Gradient Copolymer Synthesis through Self-Assembly.
ACS Macro Lett
; 12(4): 454-461, 2023 Apr 18.
Article
en En
| MEDLINE
| ID: mdl-36952321
ABSTRACT
Polymerization-induced self-assembly (PISA) is typically performed to produce polymer nanoparticles featuring specific assembly morphologies. Herein, we demonstrate the use of PISA as a synthetic tool to direct gradient copolymer synthesis. Specifically, we leverage hydrophobicity-induced reaction selectivity and the rate acceleration typically associated with polymer compartmentalization upon assembly during PISA to bias reaction selectivity. In the chain extension of a poly(ethylene glycol) macrochain transfer agent, the selectivity of diacetone acrylamide (DAAm) and N,N-dimethylacrylamide (DMA), two monomers with near-identical reactivity in water, can be modulated in situ such that DAAm is preferentially incorporated over DMA upon self-assembly. By increasing the feed ratio of DAAm, monomer differentiation can be further biased toward DAAm due to the locus of polymerization becoming increasingly hydrophobic. This change in selectivity affords the autonomous generation of DAAm-DMA gradient sequences, otherwise inaccessible without outside intervention. Finally, a mild hydrolysis protocol can then be employed to harvest DAAm-DMA sequences, yielding compositionally unique gradient copolymers.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
ACS Macro Lett
Año:
2023
Tipo del documento:
Article
País de afiliación:
Estados Unidos