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Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State

  • Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.

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Document Type:Article
Author:Hanna Hübner, Bart-Jan NiebuurORCiD, Oliver JankaORCiD, Lea Gemmer, Marcus Koch, Tobias KrausORCiD, Guido KickelbickORCiD, Bernd StühnORCiD, Markus GalleiORCiD
Parent Title (English):Macromolecular Chemistry and Physics
First Page:2200178
Year of first Publication:2023
Release Date:2022/11/18
Tag:anionic polymerization; confinement; crystallization; microphase separation; morphology
Impact:02.527 (2021)
Funding Information:Saarland University and German Science Foundation. Grant Number: INST 256/349-1
Groups:Physikalische Analytik
Open Access:Open Access
Signature:INM 2023/006
Licence (German):License LogoCreative Commons - CC BY-NC - Namensnennung - Nicht kommerziell 4.0 International