Ring-opening polymerization functionalized polyesters

Uyama H, Kobayashi S (1996) Enzymatic ring-opening polymerization of macrolides to polyesters. In Yalpani M (ed) Biomedical functions and biotechnology of natural and artificial polymers. ATL Press, Schrewsbury, p 5... 

Trollsas M, Lee VY, Mecerreyes D, Ldwenhiehn P, Moller M, Miller RD, Hedrick JL (2000) Hydrophilic aliphatic polyesters design, synthesis, and ring-opening polymerization of functional cyclic esters. Macromolecules 33 4619-4627... 

Detrembleur C, Mazza M, Halleux O, Lecomte P, Mecerreyes D, Hedrick JL, Jerome R (2000) Ring-opening polymerization of y-Bromo-E-caprolactone a novel route to functionalized aliphatic polyesters. Macromolecules 33 14-18... 

El Habnouni HS, Darcos V, Coudane J (2009) Synthesis and ring-opening polymerization of a new functional lactone, a-iodo- -caprolactone a novel route to functionalized aliphatic polyesters. Macromol Rapid Commun 30 165-169... 

Blanquer S, Tailhades J, Darcos V, Amblard M, Martinez J, Nottelet B, Coudane J (2010) Easy synthesis and ring-opening polymerization of 5-Z-Amino-8-valerolactone new degradable amino-functionalized (co)polyesters. J Polym Sci A Polym Chem 48 5891-5898... 

Tian D, Dubois P, Grandfils C, Jerome R (1997) Ring-opening polymerization of l,4,8-trioxaspiro[4.6]-9-undecanone A new route to aliphatic polyesters bearing functional pendent groups. Macromolecules 30 406 09... 

Another approach, which does not make use of either free or controlled radical polymerization, was demonstrated by Parrish et al. [20]. An aliphatic polyester with pendent acetylene groups was prepared via controlled ring-opening polymerization. Polyethylene glycol and the peptide sequence Gly - Arg - Gly - Asp - Ser (GRGDS) were functionalized with an azide moiety, and subsequently clicked to the pendent acetylenes in the... 

The melt condensation of acid and hydroxyl functional group normally requires exact stoichiometry, elevated temperature, and a long reaction cycle. Such a route would not be possible to utilize to produce block polymers from lactones and other vinyl monomers. However, a rather facile route leading to polyester formation can be realized by the ring-opening polymerization of lactones as seen from the scheme ... 

Polyesters can be synthesized either by ring-opening polymerization (ROP) or polycondensation. Both of these approaches have merit in the manipulation of properties of degradable polymers. Commercially, ROP is the most widely used practice for the synthesis of PHAs for consumer applications due to the ease of scale up, acceptable purity, and cost considerations. However, for biomedical applications where cost pressures are low and purity and function are paramount, condensation polymerization can yield superior outcomes [20]. Although the class of degradable polymers is rather large and includes poly(butyrolactones), poly(dioxanone), aliphatic poly(carbonates), poly(anhydrides), and poly(hydroxyalkanoates), the focus of the subsequent sections will be on the PGA, PLA, and poly(caprolactone) (PCL) family of polymers, as these are the most widely used polymers in both medical and consumer products arena. 

P. Lecomte, et al.. New prospects for the grafting of functional groups onto aliphatic polyesters. Ring-opening polymerization of a- or y-substituted e-caprolactone followed by chemical derivatiza-tion of the substituents. Macromol. Symp. 240 (2006) 157-165, doi 10.1002/masy.200650820. 

The functional group compatibility of the click cyclization approach also makes it amenable to a variety of other polymerization techniques. For example, cyclic polyesters have been prepared using the Lewis acid-catalyzed ring-opening polymerizations (ROPs) of lactone monomers, including e-caprolactone [47, 48] and 5-valerolactone [49] from an azide-functionaUzed alcohol. Esterification of the terminal alcohol with pentynoic anhydride provided the complementary functional groups to enable an efficient click cycHzation for molecular weights up to 15 kDa. 

Functional (Bio)degradable Polyesters by Radical Ring-Opening Polymerization... 

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