Oxo‐crown‐ethers as comonomers for tuning polyester properties

Abstract

Abstract2‐Oxo‐12‐crown‐4‐ether (OC) was procured in a novel, two‐step procedure in a 37% overall yield. This interesting hydrophilic lactone was effectively polymerized with Novozym 435 as the catalyst: within 10 min, the monomer conversion was greater than 95%. Poly(2‐oxo‐12‐crown‐4‐ether) [poly(OC)] was obtained as a viscous oil with a glass‐transition temperature of approximately −40 °C, and it was soluble in water. Subsequently, OC was copolymerized with ω‐pentadecanolactone (PDL). A kinetic evaluation of both monomers showed that for OC, the Michaelis–Menten constant (KM) and the maximal rate of polymerization (Vmax) were 2.7 mol/L and 0.24 mol/L min, respectively, whereas for PDL, KM and Vmax were 0.5 mol/L and 0.09 mol/L min, respectively. Although OC polymerized five times faster than PDL, 1H NMR analysis of the copolymers revealed a random copolymer structure. Differential scanning calorimetry traces of the copolymers showed that they were semicrystalline and that the melting temperature and melting enthalpy of the copolymers linearly decreased with an increasing amount of OC. The melting temperature of the copolymers could be adequately predicted by the Baur equation, and this suggested that poly (OC) was rejected from the poly(ω‐pentadecanolactone) [poly(PDL)] crystals. Solid‐state NMR studies confirmed that the crystalline phase exclusively consisted of poly (PDL), whereas the amorphous phase was a mixture of OC and PDL units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2166–2176, 2006

Enzymatic Polymerization of Polyester

“…The polycarbonates have potential in biomedical applications. Enzymatic ROP of 2 -oxo -12 -crown -4 -ether (OC) was studied by Meijer and coworkers [106] . OC is different from other ether containing lactone monomers previously studied as it combines high hydrophilicity with a large ring size.…”

“…[103] investigated copolymerizations of 3(S) -isopropylmorpholine -2,5 -dione ( IPDM ) with d , l -lactide ( DLLA ), using porcine pancreatic lipase as catalyst at 100 ° C for 168 h. By varying the feed composition, copolymers with different yields (between 13 and 57%) and molecular weights (between 8600 and 18 100 g mol − 1 ) were obtained (Scheme 4.23 ). Furthermore, using Novozym 435 as catalyst, 2 -oxo -12 -crown -4 -ether ( OC ) was copolymerized with PDL giving copolyesters with random sequence distributions [106] .…”

“…PDL / p -dioxanone [108] 2 -oxo -12 -crown -4 -ether / PDL [106] PDL / TMC [114] PDL / sugar carbonate (IPXTC) [115] 5 -benzyloxy -trimethylene carbonate / 1,4 -dioxan -2 -one [116] poly -(butylene carbonate) / poly(butylene succinate)…”

Bark Suberin as a Renewable Source of Long‐Chain ω‐Hydroxyalkanoic Acids

“…[6] Toluene has been shown to be an efficient solvent for Novozym 435 catalyzed polymerizations. [7] In Figure 2 polymerization with toluene as solvent in presence of molecular sieves is compared with bulk polymerization without any drying agent present. The temperature used for the toluene polymerization was 75 8C.…”

Conformational isomerization of polymethyl-substituted six-membered cyclic carbonates

“…Interest in cyclic carbonates that are important products of chemical fixation of atmospheric carbon dioxide [1] is related to their specific conformational behavior [2][3][4] and possible applications for the synthesis of practically important copolymers [5,6] and in electrochemical processes [7,8]. In addition, these compounds can be used to synthesize chiral diols [9].…”