Star macromolecules for personal and home care
View Patent ↗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.
1. A polymer composition comprising one or more star macromolecules formed by an arm-first living-controlled radical polymerization and having a core and a plurality of polymeric arms, wherein:
a) at least one arm of the plurality of polymeric arms is a hydrophilic polymeric arm, and at least one arm of the plurality of polymeric arms is a copolymeric arm, wherein:
1) the copolymeric arm comprises a longer hydrophilic segment proximal to the core and a shorter hydrophobic segment distal to the core; and
2) the hydrophilic polymeric arm is shorter than the copolymer arm.
2. The polymer composition of claim 1 , wherein arm-first living-controlled radical polymerization, comprises:
1) preparing the plurality of polymeric arms, comprising:
i) initiating chain-extension of a macro-initiator by polymerizing hydrophilic monomeric units to form an intermediate block copolymeric arm in a reaction mixture;
ii) introducing an ATRP initiator to the reaction mixture;
iii) polymerizing additional hydrophilic monomeric units onto the ATRP initiator to form an hydrophilic polymeric arm; and
iv) polymerizing additional hydrophilic monomeric units onto the intermediate block copolymeric arm to form an extended block copolymeric arm;
2) forming the one or more star macromolecules by reacting:
i) a crosslinker;
ii) an end of the hydrophilic polymeric arm; and
iii) an end of the hydrophilic end of the extended block copolymeric arm; and
3) optionally, deprotecting one or more protection groups present on the one or more star macromolecules, introducing further functionality on one or more of the polymerized hydrophilic monomeric unit residues, or combinations thereof.
3. The polymer composition of claim 2 , wherein the plurality of polymeric arms is a plurality of ATRP polymeric arms.
4. The polymer composition of claim 2 , wherein the ratio of the at least one hydrophilic polymeric arm to the at least one copolymeric arm is 4:1.
5. The polymer composition of claim 4 , wherein the macroinitiator is a hydrophobic polymeric segment.
6. The polymer composition of claim 5 , wherein the hydrophobic polymeric segment comprises a living chain end.
7. The polymer composition of claim 5 , wherein the hydrophobic polymeric segment is formed by controlled polymerization.
8. The polymer composition of claim 7 , wherein hydrophobic polymeric segment comprises residues of: styrene; t-butyl-styrene; methyl methacrylate; n-butyl acrylate; methyl acrylate; octyl acrylate; decyl acrylate; dodecyl acrylate; decyl methacrylate; decyl ethacrylate; or mixtures thereof.
9. The polymer composition of claim 8 , wherein the at least one hydrophilic polymeric arm comprises residues of: acrylic acid; 2-hydroxyethyl acrylate; N-isopropylacrylamide; poly(ethylene glycol) methacrylate; N,N-dimethylaminoethyl methacrylate; quaternized N,N-dimethylaminoethyl methacrylate; 2-acrylamido-2-methylpropane sulphonic acid; styrene sulphonic acid; or mixtures thereof.
10. The polymer composition of claim 8 , wherein the at least one hydrophilic polymeric arm comprises residues of acrylate esters or methacrylate esters.
11. The polymer composition of claim 10 , wherein the plurality of polymeric arms comprises an average number of polymeric arms in the range of between 5 and 500.
12. The polymer composition of claim 2 , wherein living-controlled radical polymerization is stable free radical polymerization (SFRP), degenerative chain transfer polymerization (DT), or atom transfer radical polymerization (ATRP).
13. The polymer composition of claim 2 , wherein the core a crosslinked hydrophobic core.
14. The polymer composition of claim 2 , wherein the one or more macromolecules has an average molecular weight of up to 5,000,000.
15. The polymer composition of claim 1 , wherein the at least one hydrophilic polymeric arm exhibits a different solubility from the at least one copolymeric arm.
16. The polymer composition of claim 1 , wherein:
i) at least one arm of the plurality of polymeric arms is a hydrophilic polymeric arm, wherein the at least one hydrophilic polymeric arm has a polydispersity index of between 1.0 and 2.5; or
ii) at least one arm of the plurality of polymeric arms is a copolymeric arm, wherein the at least one copolymeric arm has a polydispersity index of between 1.0 and 2.5.
17. The polymer composition of claim 1 , wherein the polymer composition behaves as a thickening agent in an aqueous medium at concentration of less than 5 wt. %.
18. The polymer composition of claim 1 , wherein the composition displays shear thinning behavior.
19. The polymer composition of claim 1 , wherein the composition is an enhanced oil recovery additive composition.
20. The polymer composition of claim 1 , wherein the composition is an oil-well drilling fluid additive composition.