 09 / 034,187; 09 / 018,554; 09 / 359,359; 09 / 359,591; 09 / 369,157; 09 / 126,768 and 09 / 534,827, and described in numerous publications listed elsewhere with Matyjaszewski as a co-author, which are incorporated into this application, is that convenient procedures are described for the preparation of polymers that exhibit control over the molecular weight of the polymer, molecular weight distribution, composition, architecture, functionality and the preparation of molecular compounds and closed polymeric structures containing radical (co) polymerizable monomers, and the preparation of controllable macromolecular structures under mild reaction conditions.

One aspect of the present invention relates to the preparation and use of multi-arm star macromolecules by means of a proposed first arm, described by Gao, H .; Matyjaszewski, K. JACS; 2007, 129, 11828. Paper references and references mentioned therein are incorporated herein by reference to describe the

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INSTITUTO MEXICANO m LA PROPERTY industrial foundations of the synthetic procedure. The supplementary information available within the aforementioned references provides a procedure for calculating the number of arms in the star macromolecule formed.

It is expected that biphasic systems such as a mini-emulsion system or an ab initio emulsion system would also be suitable for this procedure because mini-emulsion systems have been shown to function as dispersed bulk reactors [Min, K .; Gao, H .; Matyjaszewski, K. Journal of the American Chemical Society 2005, 127, 3825-3830] with the added advantage of minimizing core-core coupling reactions based on compartmentalization considerations.

In one embodiment the star macromolecules are prepared with predetermined composition and molecular weight of each segment to function as rheology modifiers in aqueous solutions. The first segmented linear (co) polymer chains formed are chains extended with a crosslinker that forms a crosslinked core.

In another embodiment a simple industrially scalable process for the preparation of star macromolecules is provided wherein the arms contain selected segments to induce self-assembly and where the self-assembling star macromolecules are suitable for use as rheology control agents in non-aqueous coatings. or in solvent, adhesives, cosmetics, and personal care compositions.

The invention is not limited to the specific compositions, components, or process steps described herein as they may vary.

It should also be understood that the terminology used herein is solely for the purpose of describing the particular modalities and is not intended to be limiting.

The process for the preparation of star macromolecules can be exemplified by the (co) polymerization of linear macromolecules, including macroinitiators (MI) and macromonomers (MMs), with a multi-vinyl crosslinker, a divinyl crosslinker is employed in the exemplary examples described in the present, to form a core of the star. The formation of the core of the star can also be

<img file="MX347644B_D0086.tif" />

form through a copolymerization reaction where monovinyl monomer is added to expand the free volume of the core to allow incorporation of additional arms into the congested nucleating environment or to provide sufficient free volume within the core of the star to encapsulate small molecules with functionality. A molecule that functions as an initiator and a monomer, an inimer, can also be used in preparing the core of the star macromolecule. When added to the reaction it works to form a three-armed branch in the nucleus of the molecule and therefore acts in a similar way to the added monomer to increase the free volume within the core of the star.

The volume fraction of the star core can be controlled by appropriate selection of the crosslinker molecule or by conducting a copolymerization between the crosslinker and a vinyl monomer or an inimer. The composition of the core can be selected to provide an environment for encapsulating small molecules, such as fragrances, and to control the rate of diffusion of the fragrance from the self-assembled thickening agent after deposition on a part of the human body.

<img file="MX347644B_D0087.tif" />

The core of star polymers can contain additional functionalities. This additional functionality can be of direct utility in certain applications or it can be used to enclose or encapsulate other materials with functionality such as fragrances, molecules sensitive to stimuli or molecules biosensitive to the core of the star through chemical or physical interactions.

Star macromolecules can be prepared in dilute solution when crosslinker and reaction conditions are chosen to avoid or reduce star-star coupling reactions.

Synthesis of multi-arm star polymers where the periphery of the star polymers contains additional functionalities is possible. This functionality can be introduced using an initiator that contains the desired "-functionalities where the low molecular weight initiator residue remains at the end of the cx-chain of each arm.

An embodiment of the exemplified by the multi-arm star in the present invention can be prepared from a macromolecule where the number of arms in the

INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL Star macromolecule is between 5 and 500, preferably between 10 and 250, with segments selected to induce self-assembly when the star macromolecule is dispersed in a liquid where self-assembling 5-star macromolecules are suitable for use as thickening agent or rheology modifiers in cosmetic and personal care compositions at low concentrations of the solid in the thickened solution, preferably less than 5% by weight, and optimally less than 1% by weight. The dispersion medium can consist of aqueous systems or oil-based systems.

The structure of an exemplary new thickening agent, or rheology modifier, of one embodiment is a multi-arm segmented star macromolecule wherein the core is prepared by controlled radical polymerization using a first arm method. Scheme 3 provides a simple four-step procedure that can be employed in preparing a non-limiting exemplary initial case. The procedure is a method of radical polymerization by atom transfer of the first arm macroinitiator. In this proposal, the precursor of the arm or arms contains a linear copolymer chain with a single terminal group.

