title: Highly Effective and Green Catalytic Approach Toward α,ω-Dihydroxy-Telechelic Poly(trimethylenecarbonate).
abstract: α,ω-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 ZnEt(2) or, more efficiently, [(BDI)Zn(N(SiMe(3) )(2) )] (BDI = CH(CMeNC(6) H(3) -2,6-iPr(2) )(2) ) as catalyst precursor, in the presence of a diol HO-R-OH (R = (CH(2) )(2) or CH(2) C(6) H(4) CH(2) ; 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-OCH(2) Ph, initially prepared from the ROP of TMC using the [(BDI)Zn(N(SiMe(3) )(2) )]/PhCH(2) OH system, under smooth operating conditions using Pd/charcoal. Well-defined dihydroxy-functionalized PTMCs of molar mass ranging from $\overline M _{\rm n}$ = 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 α,ω-functional polyester such as linear HO-poly(lactide)-OH, as well as star polymers such as the glycerol-based PTM-OH(3) .
authors.affiliation: Laboratoire Catalyse et Organométalliques, CNRS, Université de Rennes 1, Sciences Chimiques de Rennes (UMR 6226), Campus de Beaulieu, 35042 Rennes Cedex, France.
authors.forename: Marion
authors.initials: M
authors.lastname: Helou
authors.forename: Olivier
authors.initials: O
authors.lastname: Miserque
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Brusson
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.forename: Sophie M
authors.initials: SM
authors.lastname: Guillaume