Four new homogeneous chromium complexes with [OSSO]-type bis(phenolato) dianionic ligand catalysts for the ring-opening copolymerization of phthalic anhydride (PA) and epoxides are reported. Through the structure design, the ligand with a cyclohexylene ring backbone of the chromium complexes is quite beneficial to improving the activity. Of all the cocatalysts employed, DMAP is found to be the most efficient. 1 H NMR spectra of the copolymers confirmed the alternating microstructures. This is the first example of a well-defined metal complex with a soft Lewis base as donor for the efficient copolymerization of anhydride and epoxides. Additionally, we demonstrate that poly(4-VCHO-alt-PA) can be conveniently functionalized using a robust free-radical mediated thiol-ene reaction of the pendant vinyl groups. † Electronic supplementary information (ESI) available. See

A series of isocyanate-free polyurethanes (NIPUs), showing intrinsic thermo-healing performance, have been synthesized from sustainable vegetable oil-based cyclic carbonates and bio-resourced amines. The bio-based contents of the NIPUs are higher...

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.

An oligo(carbonate-ether) triol has been synthesized by the copolymerization of propylene oxide (PO) and CO2 using zinc-cobalt double metal cyanide (Zn/Co DMC) catalyst in the presence of trifunctional 1,1,1-tris(4-hydroxyphenyl)ethane (THPE)...

Using carbon dioxide-based poly(propylene ether carbonate) diol (PPCD), isophorone diisocyanate (IPDI), dimethylolbutyric acid (DMBA), ferric chloride (FeCl3), and ethylene glycol (EG) as the main raw materials, a novel thermoplastic polyurethane (TPU) is prepared through coordination of FeCl3 and DMBA to obtain TPU containing coordination enhancement directly. The Fourier transform infrared spectroscopy, 1H NMR, gel permeation chromatography, UV−Vis spectroscopy, tensile testing, dynamic mechanical analysis, X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were explored to characterize chemical structures and mechanical properties of as-prepared TPU. With the increasing addition of FeCl3, the tensile strength and modulus of TPU increase. Although the elongation at break decreases, it still maintains a high level. Dynamic mechanical analysis shows that the glass-transition temperature moves to a high temperature gradually along with the increasing addition of FeCl3. X-ray diffraction results indicate that TPUs reinforced with FeCl3 or not are amorphous polymers. That FeCl3 coordinates with DMBA first is an effective strategy of getting TPU, which is effective and convenient in the industry without the separation of intermediate products. This work confirms that such Lewis acids as FeCl3 can improve and adjust the properties of TPU contenting coordination structures with an in-situ reaction in a low addition amount, which expands their applications in industry and engineering areas.