<img file="MX347644B_D0088.tif" />

<img file="MX347644B_D0089.tif" />

INSTITUTO MEXICANO DE CA PROPIEDAD INDUSTRIAI activatable, as an expert in the art will understand, taking this description as a guide, the precursor of the activatable arm _ will have terminal functionality ω that under the conditions of the reverse polymerization procedure can generate a radical. Scheme 3 shows the concept by the sequential polymerization of styrene and tBA. These monomers are purely exemplary monomers and should not limit the applicability of the process in any way as other monomers of similar filicity or affinity may be employed. At

Scheme 3 the polystyrene segment can be considered the outer lining of the star and the final poly (acrylic acid) segments the internal water soluble lining and the segment formed by the chain that extends the linear copolymer macroinitiators by reaction with the divinylbenzene crosslinker of the star core.

<img file="MX347644B_D0090.tif" />

PSt-b-PíBA PSt-b-PAA

Star star

Step 1 Step 2 Step 3 Step 4

Scheme 3. Multistep synthesis of PSt-b-PAA block copolymer stars

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<img file="MX347644B_D0091.tif" />

Similar structures can also be prepared using the macromonomer method or a combination of the macromonomer and macroinitiator method in a controlled polymerization process, or even conducted with free radical copolymerization into macromonomers, as is known to those skilled in the art. [Gao, H .; Matyjaszewski, K. Chem. — Eur. J. 2009, 15,

6107-6111.]

Both macromonomer and macroinitiator procedures allow the incorporation of polymer segments prepared by procedures other than CRP [WO 98/01480] into the final star macromolecule. The polymer segments can contain segments that are bio-degradable formed from monomers prepared from biological sources.

As noted above, the first ATRP macroinitiator formed can be prepared by performing a sequential ATRP (co) polymerization of hydrophobic and hydrophilic monomers or precursors thereof or can be prepared by other polymerization procedures that provide a functional terminal atom or group that can be converting into an ATRP initiator with a bifunctional molecule where one functionality contains an atom or transfer group and the other functionality an atom or group that can react with the first functionality present in the (co) polymer prepared by a non-ATRP method. [WO 98/01480]

In aqueous solutions, the composition and molecular weight of the outer shell of hydrophobes, or agents that participate in molecular recognition, can be selected to induce self-assembly into aggregates and act as physical cross-linkers. Above a certain concentration, corresponding to the formation of a reversible three-dimensional, the solutions will behave like physical gels, thereby modifying the rheology of the solution.

In one embodiment, the polymer compositions of the invention have significantly lower critical concentration for network (gel) formation compared to networks formed with block, grafted, and star copolymers with a low specific number of attached arms due to:

· Multi-arm structure (many possible transient junctions between hydrophobic parts of stars) • very high molecular weight of each star (5 thousand to 5 million or higher) allows high swelling ratio of molecules in solution · Molecular organization on scales larger (&gt; bpm)

DE La V industriad

Considering that the previous and subsequent examples describe the preparation and use of the block copolymer as arms with a well defined transition from one segment to the segment joining a segmented copolymer with a gradient in the composition can also be used. The presence of a gradient can be created by adding a second monomer prior to consumption of the first monomer and will affect the volume fraction of monomer units present in the transition form from one domain to another. This will affect the shear sensitivity of the star macromolecule formed.

Narrow polydispersity star macromolecules containing arms with block copolymer segments can be formed with as few as 5 arms by selecting the appropriate concentration of reagents, crosslinker, and reaction temperature.

The star macromolecules can be prepared in a mini-emulsion or mini-reverse-emulsion polymerization system. The first block copolymers formed were used as reactive surfactants for the synthesis of the star by reaction with a selected crosslinker in miniemulsion.

<img file="MX347644B_D0092.tif" />

EXAMPLES

<td>Abbreviation</td><td>Nonfore</td><td>Form Purity</td><td>Commercial Source</td>

<td>Yes</td><td>Styrene</td><td>99% liquid</td><td>Sigma Aldrich</td>

<td>tBA</td><td>tert-butyl acrylate</td><td>Liquid 98%</td><td>Sigma Aldrich</td>

<td>AA</td><td>acrylic acid (fom. by</td><td colspan="2">Not available</td>

<td></td><td>vulnerability)</td><td></td><td></td>

<td>HEA</td><td>hydroxyethyl acrylate</td><td>Liquid 96%</td><td>Sigma Aldrich</td>

<td>DEBMM</td><td>diethyl 2-bromo-2-methylinalonate</td><td>Liquid 98%</td><td>Sigma Aldrich</td>

<td>TPMA</td><td>tris (2-pridimethyl) amine</td><td>solid 95%</td><td>ATRP Solutions</td>

<td>A1BN</td><td colspan="2">2,2'-Azóbis (2-methylpropionitrile) solid 98%</td><td>Sigma Aldrich</td>

<td>Sn (EH}_?</td><td>tin &lt;11&gt; 2-ethylhexanoate</td><td>Liquid 95%</td><td>Sigma Aldrich</td>

<td>DV8</td><td>divinylbenzene</td><td>Liquid 80%</td><td>Sigma Aldrich</td>

<td>TORCH</td><td>trifluxoacetic acid</td><td>Liquid 99%</td><td>Sigma Aldrich</td>

<td>THE</td><td>tetxahydxo fuxane</td><td>Liquid 99.9%</td><td>Sigma Aldrich</td>

<td>NaOH</td><td>sodium hydroxide</td><td>solid 98%</td><td>Sigma Aldrich</td>

<td>EBíB</td><td>Ethyl-a-bromoisobutyrate</td><td>Liquid 98%</td><td>Sigma Aldrich</td>

