Oil soluble rheology modifying star macromolecules

• US 10,221,285 B2
• Filed: 06/06/2016
• Issued: 03/05/2019
• Est. Priority Date: 04/23/2009
• Status: Active Grant

• Current Assignee: Pilot Polymer Technologies Incorporated
• Original Assignee: Pilot Polymer Technologies Incorporated
• Inventors: Jakubowski, Wojciech, McCarthy, Patrick, Tsarevsky, Nicolay, Spanswick, James
• Primary Examiner(s): Kaucher, Mark S
• Application Number:
  US15/174,727
• Publication Number:
  US 20170037194A1
• Time in Patent Office: 1,002 Days
• 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

Oil soluble rheology modifying star macromolecules having a core and five or more polymeric arms, and compositions comprising the same. The polymeric arms on a star are covalently attached to the core of the star; each polymeric arm comprises one or more (co)polymer segments; and at least one polymeric arm and/or at least one polymeric segment exhibits a different solubility from at least one other polymeric arm or one other polymeric segment, respectively, in a reference liquid of interest. The oil soluble rheology modifying star macromolecules and compositions comprising the same for use in oil based systems.

Claims

1. An oil composition comprising at least one rheology-modifying star macromolecule represented by Formula A:

[(P1)_q1-(P2)_q2]_t-Core-[(P3)_q3]_r 

 

Formula A

wherein;

Core represents a crosslinked polymeric segment;

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

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

P3 represents a hydrophobic polymeric segment comprised of repeat units of monomeric residues of polymerized monomers;

q1 represents the number of repeat units in P1 and has a value between 10 and 1000;

q2 represents the number of repeat units in P2 and has a value between 50 and 1000;

q3 represents the number of repeat units in P3 and has a value between 20 and 500;

t represents the number of copolymeric arms covalently attached to the Core;

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

wherein;

i) the molar ratio of r to t is in the range of between 40;

1 and 1;

40;

ii) the arms represented by [(P1)_q1-(P2)_q2]_t extend beyond the arms represented by [(P3)_q3]_r; and

wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 comprise a monomeric residue of a polymerized;

N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylamide, quaternised N,N-dimethylaminoethyl acryl amide, N,N-dimethylaminoethyl methacrylamide, quaternised N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, quaternised N,N-dimethyl-aminoethyl acrylate, quaternised N,N-dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-(trimethylamino)ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acylate, or octyl acrylate.

2. The oil composition of claim 1, wherein the at least one rheology-modifying star macromolecule is an oil-soluble rheology-modifying star macromolecule.

3. The oil composition of claim 1, wherein the at least one rheology-modifying star macromolecule is soluble in a reference liquid of interest comprising oil.

4. The oil composition of claim 1, wherein the at least one rheology-modifying star macromolecule is a thickener for an oil-based system.

5. The oil composition of claim 1, wherein the at least one rheology-modifying star macromolecule provides rheology control over viscosity in an oil based system.

6. The oil composition of claim 1, wherein the number of polymeric arms (r+t) is between 5 and 500.

7. The oil composition of claim 1, wherein (r+t) is greater than 15.

8. The oil composition of claim 1, wherein q2 is greater than q3.

9. The oil composition of claim 1, wherein P2 represents a hydrophobic polymeric segment comprised of repeat units of monomeric residues of polymerized monomers.

10. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 further comprise a monomeric residue of a polymerized alkyl(meth)acrylate.

11. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 further comprise a monomeric residue of a polymerized methyl methacrylate.

12. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, and P3 further comprise a monomeric residue of a polymerized methyl methacrylate.

13. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 further comprise a monomeric residue of a polymerized styrene optionally substituted with one or more C1-C12 straight or branched chain alkyl groups.

14. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 further comprise a monomeric residue of a polymerized:

dodecyl acrylate, N-dodecyl methacrylamide, styrene or 2-ethylhexyl methacrylate.

15. The oil composition of claim 1, wherein the repeat units of monomeric residues of polymerized monomers within P1, P2, or P3 further comprise a monomeric residue of a polymerized acrylamide.

