Highly Effective and Green Catalytic Approach Toward a,w-Dihydroxy-Telechelic Poly(trimethylenecarbonate)

• Published in: Macromolecular rapid communications. Vol. 30; no. 24; pp. 2128 - 2135
• Main Authors: Helou, Marion, Miserque, Olivier, Brusson, Jean-Michel, Carpentier, Jean-Francois, Guillaume, Sophie M
• Format: Journal Article
• Language: English
• Published: 16.12.2009
• Subjects: Carbonates; Catalysts; Chain transfer; Charcoal; Diols; Hydrogenolysis; Polymers; Precursors
• ISSN: 1022-1336
• DOI: 10.1002/marc.200900498

,-Dihydroxy-telechelic poly(trimethylenecarbonate), HO-PTMC-OH, is synthesized from the controlled immortal ring-opening polymerization (ROP) of trimethylene carbonate under mild conditions (bulk, 60 C), using ZnEt2 or, more efficiently, [(BDI)Zn(N(SiMe3)2)] (BDI = CH(CMeNC6H3-2,6-iPr2)2) as catalyst precursor, in the presence of a diol HO-R-OH (R = (CH2)2 or CH2C6H4CH2; 0.5-10 equiv. vs Zn) acting both as co-initiator and chain transfer agent. Alternatively, HO-PTMC-OH is prepared upon hydrogenolysis of HO-PTMC-OCH2Ph, initially prepared from the ROP of TMC using the [(BDI)Zn(N(SiMe3)2)]/PhCH2OH system, under smooth operating conditions using Pd/charcoal. Well-defined dihydroxy-functionalized PTMCs of molar mass ranging from = 2 000 to 109 500 g . mol-1 were thus quantitatively obtained and fully characterized by NMR, MALDI-TOF-MS and SEC analyses. The versatility of this immortal ROP allows the preparation of alike ,-functional polyester such as linear HO-poly(lactide)-OH, as well as star polymers such as the glycerol-based PTM-OH3.