title: Influence of peripheral hydrogen bonding on the mechanical properties of photo-cross-linked star-shaped poly(D,L-lactide) networks.
abstract: Four-arm, star-shaped poly(D,L-lactide) (PDLLA) oligomers of controlled molar mass and narrow molar mass distribution were successfully synthesized by use of an ethoxylated pentaerythritol initiator. Derivatization of the terminal hydroxyl groups with either methacrylic anhydride (MAAH) or 2-isocyanatoethyl methacrylate (IEM) to yield PDLLA-M (M = methacrylate end group) and PDLLA-UM (UM = urethane methacrylate end group), respectively, was monitored by in situ Fourier transform infrared (FTIR) spectroscopy. Photo-cross-linking of the functional oligomers yielded networks with high gel contents (>95%). The glass transition temperature (T(g)) of these networks was strongly dependent on prepolymer molar mass, and networks based on low molar mass precursors were more rigid than the networks obtained from higher molar mass oligomers. The tensile strength (TS) and Young's modulus of the PDLLA-M samples, approximately 7 and 17 MPa, respectively, were significantly lower than the values of 19 MPa (TS) and 113-354 MPa (Young's modulus) for the PDLLA-UM samples. The introduction of terminal hydrogen-bonding sites that were adjacent to the photo-cross-linking site resulted in higher performance poly(lactide)-based bioadhesives.
authors.affiliation: Department of Chemistry, Macromolecules and Interfaces Institute, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, USA.
authors.forename: Afia S
authors.initials: AS
authors.lastname: Karikari
authors.forename: Wesleigh F
authors.initials: WF
authors.lastname: Edwards
authors.forename: Jeffrey B
authors.initials: JB
authors.lastname: Mecham
authors.forename: Timothy E
authors.initials: TE
authors.lastname: Long
mesh_terms: D002152:Calorimetry, Differential Scanning; D002845:Chromatography; D003432:Cross-Linking Reagents / Q000494:pharmacology; D005898:Glass; D006358:Hot Temperature; D006860:Hydrogen Bonding; D017953:Isocyanates / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008689:Methacrylates / Q000737:chemistry; D008956:Models, Chemical; D011091:Polyesters / Q000737:chemistry*; D011109:Polymethacrylic Acids / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013314:Stress, Mechanical; D013696:Temperature; D013718:Tensile Strength; D000267:Tissue Adhesions; D014520:Urethane / Q000737:chemistry
chemical_list: D003432:Cross-Linking Reagents; D017953:Isocyanates; D008689:Methacrylates; D011091:Polyesters; D011109:Polymethacrylic Acids; D014520:Urethane; C033616:poly(lactide); C029845:2-isocyanatoethyl methacrylate