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.
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http://dx.doi.org/10.3390/polym15040848 | DOI Listing |
J Am Chem Soc
December 2024
Polymer Synthesis Laboratory, Laboratory, Chemistry Program, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia.
Uniform sugar-functionalized polyesters combine the benefits of sugar's structural diversity, biocompatibility, and biodegradability with precise postfunctionalization capabilities, making them a highly valuable class of materials with extensive application potential. However, the irregular placement of hydroxyl groups has limited the synthesis of these polyesters. Here, we present the first platform for uniform sugar-functionalized polyesters via regioselective ring-opening copolymerizations (ROCOPs) of allopyranoside anhydrosugar epoxide (, derived from d-glucose) with cyclic anhydrides, followed by complete selective deprotection.
View Article and Find Full Text PDFACS Macro Lett
December 2024
Department of Materials Science and Engineering, School of Materials and Chemical Technology, Institute of Science Tokyo, 2-12-1 S8-36 Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
Mesoporous carbons (MPCs) with a bimodal distribution of pore diameters are more advantageous than their monomodal counterparts for applications in adsorption, catalysis, and drug delivery systems; however, reports on their fabrication remain limited. In this study, we successfully fabricated bimodal MPCs using a soft template method with poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA)--poly(4-vinylpyridine) (P4VP)--polystyrene (PS) and resol. The blend samples formed microphase-separated structures comprising PTFEMA spheres, PS cylinders, and matrix domains composed of P4VP and resol, leading to the separation of the PTFEMA and PS domains.
View Article and Find Full Text PDFACS Nano
October 2024
Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, 1700 Fribourg, Switzerland.
Block copolymers are recognized as a valuable platform for creating nanostructured materials. Morphologies formed by block copolymer self-assembly can be transferred into a wide range of inorganic materials, enabling applications including energy storage and metamaterials. However, imaging of the underlying, often complex, nanostructures in large volumes has remained a challenge, limiting progress in materials development.
View Article and Find Full Text PDFAn ongoing challenge in polymer chemistry is accessing diverse block copolymers from multiple polymerization mechanisms and monomer classes. One strategy to accomplish this goal without intermediate compatibilization steps is the use of universal mediators. Thiocarbonyl thio (TCT) functional groups are well-known mediators to combine radical with either cationic or anionic polymerization, but a sequential cationic-anionic universal mediator system has never been reported.
View Article and Find Full Text PDFMacromolecules
July 2024
Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States.
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