Olefin metathesis polymerization: Some recent developments in the precise polymerizations for synthesis of advanced materials (by ROMP, ADMET)

• Published in: Tetrahedron Vol. 74; no. 6; pp. 619 - 643
• Main Authors: Chen, Yanjun, Abdellatif, Mohamed Mehawed, Nomura, Kotohiro
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 08.02.2018
• Subjects: ADMET polymerization; Endfunctionalization; Olefin metathesis; Ring opening metathesis polymerization; ROMP; ADMET polymerization; Endfunctionalization; Olefin metathesis; ROMP; Ring opening metathesis polymerization
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2017.12.041

Recent results for synthesis of end-functionalized polymers (EFP) by using olefin metathesis polymerization have been introduced including basic characteristics in ring-opening metathesis polymerization (ROMP) of cyclic olefins and acyclic diene metathesis (ADMET) polymerization for synthesis of conjugated polymers. Several approaches were demonstrated for synthesis of EFP by living ROMP using molybdenum (exclusive coupling with aldehyde) and ruthenium catalysts (sacrificial ROMP, chain transfer). Cis specific (Z selective) ROMPs were achieved by molybdenum, ruthenium, and vanadium catalysts by the ligand modification. The catalytic synthesis of EFP with high cis selectivity has been achieved by combined ROMP with chain transfer by V(CHSiMe3)(N-2,6-Cl2C6H3)[OC(CF3)3](PMe3)2. The ADMET polymerization using molybdenum and ruthenium catalysts afforded defect-free, high molecular weight poly(arylene vinylene)s containing all trans olefinic double bonds. The methods for precise synthesis of EFPs, exhibiting unique optical properties combined with the end groups, were developed. The catalytic one-pot syntheses for EFPs have also been developed. [Display omitted]