Star macromolecules for personal and home care

• US 9,382,370 B2
• Filed: 09/25/2013
• Issued: 07/05/2016
• 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:
  US14/037,031
• Publication Number:
  US 20140024783A1
• Time in Patent Office: 1,014 Days
• US Class Current: 1/1
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 2800/48 Thickener, Thickening system
• CPC Class Codes: A61K 8/72 containing organic macromolecular compounds
• CPC Class Codes: A61K 8/8147 Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such 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 265/02 on to polymers of acids, salts or anhydrides
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 299/04 from polyesters
• CPC Class Codes: C08F 299/0492 the unsaturation being in acrylic or methacrylic groups
• 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 compound represented by Formula X:

[(P1)_q1-(P2)_q2]_t-Core-[(P3)_q3]_r 

 

Formula X

wherein;

Core represents a crosslinked polymeric segment;

P1 represents a polymeric segment comprised of monomeric residues of polymerized hydrophobic monomers;

P2 represents a polymeric segment comprised of monomeric residues of polymerized hydrophilic monomers;

P3 represents a polymeric segment comprised of monomeric residues of polymerized hydrophilic monomers;

q1 represents the number of the monomeric residues in P1;

q2 represents the number of the monomeric residues in P2;

q3 represents the number of the monomeric residues in P3 of between 30 and 500;

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

t represents the number of polymeric arms covalently attached to the Core; and

wherein;

i) the ratio of r to t is in the range of between 20;

1 and 2;

1; and

ii) at least one polymeric arm has a number average molecular weight of greater than 10,000 g/mol.

2. The compound of claim 1, wherein q2 is greater than q3.

3. The compound of claim 1, wherein the number average molecular weight of the at least one polymeric arm is between 10,000 g/mol and 200,000 g/mol.

4. The compound of claim 1, wherein:

i) the polymeric segment P1 has an HLB less than 8;

ii) the polymeric segment P2 has an HLB equal to or greater than 8;

or

iii) the polymeric segment P3 has an HLB equal to or greater than 8.

5. The compound of claim 1, wherein the arms represented by [(P1)_q1-(P2)_q2] have an HLB value greater than 18.

6. The compound of claim 1, wherein the polymeric segment P1 is a hydrophobic polymeric segment having an HLB value of less than 7.

7. The compound of claim 1, wherein the arms represented by [(P1)_q1-(P2)_q2] extend beyond the arms represented by [(P3)_q3].

8. The compound of claim 7, wherein the polymeric segment P1 is a hydrophobic homopolymeric segment.

9. The compound of claim 1, wherein the arms represented by [(P1)_q1-(P2)_q2] have a hydrophilic segment at its proximal end and a hydrophobic segment at its distal end, relative to the crosslinked core.

10. The compound of claim 1, wherein the crosslinked core comprises a hydrophobic crosslinked polymeric segment.

11. The compound of claim 1, wherein the crosslinked core contains additional functionality and/or expanded free volume.

12. The compound of claim 1, wherein at least one polymeric segment is prepared by living ionic polymerization.

13. The compound of claim 12, wherein the living ionic polymerization is anionic polymerization.

14. The compound of claim 1, wherein at least one polymeric segment is prepared by free radical polymerization.

15. The compound of claim 1, wherein at least one polymeric segment is prepared by living/controlled radical polymerization (CRP).

16. The compound of claim 15, wherein living/controlled radical polymerization is stable free radical polymerization (SFRP), degenerative chain transfer polymerization (DT), or atom transfer radical polymerization (ATRP).

17. The compound of claim 1, wherein the compound has a molecular weight of greater than 100,000 g/mol and forms a clear, homogeneous gel when dissolved in water at a concentration of at least 0.2 wt. %;

wherein the gel has;

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

ii) a salt-induced break value of at least 60%;

iii) a shear-thinning value of at least 10; and

/or

iv) an emulsion value of greater than 12 hours.

18. The compound of claim 17, wherein the gel has a viscosity of greater than 40,000 cP at a pH between 6 to 11.

19. The compound of claim 17, wherein the gel has a viscosity of less than 5,000 cP at a shear rate of 4 sec-1.

20. The compound of claim 1, wherein the compound is a rheology-modifying compound.

21. The compound of claim 1, wherein the compound is an enhanced oil recovery additive.

24. A composition, comprising the compound of claim 1.

22. A compound represented by Formula X:

[(P1)_q1-(P2)_q2]_t-Core-[(P3)_q3]_r 

 

Formula X

wherein;

Core represents a crosslinked polymeric segment;

P1 represents a polymeric segment comprised of monomeric residues of polymerized water-insoluble monomers;

P2 represents a polymeric segment comprised of monomeric residues of polymerized water-soluble monomers;

P3 represents a polymeric segment comprised of monomeric residues of polymerized water-soluble monomers;

q1 represents the number of the monomeric residues in P1;

q2 represents the number of the monomeric residues in P2;

q3 represents the number of the monomeric residues in P3 of between 30 and 500;

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

t represents the number of polymeric arms covalently attached to the Core; and

wherein;

i) the ratio of r to t is in the range of between 20;

1 and 2;

1; and

ii) at least one polymeric arm has a number average molecular weight of greater than 10,000 g/mol.

23. A compound represented by Formula X:

[(P1)_q1-(P2)_q2]_t-Core-[(P3)_q3]_r 

 

Formula X

wherein;

Core represents a crosslinked polymeric segment;

P1 represents a polymeric segment having an HLB less than 8 and comprised of monomeric residues of polymerized monomers;

P2 represents a polymeric segment having an HLB equal to or greater than 8 and comprised of monomeric residues of polymerized monomers;

P3 represents a polymeric segment having an HLB equal to or greater than 8 and comprised of monomeric residues of polymerized monomers;

q1 represents the number of the monomeric residues in P1;

q2 represents the number of the monomeric residues in P2;

q3 represents the number of the monomeric residues in P3 of between 30 and 500;

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

t represents the number of polymeric arms covalently attached to the Core; and

wherein;

i) the ratio of r to t is in the range of between 20;

1 and 2;

1; and

ii) at least one polymeric arm has a number average molecular weight of greater than 10,000 g/mol.