<td></td><td>Inethylene chloride</td><td>Liquid 99.6%</td><td>Sigma Aldrich</td>

<td></td><td>Acetonitxil</td><td>Liquid 99.8%</td><td>Sigma Aldrich</td>

<td>I was born</td><td>Sodium chloride</td><td>solid 99.7%</td><td>Fisher Chemical</td>

<td>DMAEMA</td><td colspan="2">2- (dimethylamino) ethyl nethacrylate</td><td></td>

<td>PEGMA</td><td colspan="2">methacrylate (polyethylene glycol)</td><td></td>

<td>NIPAM</td><td>N-is &lt;q&gt; ropilacxilaiiiida</td><td></td><td></td>

Example 1: Synthesis, purification and properties of the star thickening agent

Initial examples of a star thickening agent with the structure shown in Figure 1 as structure A are star macromolecules with PStb-PAA arms or PSt-bP arms (HEA).

<img file="MX347644B_D0093.tif" />

Example 1: Preparation of a star Macromolecule (PSt-b-PAA)_x.

The simple four-step procedure was developed for the preparation of a star macromolecule based on poly (acrylic acid) described in Scheme 3. 1 kg of the star macromolecule with arms PSt-b-PtBA was prepared as follows.

STEP 1: Synthesis of a polystyrene macroinitiator using ICAR ATRP. The reaction conditions are St / DEBMM / CuBr₂ / TPMA / AIBN = 50/1 / 0.002 / 0.003 / 0.05 in bulk at T = 60 ° C, t = 10.2 h. The reaction was run at -30% conversion resulting in the molecular weight of the polystyrene, hydrophobic segment = 1600 which is equivalent to an average degree of polymerization (DP) of 16.

The GPC graph obtained for the macroinitiator is shown in Figure 2.

STEP 2: Synthesis of the polystyrene-b-poly (t-butyl acrylate) segmented block copolymer macroinitiator. The reaction conditions for the synthesis of the PSt-b-PtBA macroinitiator arm are: tBA / PSt /

<img file="MX347644B_D0094.tif" />

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CuBr₂ / TPMA / Sn (EH)₂ = 200/1 / 0.01 / 0.06 / 0.008 in anisole (0.5 equivalent volume against tBA), T = 55 ° C, t = 18.0 h. A higher molecular weight precursor of the water soluble segment was indicated to allow a significant degree of swelling of the inner lining of the star macromolecule with final functionality. The final molecular weight of the poly (t-butyl acrylate) segment in the block copolymer was -15,400 which is equivalent to a DP = 120. The GPC curves of the polystyrene macroinitiator and the formed block copolymer macroinitiator are shown in Figure 3 and clearly indicate that a clean chain extension has occurred.

STEP 3: Synthesis of the star macromolecule (PSt-bPtBA)_x.

A multi-arm star macromolecule was prepared by performing another chain extension reaction with the block copolymer macroinitiator formed in step 2. The reaction was carried out with a mole ratio of 1:12 divinylbenzene block copolymer in anisole. The reaction conditions are: DVB / PSt-b-PtBA / CuBr₂ / TPMA / Sn (EH)₂ = 12/1 / 0.02 / 0.06 / 0.1 in anisole (38 equivalent volume against DVB), T = 80 ° C, t =

<img file="MX347644B_D0095.tif" />

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21.0 h). The GPC curves and the results of the star-forming reaction are provided in Figure 4. It can be seen that a multilink star macromolecule with a cross-linked core was formed. The GPC molecular weight of the star was 102,700 with a PDI of 1.29, which would indicate an average of six arms but this is an underestimate of the actual number of arms because the star molecule is a compact molecule. In fact in this situation the number of arms in the 10 star molecule is about 30.

The number of arms can be modified by running the nucleating reaction with a different ratio of crosslinking agent to arm precursor or by running the reaction with a different concentration of reagents.

STEP 4: Deprotection of the star macromolecule (PSt-b-PtBA) x to the star block copolymer (PSt-b20 PAA) x to provide water-soluble poly (acrylic acid) segments in the multi-arm star macromolecule. The PSt-b-PtBA arms of the star macromolecule were transformed into PSt-b-PAA arms using a new procedure. The polymer was dissolved in methylene chloride and trifluoroacetic acid to deprotect the

<img file="MX347644B_D0096.tif" />

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INSTmrro MEXICANO of the raonmAD 'NDWTUlAi groups tBu, the reaction was carried out at room temperature for 60.0 h. The polymer was then decanted and washed 3 times with acetonitrile. The polymer was then solubilized in THE and precipitated in acetonitrile. The star macromolecule was dried in a vacuum oven for 3 days at 50 ° C. The amount of polymer obtained after purification was 550 g, which would correspond to the complete conversion of PtBA to PAA.

Example 2: Properties of the star macromolecule (PStb-ΡΆΑ) as a thickening agent

The thickening properties of the final star macromolecule were investigated in the aqueous solution. 100 mg of star macromolecule (PSt-b-PAA) were dissolved in 0.5 ml of THE and transferred to 10 ml of water. The solution was then neutralized with 2 mL of basic water (with NaOH). After few minutes of stirring, gel formed, see image in Figure 5.

