Artopoiadis Konstantinos, Miskaki Christina, Manesi Gkreti-Maria, Moutsios Ioannis, Moschovas Dimitrios, Piryazev Alexey A, Karabela Maria, Zafeiropoulos Nikolaos E, Ivanov Dimitri A, Avgeropoulos Apostolos
Department of Materials Science Engineering, University of Ioannina, University Campus-Dourouti, 45110 Ioannina, Greece.
Institut de Sciences des Matériaux de Mulhouse-IS2M, CNRS UMR7361, 15 Jean Starcky, 68057 Mulhouse, France.
Polymers (Basel). 2023 Feb 8;15(4):848. doi: 10.3390/polym15040848.
We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB in all three terpolymer samples. To justify the successful incorporation of -OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications.
我们报道了三种线性三嵌段三元共聚物的合成，其中两种为ABC型，一种为BAC型，其中A、B和C分别对应三种化学不相容的链段，如聚苯乙烯（PS）、具有唯一（约100%乙烯基型）-1,2微观结构的聚丁二烯（PB）和聚二甲基硅氧烷（PDMS）。活性阴离子聚合能够合成具有低平均分子量和不同组成比的窄分布三元共聚物，这已通过多种分子表征技术得到验证。为了评估它们的自组装行为，进行了透射电子显微镜和小角X射线散射实验，结果表明不对称组成和相互作用以及链段序列反转对所采用形态的影响。此外，对所有三种三元共聚物样品中极低分子量的PB进行了后聚合化学改性反应，如硼氢化和氧化反应。为了证明在聚二烯链段中成功引入了-OH基团并制备了聚合物刷，进行了各种分子、热和表面分析测量。据我们所知，首次对这种三嵌段三元共聚物进行了合成和化学改性反应，这为设计用于纳米技术应用的聚合物提供了一条有前景的途径。
