Synthesis of linear and star miktoarm ABC terpolymers and their self-assembly in thin films

Abstract : The first objective of this work was to develop a synthesis method enabling the preparationof linear and star ABC terpolymers. The molecular weights of the A and B (PS and P2VP) blockswere kept constant while the size of the C (PI) block was varied to achieve different morphologies.The second objective of this work was devoted to the study of the self-assembly of linear and starABC terpolymer thin films. A synthesis route combining the anionic polymerization with acoupling method was developed. The PS and P2VP blocks were synthesized by a sequential anionicpolymerization. The PI block separately synthesized by anionic polymerization was then coupledto the PS-b-P2VP diblock via a Steglich esterification. This method revealed to be efficient sinceit is a catalyst metal-free reaction enabling to achieve well-defined terpolymers with a dispersitybelow 1.1The study of star and linear ABC terpolymer self-assembly led to new morphologies in thinfilm. A solvent vapor annealing treatment was used to promote the mobility of the polymericchains. A core-shell double gyroid structure was produced from the self-assembly of linear PS-b-P2VP-b-PI thin films. Four different crystallographic planes were observed depending on the filmthickness. Moreover, the self-assembly of star ABC terpolymer chains into a thin film (4.6.12)Archimedean tilling pattern was demonstrated for the first time. Here, the PS and PI blocksoccupied different places within the (4.6.12) tiling pattern depending on the PI volume ratio andthe solvent selected to swell the film.
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Ségolène Antoine. Synthesis of linear and star miktoarm ABC terpolymers and their self-assembly in thin films. Polymers. Université de Bordeaux, 2017. English. ⟨NNT : 2017BORD0964⟩. ⟨tel-01767225⟩

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