Synthesis of well‐defined rod‐coil block copolymers containing trifluoromethylated poly(phenylene oxide)s by chain‐growth condensation polymerization and atom transfer radical polymerization

Abstract

Well-defined trifluoromethylated poly(phenylene oxide)s were synthesized via nucleophilic aromatic substitution (S N Ar) reaction by a chain-growth polymerization manner. Polymerization of potassium 4-fluoro-3-(trifluoromethyl)phenolate in the presence of an appropriate initiator yielded polymers with molecular weights of $4000 and polydispersity indices of <1.2, which were characterized by 1 H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Initiating sites for atom transfer radical polymerization (ATRP) were introduced at the either side of chain ends of the poly(phenylene ox-ide), and used for ATRP of styrene and methyl methacrylate, yielding well-defined rod-coil block copolymers. Differential scanning calorimetry study indicated that the well-defined trifluoromethylated poly(phenylene oxide)s showed high crystallinity and were immiscible with polystyrene. EXPERIMENTALMaterials 4-Fluoro-3-(trifluoromethyl)phenol (Fluorochem), 4-fluoro-3-(trifluoromethyl)aniline (Aldrich), 4-nitro-3-(trifluoromethyl)benzonitrile (2, Aldrich), 2-bromoisobutyryl bromide (Aldrich), and 2,2 0 -bipyridine (bpy, Aldrich) were used as received. Phenol was distilled under reduced pressure. 2-*Present address:

Grafting of trifluoromethylated poly(phenylene oxide)s on a single‐walled carbon nanotube via surface‐initiated chain‐growth condensation polymerization

“…CF 3 ‐PPO were grown from the SWNT surface according to the synthetic route shown in Scheme . Previously, we developed a novel synthesis of narrow‐disperse CF 3 ‐PPO by CGCP using 1‐fluoro‐2‐(trifluoromethyl)benzene as an initiator . To functionalize the SWNT with a 1‐fluoro‐2‐(trifluoromethyl)benzoyl group, 4‐fluoro‐3‐(trifluoromethyl)benzenediazonium tetrafluoroborate was synthesized and reacted with SWNT under the reported reaction conditions to obtain SWNT‐I (Supporting Information, Fig.…”

Scope of controlled synthesis via chain-growth condensation polymerization: from aromatic polyamides to π-conjugated polymers

“…16). 36 The ATRP of methyl methacrylate with 16a successfully afforded poly13a-b-poly(methyl methacrylate), but 16a was not suitable for controlled ATRP of styrene, presumably because of poor initiation efficiency at the site adjacent to the amide bond. 49,50 On the other hand, 16b afforded both poly13ab-poly(methyl methacrylate) and poly13a-b-polystyrene.…”

Preparation and Characterization of Thermo-Responsive Rod-Coil Diblock Copolymers

“…The aggregation and microphase separation of such block copolymers driven by various novel functionalities of p–p interaction through solvent selection or rigid segmentation may result in various nanosized morphologies [ 4 , 5 , 6 ]. Different conjugated rod-coil block copolymers have been reported in the literature, including those of thiophene [ 7 , 8 ], phenylene [ 9 , 10 , 11 ], and quinolone [ 12 , 13 ]. The fluorene-based rod-coil block copolymers were used in this study because of their high thermal/chemical stability and good fluorescence quantum yield [ 14 , 15 , 16 ].…”