Synthesis, characterization, and properties of poly(ester‐phosphoester)s by lanthanum triphenolate‐catalyzed ring‐opening copolymerization

Abstract

The ring‐opening copolymerization of methyl ethylene phosphate (MEP, 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane) and ε‐caprolactone (CL) was performed in bulk with lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s as single‐component catalyst, resulting in poly(ester‐phosphoester) random copolymers with high molecular weight and moderate molecular weight distribution. The properties of the copolymers were characterized by differential scanning calorimetry, X‐ray diffractometer, dynamic mechanical analysis, and static water contact angle measurement. The crystallinities of the copolymers were reduced with the increase of MEP molar fraction in the products. Moreover, copolymers with enhanced hydrophilicity and lower glass transition temperature could be obtained with higher MEP content, which may provide potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

Fully degradable antibacterial poly(ester‐phosphoester)s by ring‐opening polymerization, “click” chemistry, and quaternization

“…Our research group has been working on the study of rare‐earth catalysts, and developed a series of effective catalysts for the ROP of lactones, lactides, and cyclic carbonates . Recently, we reported the ring‐opening copolymerization of 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane (methyl ethylene phosphate, MEP) or 2‐(2‐chloroethoxy)‐2‐oxo‐1,3,2‐dioxaphospholane (CEP) with CL catalyzed by lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s (La(DBMP) 3 ), to give poly(ester‐phosphoester) random copolymers with high molecular weight and moderate molecular weight distribution.…”

Cationic poly(ester‐phosphoester)s: Facile synthesis and antibacterial properties

“…47-49 2-(2-Chloroethoxy)-2-oxo-1,3,2-dioxaphospholane (CEP) was synthesized by a method similar to our previous report. 46 Characterization 1 H-and 31 P-nuclear magnetic resonance (NMR) spectroscopy spectra were recorded on a Bruker Avance DMX500 spectrometer in CDCl 3 with tetramethylsilane as internal standard. Gel permeation chromatography (GPC) measurements were performed on a Waters 208 apparatus equipped with Waters 2410 RI detector in THF (1.0 mL/min) at 30.0 C and calibrated with commercial polystyrene standards.…”

“…La(DBMP) 3 was synthesized as we reported formerly . 2‐(2‐Chloroethoxy)‐2‐oxo‐1,3,2‐dioxaphospholane (CEP) was synthesized by a method similar to our previous report …”

“…Additionally, the pentavalent nature of phosphorus atom makes polyphosphates easy to be functionalized . In our previous work, the ring‐opening copolymerization of 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane (MEP) and CL has been successfully carried out to prepare poly(ester‐phosphoester)s with high molecular weight and controlled composition, using lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s (La(DBMP) 3 ) as single‐component catalyst under mild conditions . In this study, a novel functional cyclic phosphate, 2‐(2‐chloroethoxy)‐2‐oxo‐1,3,2‐dioxaphospholane (CEP), was designed and synthesized as functional monomer to copolymerize with CL in the presence of La(DBMP) 3 .…”

Improved cell adhesion of poly(amino acid) surface by cyclic phosphonate modification for bone tissue engineering

“…Polyphosphoester (PPE), with an analogous structure to nucleic and teichoic, also attracts much interest into tissue engineering . By copolymerization with PPE, polymers often enjoy a remarkable improvement in biocompatibility as well as surface wettability . The improved surface wettability is owing to the significant impact of PPE on the crystallinity of polymer, and the hydrophilic OPO bond in PPE.…”