Performance polymers from renewable monomers: high molecular weight poly(pentadecalactone) for fiber applications

Abstract

Enzymatic ring-opening polymerization was applied to synthesize high molecular weight polypentadecalactone (PPDL). The synthetic procedure was optimized on a small-scale and subsequently transferred to 30 g scale to yield sufficient material for fiber spinning. Molecular weights (Mw) of 143 000 g mol(-1) were obtained. Mechanical and thermal properties of the non-oriented, high molecular weight PPDL were determined and are largely in agreement with the literature data. The high molecular weight PPDL was melt-processed into fibers, which were further elongated to about 9-10 times their original length. Analysis of the fibers revealed differences in crystal orientation as a function of the processing conditions. Preliminary fiber tensile measurements confirm a high strength of up to 0.74 GPa for the fiber with the highest crystal orientation

Characterization of Polyesters Obtained by Enzyme-Catalyzed Ring-Opening Polymerization of Pentadecanolide at high Temperature

“…The fact that the molecular weight distribution is not affected is an indication that the reaction mechanism of ring opening and monomer addition during the enzymatic polymerization is preserved but the number of chains formed is higher. These results are compared to PS standards and given the fact that they have been performed in 1,2,4-tricholoro benzene, a solvent used for polyolefins, at high temperature, the results are not comparable with other results reported in the literature in terms of absolute molecular weight; however, they present similar values of molecular weight with those reported at 70 o C. [7,9].…”

“…The procedure for the synthesis of polymers by ring opening polymerization using Novozyme 435 as catalyst has been previously described [7]. In a typical enzymatic polymerization, as shown in scheme 1, the Novozyme 435 in the form of small spheres (10 w/w % respects to monomer, 0.25g) was dried in a 25 ml flask with molecular sieves (3Å).…”

Functional Brush-Decorated Poly(globalide) Films by ARGET-ATRP for Bioconjugation

“…Macrolactones are an interesting alternative class of renewable monomers for the synthesis of aliphatic polyesters with enhanced physical properties compared to polymers from small and medium size lactones . Polyesters from macrolactones are readily accessible by enzyme catalyzed ring‐opening polymerization or, more recently, using (organo)catalytic approaches . We have lately focused on polymers from unsaturated macrolactones as the double bond offers perfect anchor points for further polymer functionalization or cross‐linking .…”

Hydrolases Part I: Enzyme Mechanism, Selectivity and Control in the Synthesis of Well-Defined Polymers

“…In the absence of water, high molecular weight polyesters are typically obtained [74,75,108], whereas increasing the water content (which acts as an initiator) leads to a higher number of polymer chains and thus lower molecular weight polyesters [64,101]. Also, the use of initiators containing an alcohol allows the preparation polymers of predictable molecular weight [72,76,109,110].…”