期刊
POLYMER CHEMISTRY
卷 5, 期 10, 页码 3466-3475出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4py00201f
关键词
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资金
- Engineering and Physical Sciences Research Council [EP/G007950/1] Funding Source: researchfish
- EPSRC [EP/G007950/1] Funding Source: UKRI
A series of well-defined amphiphilic poly(methacrylic acid)-poly(benzyl methacrylate) (PMAA-PBzMA) diblock copolymers are synthesized via polymerization-induced self-assembly using an alcoholic dispersion polymerization formulation. Chain growth is mediated via reversible addition-fragmentation chain transfer polymerization (RAFT) chemistry using a trithiocarbonate-based chain transfer agent (CTA) at 70 degrees C. The poly(methacrylic acid) block is soluble in ethanol and acts as a steric stabilizer for the growing insoluble PBzMA chains, resulting in the in situ generation of diblock copolymer nano-objects in the form of spheres, worms or vesicles, depending on the precise reaction conditions. Copolymer morphologies can be covalently stabilized via cross-linking to prevent their dissociation when transferred into aqueous solution, which leads to the formation of highly anionic nano-objects due to ionization of the PMAA stabilizer chains. ABC triblock copolymer nanoparticles can also be prepared using this approach, where the third block is based on the semi-fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEMA). GPC studies confirm that chain extension is efficient and high TFEMA conversions can be achieved. Microphase separation between the mutually incompatible PBzMA and semi-fluorinated PTFEMA core-forming blocks occurs, producing a range of remarkably complex semi-fluorinated triblock copolymer morphologies.
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