Phase Transition and Crystallization of Bio-based Comb-like Polymers Based on Renewable Castor Oil-Derived Epoxides and CO₂

Abstract

A series of bio-based comb-like polymers with various lengths of alkyl chains were synthesized through combining the ring-opening copolymerization of sustainable CO2 with bio-renewable castor oil-derived epoxides and the S-alkylated technique of the thiol–ene click reaction. The structure, thermal property, side-chain crystallization, and phase transition behavior of comb-like polymers were investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and wide-angle X-ray diffraction. The chain packing manner and phase transformation of side-chain crystallites for the pendent side alkyl chains on the CO2-based copolymer backbone exhibit a dependence on side-chain length, showing an increased phase-transition temperature (T m) and phase-change enthalpy (ΔH m) from −15.0 to 70.3 °C and from 34.1 to 108.5 kJ/mol, respectively. Phase transition of the side-chain crystallites, varying from a regular trans conformation to a trans disordered conformation and then to a gauche conformation, occurs during the phase transition process. This work provides a promising strategy to achieve crystallized CO2-based copolymers and affords a facile approach to develop the structuralized polymeric materials from the molecular regulation aspect.

From plastic to elastomers: introducing reversible copper–thioether coordination in CO2-based polycarbonate

“…S3 †), which is a common result of using the heterogeneous DMC catalyst. [56][57][58] Synthesizing polymers with sulfur via the thiol-ene click reaction Using the terpolymers, we were able to functionalize PCHC by the thiol-ene click reaction. 59,60 The reaction has the advantages of inexpensive reaction material, facile operation, and mild reaction conditions, making it applicable to most systems.…”

Recent Advances in the Synthesis of Bio‐based Carbonate by the Catalytic Reaction of CO2 with Bio‐based Compounds

“…Synthetic route of P(EUA/CO 2 )-g-C n H 2n + 1 comb-like polymers. [52] Reprinted with permission from ref. [52].…”

“…[49] Moreover, the combination of copolymerization of biomass castor oil-derived epoxide, epoxy undec-10-enoate (EUA), with CO 2 to prepare the EUA-CO 2 copolymer. [52] Subsequently, a series of alkyl-substituted comb-like polymers with variable side chain length were successfully synthesized by the S-alkylated technique of the thiol-ene click reaction (Figure 9). Their phasechange temperature, Tm and Tc, and enthalpy, ΔHm, are highly dependent on the side-chain length.…”

4D Photopolymers Derived From Ring-Opening Copolymerization of Cyclic Anhydrides and Limonene Oxide

“…Terpene oxides offer a route toward degradable polymers with the added benefit of other potential functional groups. − Numerous reported examples include limonene oxide, elemene oxide, fatty acid oxides, castor oil epoxides, and pinene oxide, among others, for the incorporation into polyesters or polycarbonates. ,− Limonene oxide is one of the most interesting moieties because of its possession of both an epoxide and an alkene and has been the subject of a wide range of studies. ,,,,,,, It also has found use in coatings, while limonene dioxide, which possesses two epoxides and no alkenes, has been demonstrated in low-viscosity 3D printing resins after functionalization with methacrylate moieties as a substitute for bisphenol A containing polycarbonates. ,, Limonene oxide has further been incorporated into co- and terpolymers, with the residual alkene side chains leveraged for thiol–ene functionalization postpolymerization to tailor glass transition temperature ( T g ) or physical properties. ,,, …”