Synthesis and characterization of fluorinated diblock copolymer of 2,2,2-trifluoroethyl methacrylate and methyl methacrylate based on RAFT polymerzation

•A fluorinated diblock copolymer of MMA and TFEMA was prepared by RAFT polymerization.•The diblock copolymer was characterized with a narrow MWD and its structure is a confirmation to the design.•The surface of the self-assembly microspheres of P(MMA-b-TFEMA) become structured when heated up close to its Tg.•The surface property of block copolymer is closed to PTFEMA and better than the random copolymer.•The optical property and thermal property are also closed to PTFEMA and much better than PMMA.

A fluorinated diblock copolymer of methyl methacrylate (MMA) and 2,2,2-trifluoroethyl methacrylate (TFEMA) was prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization in the presence of cumyl dithiobenzoate (CDB) as the chain transfer agent (CTA). 1H NMR spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography and different scanning calorimetry were used to characterize the block copolymers obtained. Contact angle measurement indicated that the diblock copolymer has considerable hydrophobicity (θwater = 104.3°) and lipophobicity (θoil = 80.0°). The results are almost the same as those for PTFEMA and superior to those for a random copolymer of MMA and TFEMA. It was also found that P(MMA-b-TFEMA) has high thermostability. The self-assembly behaviour of the copolymer in selective solvents was evaluated by SEM, and stable micelles with a diameter of 400–600 nm were observed when the copolymer content was approximately 0.2 wt.%. Comparison studies with P(MMA-b-TFEMA), PTFEMA and PMMA revealed that the copolymer with a controllable distribution of fluorine atoms possesses a good performance.

Graphical abstractA fluorinated diblock copolymer of methyl methacrylate (MMA) and 2,2,2-trifluoroethyl methacrylate (TFEMA) was prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization. Its structure was well characterized and exhibited excellent performance than PMMA and random copolymer of MMA and TFEMA.Figure optionsDownload full-size imageDownload as PowerPoint slide