16. The oil composition of claim 1, wherein the Core comprises monomeric residues of polymerized monomers comprising:

1,2-divinylbenzene;

1,3-divinylbenzene;

1,4-divinylbenzene;

1,2-ethanediol di(meth)acrylate;

1,3-propanediol di(meth)acrylate;

1,4-butanediol di(meth)acrylate;

1,5-hexanediol di(meth)acrylate;

divinylbenzene;

ethyleneglycol di(meth)acrylate;

di(ethylene glycol) di acrylate (DEGlyDA);

propyleneglycol di(meth)acrylate;

butyleneglycol di(meth)acrylate;

triethyleneglycol di(meth)acrylate;

polyethyleneglycol di(meth)acrylate;

polypropyleneglycol di(meth)acrylate;

polybutyleneglycol di(meth)acrylate;

allyl(meth)acrylate;

glycerol di(meth)acrylate;

trimethylolpropane ti(meth)acrylate;

pentaerythritol tetra(meth)acrylate;

ally′

methacrylate;

allyl acrylate, di(ethylene glycol) diacrylate (DEGlyDA), or divinylbenzene.

17. An oil based system additive, comprising the oil composition of claim 1.

18. The oil composition of claim 1, wherein the polymeric segments P1, P2, and/or P3 are random polymeric segments.

19. The oil composition of claim 1, wherein the core comprises, by weight:

about 0.5%, or more, monomeric residues of polymerized monomers from P2 and P3, and

about 0.5%, or more, monomeric residues of polymerized monomers different from the monomeric residues of polymerized monomers from P1, P2, or P3.

20. The oil composition of claim 1, wherein the Core is crosslinked by a crosslinker comprising ethyleneglycol di(meth)acrylate;

trimethylolpropane tri(meth)acrylate;

propyleneglycol di(meth)acrylate;

di(ethylene glycol) diacrylate (DEGlyDA);

triethyleneglycol di(meth)acrylate;

polyethyleneglycol di(meth)acrylate;

polypropyleneglycol di(meth)acrylate;

1,4-divinylbenzene;

1,2-divinylbenzene;

1,3-divinylbenzene;

1,2-ethanediol di(meth)acrylate;

1,3-propanediol di(meth)acrylate;

1,4-butanediol di(meth)acrylate;

1,5-hexanediol di(meth)acrylate;

divinylbenzene;

butyleneglycol di(meth)acrylate;

polybutyleneglycol di(meth)acrylate;

allyl(meth)acrylate;

glycerol di(meth)acrylate;

pentaerythritol tetra(meth)acrylate;

allyl methacrylate;

allyl acrylate;

or divinylbenzene.

21. An oil composition comprising at least one rheology-modifying star macromolecule represented by Formula A:

[(P1)_q1-(P2)_q2]_t-Core-[(P3)_q3]_r 

 

Formula A

wherein;

Core represents a crosslinked polymeric segment;

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

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

P3 represents a hydrophobic polymeric segment comprised of repeat units of monomeric residues of polymerized monomers;

q1 represents the number of repeat units in P1 and has a value between 10 and 1000;

q2 represents the number of repeat units in P2 and has a value between 50 and 1000;

q3 represents the number of repeat units in P3 and has a value between 20 and 500;

t represents the number of copolymeric arms covalently attached to the Core;

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

wherein;

i) the molar ratio of r to t is in the range of between 40;

1 and 1;

40;

ii) the arms represented by [(P1)_q1-(P2)_q2]_t extend beyond the arms represented by [(P3)_q3]_r; and

wherein;

the arms represented by [(P1)_q1-(P2)_q2]_t comprise monomeric residues of polymerized monomers comprising;

methyl methacrylate;

decyl methacrylate;

2-ethylhexyl methacrylate;

n-butyl methacrylate;

iso-butyl methacrylate;

t-butyl methacrylate;

2-(trimethylamino)ethyl methacrylate;

2-(dimethylamino)ethyl methacrylate;

N,N-dimethylaminoethyl methacrylate;

N,N-dimethylaminoethyl methacrylamide, methyl acrylate;

ethyl acrylate;

n-butyl acrylate;

iso-butyl acrylate;

t-butyl acrylate;

2-ethylhexyl acrylate;

decyl acrylate;

octyl acrylate;

N,N-dimethylaminoethyl acrylate;

or N,N-dimethylaminoethyl acrylamide.