Star macromolecules for personal and home care

• US 8,569,421 B2
• Filed: 04/23/2010
• Issued: 10/29/2013
• Est. Priority Date: 04/23/2009
• Status: Active Grant

• Current Assignee: Pilot Polymer Technologies Incorporated
• Original Assignee: ATRP Solutions, Inc. (Pilot Chemical Corp.)
• Inventors: Jakubowski, Wojciech, McCarthy, Patrick, Tsarevsky, Nicolay, Spanswick, James
• Primary Examiner(s): KAUCHER, MARK S
• Application Number:
  US12/799,411
• Publication Number:
  US 20100273949A1
• Time in Patent Office: 1,285 Days
• Field of Search: 525/244, 525/50, 525/70, 525/191, 525/193, 525/241, 525/301, 525/221, 525/227, 525/223
• US Class Current: 525/244
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 2800/48 Thickener, Thickening system
• CPC Class Codes: A61K 2800/544 Dendrimers, Hyperbranched polymers
• CPC Class Codes: A61K 8/8152 Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• CPC Class Codes: A61K 8/90 Block copolymers A61K8/89 takes precedence
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: C08J 2300/206 Star polymers

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.

Claims

1. A polymer composition comprising mikto star macromolecules, wherein each mikto star macromolecule comprises:

a core and a plurality of ATRP arms, said plurality of ATRP arms comprising;

a) at least one arm of the plurality of ATRP arms is a hydrophilic homopolymeric ATRP arm, wherein the homopolymeric ATRP arms of the polymer composition have a polydispersity index of between 1.0 and 2.5; and

b) at least one arm of the plurality of ATRP arms is a copolymer ATRP arm, wherein the copolymer ATRP arms of the polymer composition have a polydispersity index of between 1.0 and 2.5, and said copolymer ATRP arm comprises;

1) a longer hydrophilic segment proximal to the core; and

2) a shorter hydrophobic segment distal to the core;

wherein;

i) the homopolymeric ATRP arms are shorter than the copolymer ATRP arms; and

ii) the polymer composition behaves as a thickening agent in an aqueous medium at concentration of less than 5 wt. %.

2. The polymer composition of claim 1, wherein the ratio of the hydrophilic homopolymeric ATRP arms to the copolymer ATRP arms is 4:

1.

3. The polymer composition of claim 1, wherein the hydrophilic segment comprises residues of:

acrylic acid;

2-hydroxyethyl acrylate;

N-isopropylacrylamide;

poly(ethylene glycol) methacrylate;

quaternized N,N-dimethylaminoethyl methacrylate;

or mixtures thereof.

4. The polymer composition of claim 3, wherein the hydrophilic segment comprises protected or unprotected acrylic acid residues or esters thereof.

5. The polymer composition of claim 4, wherein hydrophobic segment comprises residues of:

styrene;

methyl methacrylate;

n-butyl acrylate;

methyl acrylate;

or mixtures thereof.

6. The polymer composition of claim 5, wherein the hydrophilic segment is covalently attached to the core.

7. The polymer composition of claim 6, wherein the core is derived from one or more olefinic-containing cross-linking agents.

8. The polymer composition of claim 7, wherein the core is hydrophobic.

9. The polymer composition of claim 8, wherein the core is derived from divinylbenzene.

10. The polymer composition of claim 9, wherein the mikto star macromolecules comprise a functional group which exhibits H-bonding, coordination, hydrophobic, metal chelating and/or electrostatic forces.

11. The polymer composition of claim 10, wherein the average number of ATRP arms is between 5 and 500.

12. The polymer composition of claim 10, wherein the average number of ATRP arms is between 10 and 250.

13. The polymer composition of claim 12, wherein the composition displays shear thinning behavior.

14. The polymer composition of claim 1, wherein the composition displays shear thinning behavior.

15. The polymer composition of claim 1, wherein the hydrophilic homopolymeric ATRP arm exhibits a different solubility from the copolymer ATRP arm.

16. The polymer composition of claim 1, wherein the hydrophilic homopolymeric ATRP arm exhibits a different aqueous solubility from the copolymer ATRP arm.

17. The polymer composition of claim 1, wherein at least one of the mikto star macromolecules is a carrier for one or more small molecules.

18. The polymer composition of claim 17, wherein the one or more small molecules are released at a controlled rate.

19. The polymer composition of claim 1, wherein at least one segment of the arm in the mikto star macromolecule is comprised of copolymers which exhibit an upper critical solution temperature (UCST).

20. The polymer composition of claim 1, wherein at least one segment of the arm in the mikto star macromolecule is comprised of copolymers which exhibit a lower critical solution temperature (LOST).

21. The polymer composition of claim 1, wherein the core contains additional functionality and/or expanded free volume.

24. A thickening agent comprising the polymer composition of claim 1.

25. A thickening agent comprising the polymer composition of claim 13.

26. A personal care or cosmetics formulation or product comprising the polymer composition of claim 1.

27. A personal care or cosmetics formulation or product comprising the polymer composition of claim 13.

28. An emulsifying agent comprising the polymer composition of claim 1.

29. An emulsifying agent comprising the polymer composition of claim 13.

30. A home care formulation or product comprising the polymer composition of claim 1.

31. A home care formulation or product comprising the polymer composition of claim 13.

32. A delivery system comprising the polymer composition of claim 1.

33. A delivery system comprising the polymer composition of claim 13.

34. A lubricant comprising the polymer composition of claim 1.

35. A lubricant comprising the polymer composition of claim 13.

36. A coating comprising the polymer composition of claim 1.

37. A coating comprising the polymer composition of claim 13.

22. A polymer composition comprising mikto star macromolecules, wherein each mikto star macromolecule comprises:

a core and a plurality of ATRP arms, said plurality of ATRP arms comprising;

a) at least one arm of the plurality of ATRP arms is a hydrophobic homopolymeric ATRP arm, wherein the homopolymeric ATRP arms of the polymer composition have a polydispersity index of between 1.0 and 2.5; and

b) at least one arm of the plurality of ATRP arms is a copolymer ATRP arm, wherein the copolymer ATRP arms of the polymer composition have a polydispersity index of between 1.0 and 2.5, and said copolymer ATRP arm comprises;

1) a longer hydrophobic segment proximal to the core; and

2) a shorter hydrophilic segment distal to the core;

wherein;

i) the homopolymeric ATRP arms are shorter than the copolymer ATRP arms; and

ii) the polymer composition behaves as a thickening agent.

23. The polymer composition of claim 22, wherein the hydrophobic segment is covalently attached to the core.