Abstract
A set of well-defined amphiphilic, semi-fluorinated di and triblock copolymers were synthesized via polymerization-induced self-assembly (PISA) under alcoholic dispersion polymerization conditions. This study investigates the influence of the length, nature and position of the solvophobic semi-fluorinated block. A poly(N,N-dimethylaminoethyl methacrylate) was used as the stabilizing block to prepare the di and tri block copolymer nano-objects via reversible addition-fragmentation chain transfer (RAFT) controlled dispersion polymerization at 70 °C in ethanol. Benzylmethacrylate (BzMA) and semi-fluorinated methacrylates and acrylates with 7 (heptafluorobutyl methacrylate (HFBMA)), 13 (heneicosafluorododecyl methacrylate (HCFDDMA)) and 21 (tridecafluorooctyl acrylate (TDFOA)) fluorine atoms were used as monomers for the core-forming blocks. The RAFT polymerization of these semi-fluorinated monomers was monitored by SEC and 1H NMR. The evolution of the self-assembled morphologies was investigated by transmission electron microscopy (TEM). The results demonstrate that the order of the blocks and the number of fluorine atoms influence the microphase segregation of the core-forming blocks and the final morphology of the nano-objects.
Highlights
Stable nano-objects from self-assembly in solution of amphiphilic block copolymers have been the subject of considerable research over the last 20 years
The morphology and size of nano-objects prepared by self-assembly of block copolymers depend on various factors of which the most important ones are the relative length of the blocks, the interaction between the solvophilic block chains and the interfacial energy of the solvophilic−solvophobic interface
They prepared ABC triblock copolymer vesicles via seeded dispersion polymerization of trifluoroethyl methacrylate (TFEMA) in ethanol with PMAAb-poly(benzyl methacrylate) (PBzMA) as the macro-CTA (MAA and BzMA stand for methacrylic acid and benzyl methacrylate, respectively)
Summary
Stable nano-objects from self-assembly in solution of amphiphilic block copolymers have been the subject of considerable research over the last 20 years. In 2014, Armes and coworkers reported the first use of a semi-fluorinated monomer in a PISA formulation [12] They prepared ABC triblock copolymer vesicles via seeded dispersion polymerization of trifluoroethyl methacrylate (TFEMA) in ethanol with PMAAb-PBzMA as the macro-CTA (MAA and BzMA stand for methacrylic acid and benzyl methacrylate, respectively). This chain extension produced a range of remarkably complex semi-fluorinated triblock copolymer morphologies, with internal phase separation driven by the enthalpic incompatibility between the PBzMA and PTFEMA core-forming blocks. The degrees of polymerization of the core-forming blocks and their order in the block sequence along with the number of fluorine atoms (7, 13 and 21) in the semi-fluorinated hydrophobic block was varied and the effects of these parameters on the final morphologies and phase segregation were studied
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