Facile Synthesis of Rod–Coil Block Copolymers with Chiral, Helical Polycarbodiimide Segments via Postpolymerization CuAAC “Click” Coupling of Functional End Groups

• Published in: Macromolecules Vol. 48; no. 10; pp. 3207 - 3216
• Main Authors: Reuther, James F, Siriwardane, Dumindika A, Kulikov, Oleg V, Batchelor, Benjamin L, Campos, Raymond, Novak, Bruce M
• Format: Journal Article
• Language: English
• Published: American Chemical Society 26.05.2015
• Subjects: alkynes; atomic force microscopy; chemical bonding; composite polymers; evaporation; matrix-assisted laser desorption-ionization mass spectrometry; melting; moieties; nickel; nuclear magnetic resonance spectroscopy; polymerization; porous media; scanning electron microscopy; solvents; toluene
• ISSN: 0024-9297; 1520-5835; 1520-5835
• DOI: 10.1021/acs.macromol.5b00453

Using the living nickel­(II)-mediated polymerization of carbodiimides, the chiral (R)- or (S)-N-1-phenethyl-N′-methylcarbodiimide (PMC) monomers were polymerized with a new TIPS protected alkyne functional nickel initiator forming PPMC with an excess single-handed screw sense and the alkyne moiety covalently attached to the terminus of the polymer, as confirmed by 1H NMR and MALDI-TOF MS. After deprotection, the alkyne end groups of rigid-rod PPMC-2 were coupled with azide-terminated, random-coil PS and PEG homopolymers forming a novel class of helical-b-coil block copolymers. In the thin-film, all synthesized diblock copolymers formed interesting nanofibular morphologies when subject to specific conditions. The triblock RCP-4, however, adopted unique macroporous morphology as identified by AFM and SEM with average pore diameters of ca. 832 ± 194 nm. The origin of this was found to be associated with the ordering of large, hollow vesicle aggregates upon solvent evaporation followed by the melting of these aggregates filling in the hollow interior forming the submicron pores observed. Furthermore, the size of these aggregates can be easily modulated in a linear fashion from 272 to 1648 nm simply by increasing the concentration of RCP-4 in THF. Finally, the three PPMC–PEG copolymers synthesized were found to adopt lyotropic cholesteric mesophases in concentrated toluene solutions (ca. 30 wt %).