The rheological properties of the multi-arm star constructed with a longer hydrophilic poly (acrylic acid (PAA) inner core segment and a short hydrophobic polystyrene (PSt) peripheral segment were then investigated. The viscosity of the solutions

<img file="MX347644B_D0097.tif" />

Aqueous containing different concentrations of the star macromolecule versus shear rate were measured; using a Brookfield LVDV-E, Spindle # 31 (or # 34, # 25) at T = 25 ° C, and the results are presented in Figure 6. It is clear that even very low concentrations of the star macromolecule in water (&lt;0.6%) the apparent viscosity of the sample is very high (in the range of 50,000 to 100,000 centipoise (cP)).

In comparison, the market-leading thickening agents in personal care products (e.g. liquid thickener derived from natural non-ionic plant Crothix Liquid from CRODA or synthetic acrylate-based copolymer DOW CORNING RM 2051) were used at level 2 -5% by weight and only increased the viscosity of a water-based solution up to 5,000 - 20,000 cP.

Figure 7 presents the viscosity of the aqueous solution of a star macromolecule (PSt-b-PAA) against concentration. The measurement was made on a Brookfield LVDV-E with spindle # 31 (or # 34, # 25) at a temperature = 25 ° C and speed = 1 RPM. It can be seen that for this particular star macromolecule the concentration of

0.3% by weight of the star macromolecule in water is a

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minimum amount for gel formation and that higher concentrations significantly increase the viscosity of the resulting solution.

The tests indicated that the thickening agent provided formulations that exhibited a lack of tack, a very pleasant sensation on the skin.

Example 3: Properties of the star macromolecule (PStb-PAA) as a thickening agent in harsh environments

The thickening properties of the final star macromolecule were investigated in the aqueous solution in the presence of an oxidizing agent and at high pH. Figure 8 presents the viscosity of an aqueous solution of the star macromolecule (PSt-b-PAA) and the viscosity of the solution in water / Windex (1: 1) of the star macromolecule (PSt-b-PAA) and Figure 9 presents the results obtained with Carbopol EDT 2020 in the same media. The pH of the aqueous solution was 6-7 while the pH for the water / Windex solution was = 9-10. (Viscosity measurement was performed using a Brookfield LVDV-E, Spindle # 31 (or # 34, # 25), T = 25 ° C.) It can be seen that the viscosity of the solution in water / Windex is higher than that of the solution in water. He

<img file="MX347644B_D0099.tif" />

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INDI 'STRIAL performance of the star macromolecule (PSt-b-PAA) as a thickening agent did not decrease in this severe environment presented by the Windex / water solution with a pH = 9-10, resulting from the presence of a high amount of ammonia D. In In comparison, the thickening properties of the market leading thickener, Carbopol EDT 2020, decreased under similar conditions and Figure 9 shows that the viscosity of the water / Windex solution is lower than that of the pure aqueous solution.

Carbopol's poor performance against the star macromolecule (PSt-b-PAA) as a thickening agent in the water / Windex solution is predicted to be a consequence of the high amount of ester linkages in its structure that can interact with ionic species. present in that harsh environment or may even degrade. On the other hand, the star macromolecule (PSt-b-PAA) has only CC bonds, which make this thickening agent stable in the water / Windex solution and do not reduce the performance of the thickener.

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<img file="MX347644B_D0100.tif" />

Example 4: Properties of the star macromolecule (PStb-PAA) against the star macromolecule (PAA) as thickening agents

A star macromolecule (PAA) was synthesized in order to compare its properties with those determined for the star macromolecule (PSt-b-PAA). The synthesis of the star (PAA) was performed in a similar way as the synthesis for the star macromolecule (PSt-b-PAA) but starting with pure PtBA arms.

The final star (PAA) had similar molecular weight, number of arms and molecular weight distribution with the star macromolecule (PSt-b-PAA), Figure 10. The only difference between the two star macromolecules is the outer lining consisting of PSt with degree of polymerization 16 in the star macromolecule (PSt-bPAA) considering that this star macromolecule has homo-polymeric arms of pure PAA. Figure 11 presents the viscosity of the aqueous solutions of the star (PSt-b-PAA) and the star macromolecules (PAA). The measurement was carried out using a Brookfield LVDV-E fitted with a # 31 spindle at a temperature = 25 ° C and pH = 7. It can be seen that the viscosity of the star macromolecule with a hydrophobic outer jacket has

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Very strong thickening properties, where pure star (PAA) has low thickening effect in water.

Therefore one can conclude that in order to thicken aqueous media the proposed multi-arm star macromolecules must have a block structure and, with a hydrophilic inner liner and a hydrophobic outer liner. Without wishing to be limited by a proposed mechanism, we believe that these results in aqueous media 10 can be explained by the induced self-assembly of the hydrophobic segments in aggregates, the hydrophobic ones act as junctions between aggregates, and above a certain concentration, a physical network is formed. reversible, three-dimensional with a behavior similar to that of conventional gels.

Example 5: star macromolecule (PSt-b-ΡΆΆ) as a thickening and emulsifying agent

Due to its very well defined structure, multi-arm star macromolecule (PSt-b-PAA) can act not only as a thickening agent but also as an efficient emulsifying agent. Figure 12 presents images demonstrating the emulsification properties of the star macromolecule (PSt-b-PAA). The first

<img file="MX347644B_D0102.tif" />

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INSTITUTO MEJUCANG PE LA FROHWAl INmiSTWlA The photograph shows the mixture of water with 2% by volume of pure lemon oil. After vigorous mixing, the water and oil quickly separate into two phases. The second photograph shows water with 2% by volume of lemon oil and 0.6% by weight of thickening agent. After vigorous mixing, phase separation does not occur and the thickening properties do not diminish. The solutions were shaken for 1 min and photographs were taken after 2 h of mixing.

