Metal-free synthesis and self-assembly of poly(ethylene glycol) methyl ether-block-poly(.epsilon.-decalactone)-block-poly(methyl methacrylate) triblock terpolymers

0553636 - ÚMCH 2023 RIV GB eng J - Journal Article
Mundil, R. - Zhigunov, Alexander - Uchman, M.
Metal-free synthesis and self-assembly of poly(ethylene glycol) methyl ether-block-poly(.epsilon.-decalactone)-block-poly(methyl methacrylate) triblock terpolymers.
European Polymer Journal. Roč. 166, 5 March (2022), č. článku 110966. ISSN 0014-3057. E-ISSN 1873-1945
Institutional support: RVO:61389013
Keywords : block copolymers * micelles * organocatalysis
OECD category: Polymer science
Impact factor: 6, year: 2022
Method of publishing: Limited access
https://www.sciencedirect.com/science/article/pii/S001430572100700X

Derived from sustainable sources, ε-decalactone (ε-DL) emerges as a renewable alternative to synthetic cyclic esters. However, its copolymerization with different monomers often requires using metal complexes potentially toxic to humans and the environment. Here, we report the synthesis and self-assembly of poly(ethylene glycol) methyl ether-block-poly(ε-decalactone)-block-poly(methyl methacrylate) (mPEG-block-PDL-block-PMMA) triblock terpolymers via two synthetic pathways using a simple phosphazene- or phosphate-based metal-free catalytic system. Our size exclusion chromatography (SEC) results showed that the two-step synthetic mechanism combining bis(4-nitrophenyl) phosphate (BNPP) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ5,4λ5-catenadi(phosphazene) (t-BuP4) provided a better polymerization control than sequential copolymerization. In addition, our SAXS and AFM analysis also demonstrated that the blocks are incompatible in the terpolymers, further promoting their self-assembly into multicompartment micelles in water, as confirmed by cryo-TEM. Therefore, mPEG-block-PDL-block-PMMA triblock terpolymers may be used as both environmentally friendly alternatives to metal-catalyzed polymers and drug delivery systems.
Permanent Link: http://hdl.handle.net/11104/0328448