Manesi Gkreti-Maria, Moutsios Ioannis, Moschovas Dimitrios, Papadopoulos Georgios, Ntaras Christos, Rosenthal Martin, Vidal Loic, Ageev Georgiy G, 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 Oct 25;15(21):4227. doi: 10.3390/polym15214227.
In this study, the use of anionic polymerization for the synthesis of living poly(dimethylsiloxane) or PDMS-Li, as well as poly(2-vinylpyridine) or P2VP-Li homopolymers, and the subsequent use of chlorosilane chemistry in order for the two blocks to be covalently joined leading to PDMS--P2VP copolymers is proposed. High vacuum manipulations enabled the synthesis of well-defined materials with different molecular weights (Μ¯n, from 9.8 to 36.0 kg/mol) and volume fraction ratios (φ, from 0.15 to 0.67). The Μ¯n values, dispersity indices, and composition were determined through membrane/vapor pressure osmometry (MO/VPO), size exclusion chromatography (SEC), and proton nuclear magnetic resonance spectroscopy (H NMR), respectively, while the thermal transitions were determined via differential scanning calorimetry (DSC). The morphological characterization results suggested that for common composition ratios, lamellar, cylindrical, and spherical phases with domain periodicities ranging from approximately 15 to 39 nm are formed. A post-polymerization chemical modification reaction to quaternize the nitrogen atom in some of the P2VP monomeric units in the copolymer with the highest P2VP content, and the additional characterizations through H NMR, infrared spectroscopy, DSC, and contact angle are reported. The synthesis, characterization, and quaternization of the copolymer structure are important findings toward the preparation of functional materials with enhanced properties suitable for various nanotechnology applications.
在本研究中，提出了使用阴离子聚合来合成活性聚二甲基硅氧烷（PDMS-Li）以及聚（2-乙烯基吡啶）（P2VP-Li）均聚物，随后使用氯硅烷化学方法使两个嵌段共价连接以生成PDMS-P2VP共聚物。高真空操作能够合成具有不同分子量（Μ¯n，从9.8至36.0 kg/mol）和体积分数比（φ，从0.15至0.67）的结构明确的材料。Μ¯n值、分散指数和组成分别通过膜/蒸气压渗透法（MO/VPO）、尺寸排阻色谱法（SEC）和质子核磁共振光谱法（H NMR）测定，而热转变则通过差示扫描量热法（DSC）测定。形态表征结果表明，对于常见的组成比，会形成片层、圆柱状和球状相，其域周期范围约为15至39 nm。报道了对具有最高P2VP含量的共聚物中一些P2VP单体单元中的氮原子进行季铵化的后聚合化学改性反应，以及通过H NMR、红外光谱、DSC和接触角进行的额外表征。共聚物结构的合成、表征和季铵化是制备具有增强性能且适用于各种纳米技术应用的功能材料的重要发现。