Its hydrophobic core (as well as its hydrophobic outer shell) can act as a storage location for small organic molecules (eg vitamins, fragrances, sun blocking agents, etc.). This provides the possibility to deliver functional organic molecules, eg. Fragrance for slow release or UV absorbing molecules in sunscreens for any part of the body in a pleasant sensation emulsion.

In order to provide an equivalent response for nonpolar media the filicity of the inner and outer liners has to be reversed.

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<img file="MX347644B_D0103.tif" />

Example 6: macromolecule stars with Mikto arm

A multi-arm star macromolecule was synthesized. The procedures for forming the PSt-b-PtBA and PtBA arms were similar to those described in Example 1. Next, two different arms were cross-linked together to form a star macromolecule. Reaction conditions for crosslinking reaction to form the core: DVB / [PSt-b-PtBA / PtBA] / CuBr2 / TPMA / Sn (EH) 2 = 17/1 / 0.02 / 0.06 / 0.2 in anisole (38 volume equivalent against DVB), (1667 ppm Cu) T = 95 ° C, t = 53.0 h, PSt-b-PtBA / PtBA = 1/4. Next, PtBA was transformed to PAA by acid deprotection as described in step 4 in Example 1.

Figure 13 shows the GPC curves of the arms and the mikto arm star macromolecule formed before and after purification by precipitation. Scheme 13B shows a representation of this mikto arm star macromolecule.

The synthesis of stars with lower amounts of the 1 outer PSt block was performed successfully. Two stars were synthesized, one with 50% and one with 20% of PSt-b-PAA arms and 50% and 80% of pure PAA arms (WJINSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIA!

08-006-234 and WJ-06-235) using the procedures detailed above. Studies show that these star macromolecules can be dispersed directly in warm water. The thickening properties of these two new stars were as good as those of the first exemplary star with 100% PSt-b-PAA arms.

Stars can be prepared with different hydrophobic outer liners. An example that provides an outer jacket that exhibits a Tg below the use temperature is a star prepared with a PnBA outer jacket.

Another proposal that can reduce the cost of preparing a hydrophobic outer shell is the conversion of commercially available α-olefins to an ATRP initiator by reaction with a haloalkyl (meth) acrylhalide.

Example 7: Stars with different hydrophobic segments

A parameter that can significantly change the viscosity of the thickening agent as well as its interaction with the surfactant in shampoo formulations is the type

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of a hydrophobic unit crowned at the peripheral end of a fraction of the arms of the star macromolecule. Two additional stars were synthesized in order to compare (PSti₆-PAAi₂₀) * (before deprotection: star macromolecule M_n,_topp = 102,700 g / mol, PDI = 1.29).

These stars include:

A) C₁₈-PAAi₄₆) x: M_n,_app = 95,600 g / mol, PDI = 1.48,

B) C12-PAA134) _x: M_n,_app = 113,900 g / mol, PDI = 1.53,

Each star was prepared in three steps: i) preparation of the PtBA arm, ii) crosslinking of arms in the star macromolecule, iii) deprotection of tBu groups. All stars had relatively low PDI with a low number of unreacted arms (&lt;15% by weight).

A new macroinitiator PtBA was prepared from an initiator containing a linear Cig alkyl chain for the preparation of the star (Ci₈-PAAi4₆) χ. The synthesis of this Ci arm precursor₈-PtBA-Br was made using ARGET ATRP from tBA using EBiB with Ci alkyl chain functionality₈. The conditions and properties of the synthesized polymer are shown in Table 1.

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Table 1. Experimental conditions and properties of PtBA prepared by ARGET ATRP^to

Molar ratios Cu Time Conv. .

Entry- ----- ...--............... , , . Μ »»

IBA I &lt;uBr_; L RA (ppm | (snm) (%)

Mn tiSUOh. 3 (W 1 0.015 0.06 Oi 50 13KO 47 1X2 (M »19 700 1.19

160 TPMA ^toI = Ci8-EBiB, L = Ligand, RA = reducing agent = Sn (EH) 2; [tBA] o = 4.67 M; T = 60 ° C, in anisole (0.5 equivalent volume against monomer);^bMn, a «H [M] p [C | vEBiB] B) _x conversion

Mn = number average molecular weight

Mw = weight average molecular weight theo = theoretical

This macroinitiator was then cross-linked using DVB on a star macromolecule. After deprotection of the tBu groups by stirring the reaction for 3 days in the presence of TFA resulting in transformation to PAA units the star was precipitated from CH2CI2. Viscosity of the star (Cig-PAA)_X resulting and the star (Ci₂-PAA) x can be compared to (PSt-b-PAA) x in water and shampoo formulations.

Example 8: Stars with an inner lining P (HEA)

Macromolecule P stars (HEA) containing water-soluble non-ionizable hydrophilic segments

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<img file="MX347644B_D0106.tif" />

selected to make the star macromolecule compatible with other solutions containing dissolved / dispersed salts that are additionally stable over a wide pH range.

