Organocatalyzed ring opening polymerization of regio-isomeric lactones: reactivity and thermodynamics considerations

Abstract

Study of the kinetics and thermodynamics of the organocatalyzed ring opening polymerization of a regio-isomeric mixture of β,δ-trimethyl-ε-caprolactones (TMCL).

Reducing the crystallinity of PCL chains by copolymerization with substituted δ/ε-lactones and its impact on the phase separation of PCL-based block copolymers

“…Comparatively, the random copolymerization of ε-CL with δ/ε-substituted lactones has less effect on the hydrophilicity/hydrophobicity balance. 17 Statistical copolymerization of ε-CL with ε-DL, 11,18 δ-CL, 19 and ε-Me-ε-CL 20 has been reported to afford amorphous copolymers provided the content in co-monomer is high enough. ε-DL and ε-CL have been copolymerized using SnOct 2 at high temperatures (110–120 °C).…”

A machine learning approach for the design of hyperbranched polymeric dispersing agents based on aliphatic polyesters for radiation‐curable inks

“…3(c)). ROP of UDL and TMCL 9 using an alcohol as initiator was followed by hydrogenolysis in order to obtain acid-functionalized polyesters (Figs 3(a) and (b)). 1 H NMR spectroscopy confirms the disappearance of the benzyl end-group (Fig.…”

“…Copolymerization with other lactones like δ ‐valerolactone allows a reduction in the crystallinity and improvement in the solubility 3,7,8 . In the work reported here, we designed branched homopolyesters of δ ‐undecalactone (UDL) and β , δ ‐trimethyl‐ ε ‐caprolactones (TMCL), which avoids the need for copolymerization and results in fully amorphous polymers that are liquid at room temperature with T g (polyTMCL) = −63 °C 9 and T g (polyUDL) = −51 °C 8 . Moreover, extra attention was paid to sustainable synthesis of the polyesters and the hyperbranched dispersants.…”

“…The enzymatic oxidation was shown to be more environmentally friendly compared to the chemical route in the case of the reaction performed at a laboratory scale with recycling of solvents and enzyme 14 . For the ring‐opening polymerization (ROP) of lactones in bulk, organocatalysts 9 were used instead of metal‐based catalysts. Lastly, dispersing agents of various grafting densities were prepared using a solvent‐free process for the formation of an amide bond between carboxylic acid‐functionalized matrixophilic polyester chains and the amines in the pigmentophilic poly(ethylene imine) (PEI) chains.…”

Modulating Polymerization Thermodynamics of Thiolactones Through Substituent and Heteroatom Incorporation

“…A variety of monomers have been explored for the use of low T c polymers in CRM, including lactones, − phthalaldehydes, , carbonates, − cyclic acetals, and others. , Early efforts largely focused on lactones, but the rates of polymerization and depolymerization are prohibitively slow for many applications. This has led to an increased interest in thiolactones, which polymerize and depolymerize more rapidly due to rapid thiol-thioester exchange reactions. , The first thiolactone ring-opening polymerization was reported by Overberger in 1968 for the synthesis of poly­(thiocaprolactone) .…”