The arm precursor PSt-b-PHEA was prepared using ICAR ATRP. The conditions for the polymerizations and characterization of the resulting polymer are shown in Table 2. The polymerization was well controlled and the well-defined block copolymer was prepared with relatively low (PDI = 1.26 and 1.20). This is the first successful example of ICAR ATRP for monomer type acrylate. The arm precursor PSt-b-PHEA was purified by precipitation in ethyl ether and dried under vacuum for two days at 50 ° C.

Table 1. Experimental conditions and properties of PSt _____________ b-PHEA prepared by ICAR ATRP^to ......

<td rowspan="2">Enerada.</td><td rowspan="2">HEA</td><td colspan="2">Relations</td><td rowspan="2">molars L</td><td rowspan="2">RA</td><td rowspan="2">Cu fppm |</td><td rowspan="2">Time (min)</td><td rowspan="2">Conv.</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">WILDEBEEST M_and</td>

<td>l</td><td>CuBrj</td>

<td>0S-006- 155</td><td> 200</td><td> !</td><td> 0.04</td><td>0.04 TPMA</td><td> 0.1</td><td> 200</td><td> 1200</td><td> 63</td><td> 16106</td><td> 30400</td><td> 1.26</td>

<td>OX-0 (J6- Bs</td><td> 500</td><td> 1</td><td> 0.05</td><td>0.05 TPMA</td><td>ft. 05</td><td> 167</td><td> 1230</td><td> 54</td><td> 20300</td><td> 42300</td><td> 1.20</td>

^toI = PSt (08-006-29, M_n= 1600 g / mol, PDI = 1.20), L = Ligand,

RA = reducing agent = AIBN; [HEA] q = 5.44

<img file="MX347644B_D0107.tif" />

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<img file="MX347644B_D0108.tif" />

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M; T = 65 ° C, in DMF (0.7 equivalent volume against monomer);

^bMn, theo = ([M] o / [PSt] o) x conversion.

Different crosslinking agents were investigated, including DVB and runs with 08-006-159 di (ethylene glycol) diacrylate (DEGlyDA) and runs with 08-006-161 DEGlyDA with small amounts of HEA monomer. The reaction was not fully controlled when the conversion of the added divinyl crosslinker was driven to high conversion as a consequence of the star-core star coupling reactions resulting in gel formation. However at lower crosslinker conversions and under more dilute conditions the star macromolecules were formed.

Example 9: Preparation of a

Mikto arm star macromolecule (PSimA ^ PAA ^ / PAAwihMf (mentioned _in j_to present as

Advan tomer)

The four-step procedure for the preparation of a polyacrylic acid-based mikto star macromolecule was developed and is described in Scheme 4. 1 kg of the arm star macromolecule

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<img file="MX347644B_D0109.tif" />

mikto with PSt-b-PAA and PAA arms (molar ratio of arms 4: 1) was prepared as follows.

HE PASSED

STEP 2

<img file="MX347644B_D0110.tif" />

ARGET ATRP

ARGET ATRP «BA at certain conversion» E®B

St fCASATAP

PSt

PSt-b-PíBA

PSt-b-PíBA and PIBA

<img file="MX347644B_D0111.tif" />

STEP 4

<img file="MX347644B_D0112.tif" />

Star star

[(PSt - &amp; - P®A)_x / (PtBAy -DVB [(PSt-b-PAA), / (PAA and -DVB

Scheme 4. Multi-step synthesis of mikto arm star copolymers [PSt-b-PAA / PAA]

STEP 1: Synthesis of a Polystyrene Macroinitiator (PSt) that has 15 DP

A polystyrene macroinitiator was formed using ICAR ATRP by introducing the following components into the reaction vessel in the following molar ratio: St / DEBMM / CuBr₂ / TPMA / AIBN = 50/1 / 0.002 / 0.003 / 0.05 in bulk at T = 60 ° C, t = 10.2 h. The reaction is

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<img file="MX347644B_D0113.tif" />

ran at -30% conversion. The resulting reaction product was purified to obtain the PSt in powder form. A portion of the PSt powder was dissolved in THE and passed through the GPC column. The GPC plot obtained for the macroinitiator is shown in Figure 2. The measured molecular weight of the polystyrene, hydrophobic segment = 1600 which is equivalent to an average degree of polymerization (DP) of approximately 15-16 and the PDI was measured which was of 1.24.

STEP 2: One-pot Synthesis of Polystyrene-bPoli (t-butyl acrylate) and Macroinitiator

Poly (t-butyl acrylate)

The following components were introduced into the reaction vessel in the following molar ratio: tBA / PSt (from step 1) / CuBr₂ / TPMA / Sn (EH)₂ = 200 / 0.2 / 0.01 / 0.06 / 0.1, in anisole (0.5 equivalent volume against tBA), T = 55 ° C. Approximately 2.0 hours after the reaction started, the tBA conversion reached approximately 6% and a portion of the PSt-b-PtBA was recovered and measured by GPC with the following results M_n = 19,800 g / mol; PDI = 1.16. It is determined that the following PSti copolymer block was obtained₅-b-PtBAi₄₀. Then 0.8 of the amount of the molar ratio, relative to the components

<img file="MX347644B_D0114.tif" />

Initially introduced, Ethyl 2-bromoisobutyrate (EBiB) was injected into the polymerization mixture. The reaction was continued and stopped after approximately 19.8 h. The reaction product was purified and the product was analyzed by GPC. Based on the measured GPC indices the final molecular weight of the product that was determined as the poly (t-butyl acrylate) segment in the block copolymer was -37,200 g / mol (PSti₅-bPtBA₂90) and the molecular weight of the poly (t-butyl acrylate) initiated from EBiB was 19,200 g / mol which is equivalent to a DP = 150.The total molecular weight of the arm mixture resulted in M_n = 20,800 g / mol and PDI = 1.27. The GPC curves of the polystyrene macroinitiator and the mixture of the PSti block copolymer arms₅-b-PtBA₂₉₀formed and the poly (t-butyl acrylate) arms PtBAi₅₀are shown in Figure 23. The signal from the block copolymer overlaps the signal from the homopolymer but this result clearly indicates that a clean chain extension of the PSt has occurred.

STEP 3: Synthesis of the Arm Star Macromolecule

Mikto (PSt-b-PtBA / PtBA) * 3rd.

A mikto multi-arm star macromolecule was prepared by performing another chain extension reaction with the

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<img file="MX347644B_D0115.tif" />

Block copolymer and homopolymer macroinitiators formed in step 2. The reaction was carried out with a mole ratio of macroinitiators to divinylbenzene of 1:16 in anisole. The following components were introduced into the reaction vessel in the following molar ratio: DVB / [PSt-b-PtBA / PtBA] (from step 2) / CuBr₂ / TPMA / Sn (EH)₂ = 16/1 / 0.02 / 0.07 / 0.15 in anisole (38 equivalent volume against DVB), T = 95 ° C, t = 20.6 h. The reaction product was purified and the product was analyzed by GPC. The GPC curves and star-forming reaction results are provided in Figure 24. It can be seen that a multi-arm star macromolecule with a lattice core was formed. The apparent GPC molecular weight of the star was 109,400 with a PDI of 1.52, which would indicate an average of six arms but this is an underestimate of the actual number of arms because the star molecule is a compact molecule. In fact in this situation, the number of arms in the star molecule is close to 30.

The number of arms can be modified by running the nucleating reaction with a different ratio of crosslinking agent to arm precursor or by running the reaction with a different concentration of reagents.

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<img file="MX347644B_D0116.tif" />

STEP 4: Deprotection of (PSt-b-PtBA / PtBA) to (PSt-b-PAA / PAA)

Deprotection of the star macromolecule (PSt-b-PtBA / PtBA), 30 to the star block copolymer (PSt-b-PAA / PAA), 30 to provide water-soluble polyacrylic acid segments in the multi star macromolecule -mikto arms. The PSt-b-PtBA / PtBA arms of the mikto arm star macromolecule were transformed into PSt-b-PAA / PAA arms with the following procedure. The polymer was dissolved in methylene chloride and trifluoroacetic acid to deprotect the tBu groups, the reaction was carried out at room temperature for 60.0 h. The polymer was then decanted and washed 3 times with acetonitrile. The polymer was then solubilized in THE and precipitated in acetonitrile. The star macromolecule was dried in a vacuum oven for 3 days at 50 ° C. The amount of polymer obtained after purification was 550 g, which corresponds to the complete conversion of PtBA to PAA.

<img file="MX347644B_D0117.tif" />

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Table of Test Results - comparing the star macromolecule formed in Example 9 (Advantomer) against the thickening agent, commercially available Carbopol ETD 2020.

<td>Properties</td><td>Advantomer (as formed in Example 9)</td><td>Carbopol ETD 2020</td>

<td>Dynamic viscosity (@ 1 rpm)</td><td>23,830 cP @ 0.2% by weight</td><td>48,000 cP @ 0.2% by weight</td>

<td>Index break Ind. Salt</td><td>87.8% @ 0.7% by weight</td><td>52.4% @ 0.4% by weight</td>

<td>Index break Ind. pH</td><td>99.3% @ 0.4% by weight</td><td>12.6% @ 0.2% by weight</td>

<td>shear thinning index</td><td>32.7 @ 0.2% by weight</td><td>12.9% @ 0.2% by weight</td>

<td>Gel firmness</td><td>Yes</td><td>Yes</td>

<td>index of emulsion</td><td>&gt; 12 hours</td><td>&lt;5 min</td>

<td>HLM</td><td> &gt;0.96</td><td>Not available</td>

HLM = hydrophilic-lipophilic macromolecule

<img file="MX347644B_D0118.tif" />

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Test Procedures

Sample Preparation

The aqueous gel compositions were prepared in various concentrations (eg, 0.2% by weight, 0.25% by weight, 0.4% by weight, 0.6% by weight, 0.7% by weight, and 1.0% by weight) by heating and stirring, as required (e.g. vigorously mixing at a temperature of about 60 ° C) the sample material (e.g. a star macromolecular powder or Carbopol ETD 2020) in pH-adjusted water, as necessary, (e.g. ., a pH of about 7.5 with addition of sodium hydroxide) to obtain a homogeneous mixture.

Dynamic Viscosity Test Procedure &amp; 15 Shear Thinning

A portion of the sample preparation was fed into a Brookfield LVDV-E Digital Viscometer, using spindle # 31 to mix, at STP (normal pressure and temperature), over a wide range of speeds (e.g., 0.3-100 rpm) and the shear rate and viscosity were recorded. Viscosity measurements were taken in the following sequence without stopping the instrument, 0.3, 0.5, 1, 2, 5, 10, 20, 30, 50, and 100 rpm. The dynamic viscosity was determined as the viscosity in centipoise (cP) at 0.3 rpm. An index of

<img file="MX347644B_D0119.tif" />

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<td rowspan="2">Shear Speed ​​(s' |</td><td rowspan="2">rpm</td><td colspan="2">Viscosity</td>

<td>AdvatHomer 0.2% by weight</td><td>Carbopol 0.2% by weight</td>

<td> 0.102</td><td> 0.3</td><td> 67100</td><td> 85000</td>

<td> ! 0 17</td><td> 0.5</td><td> 46980</td><td> 65600</td>

<td> 0.34</td><td></td><td> 25830</td><td>48000 ,. . í</td>

<td> ( 068</td><td></td><td> 13880</td><td> 23300</td>

<td> 1.7</td><td> 5</td><td> 6580</td><td> 15800</td>

<td> 3.4</td><td> 10</td><td> 3620</td><td> 10400</td>

<td> 6.8</td><td> 20</td><td> 2050</td><td> 6600</td>

<td> 10.2</td><td> 30</td><td> 1480</td><td> 4800</td>

<td> 17</td><td> 50</td><td> 1000</td><td> 3300</td>

<td> 34</td><td> 100 ...................</td><td> 690</td><td>2250 i</td>

Salt-Induced Breakdown Test Procedure

A portion of the sample preparation was filled into a 20 ml scintillation vial. A measured portion of NaCl was added (eg, 0.05% by weight relative to the total weight of the sample in the vial. After the NaCl addition was complete, the vial was closed and shaken for 10 min. Then, the viscosity of the sample was measured according to the Dynamic Viscosity and Shear Thinning Test Procedure, above, and the dynamic viscosity was recorded at 1 rpm.

This procedure was repeated for different

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<img file="MX347644B_D0120.tif" />

NaCl concentrations. The results are presented in Figures 18 and 22. The salt-induced breakage index, in percent, was determined by the following equation:

(0% NaCl) - Dynamic Viscosity (0.05% by weight NaCl) and Initial Dynamic Viscosity (0% NaCl) x 100%.

PH Efficiency Range Test Procedure

An aqueous gel composition at 0.4% by weight was prepared for the star macromolecule of Example 9, at an initial pH of approximately 5 and an aqueous gel composition separated by 0.2% by weight from the aqueous gel composition of Carbopol ETD 2020, At an initial pH of about 3, it was prepared by mixing and heating, as necessary (eg, vigorously mixing at a temperature of about 60 ° C). Then, the viscosity of the sample was measured according to the pH Efficiency Range Test Procedure, above, and the dynamic viscosity was recorded at 1 rpm. This procedure was repeated for different pH indices, adjusted by adding sodium hydroxide. The results are presented in Figure 19. The pH-induced rupture index, in percentage, was determined by the following equation:

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<img file="MX347644B_D0121.tif" />

Dynamic Viscosity (at 1 rpm) with pH 7.5 Dynamic Viscosity (at 1 rpm) with pH 5 / Dynamic Viscosity (at 1 rpm) with pH 5 (at rpm) at pH 7.5 x 100%.

Emulsion Test Procedure

340 mL of water were added to a 500 ml beaker and vigorously shaken with an overhead shaker. 1.6 g of the material to be tested for emulsification purposes was added and heated to 80C (sic). The pH of the solution was adjusted with 400 mg of NaOH and stirring was continued until a homogeneous gel was obtained. 60mL of sunflower oil were added while continuing vigorous stirring with a stirrer above 80C for 19 min or until a homogeneous emulsion was obtained. The mixture was allowed to cool to room temperature. Once the system cools to room temperature the timer starts. The emulsion index is the time, in minutes, it takes for the system to form two visible layers (phase separation).

Gel Firmness Test Procedure

A 10 mL portion of the mixture preparation material was filled into a 20 mL glass scintillation vial. After the transfer was complete, the vial was placed on a surface and remained without

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alteration for approximately 20 minutes at STP. The vial was gently inverted (turned upside down) and placed on the surface and a timer was started. If after 5 minutes, there is no visible flow then the sample is said to be a strong gel.

Calculation of the Hydrophilic-Lipophilic Arm / Segment (HLB, hydrophilic-lipophilic balance)

HLB = 20 * Mh / M where Mh is the molecular mass of the hydrophilic portion of the polymer arm or segment, and M is the molecular mass of the polymer arm or entire segment.

Calculation of the Hydrophilic-Lipophilic Macromolecule (HLM) oaflr «« + yaw »

HLM = divided by where

MW_n is the molecular weight for the respective arm,

HLB_n is the HLB, calculated from the HLB arm calculation, for the respective arm, and

MWcore is the molecular weight for the core, and

M is the total number of arms.

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<img file="MX347644B_D0123.tif" />

The star macromolecules described may find utility in a spectrum of applications including, but not limited to; personal care: including shampoos / conditioners, lotions, serums, creams, 5 solids, gelatins, cosmetics: including mascara, blush, lipstick, powders, perfumes and home care: including cleaners for windows, work and household surfaces, bathroom, laundry, and in dish and dishwasher applications.

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