A sol/gel curing method is used in this work to synthesize hybrid partially bio-based polyhydroxyurethanes (PHUs) from dicarbonates derived from glycerol and various diamines. The method consists of end-capping the PHU prepolymers with moisture-sensitive groups, so sealants and adhesives can be produced from partially sustainable hybrid PHUs (HPHUs), similar to their preparation from end-capped conventional polyurethanes. Diglycerol dicarbonate (DGC) is synthesized and polymerized with different diamines of various chain lengths, and the resulting structural and thermal properties of the PHUs are qualitatively and quantitively characterized. This characterization led to two potential candidates: PHU 4, made of DGC and a poly­(propylene glycol) diamine, and PHU 10, prepared from DGC and a poly­(dimethylsiloxane) diamine. These polymers, with respective relative number-average molecular weights of 3200 and 7400 g/mol, are end-capped and left to cure under ambient lab conditions (22 °C and 40–50% humidity), and the curing processes are monitored rheologically. Notably, moisture curing does not require any catalyst. The chemical stability of the resulting hybrid PHUs (HPHUs) 4 and 10 in pure water is investigated to check the viability of applying them under outdoor conditions. Only HPHU 10 is found to be resistant to water and shows hydrophobicity with a contact angle of 109°. Tensile tests are conducted on HPHU 10 samples cured under lab conditions for a week and others cured for another week while being immersed in water. The mechanical properties, tensile strength and elongation at break, improve with the samples cured in water, indicating the high-water repellency of HPHU 10.

The terpolymerization of bio-based diglycerol dicarbonate (DGC) and Priamine 1074 is conducted with aminopropyl terminated polydimethylsiloxane (M n = 1000 g/ mol, PDMS) or 1,10-diaminodecane (DAD). Depending on DGC contents and PDMS/Priamine 1074 ratios, the resulting amorphous thermoplastic polyhydroxyurethanes (TPHUs) present random or block copolymer-like segmented structures. These TPHUs exhibit nanophase separation of small interdomain spacing (3−3.5 nm) mainly caused by DGC. As for DAD, it introduces crystallinity (8%) and chain ordering into the TPHU structure as observed from X-ray measurements. Some PDMS-based TPHUs are blended with PLA, and the blends are found to be partially miscible as they exhibit two T g 's, and their estimated relative energy differences (RED), calculated from Hoftyzer−Van Krevelen's group contribution method, are nearly unity. Based on the type of hydrogen bonding interactions and the extent of immiscibility (RED) of each of the blends, the TPHUs find potential applications as toughening agents and/or plasticizers for PLA.

A new set of polyhydroxyurethanes (PHUs) is synthesized from bio‐based sorbitol bicarbonate (SBC) and mannitol bicarbonate (MBC). The synthesized dicarbonates are polymerized with two long chain diamines, telelechelic amine terminated poly(propylene glycol) (PPG), and poly(dimethylsiloxane) (PDMS). Despite the high melting points of SBC and MBC, PHU prepolymers are prepared in bulk at moderate temperatures of 60–100 °C. The structural and thermal properties of the resulting PHUs are qualitatively and quantitatively characterized in order to evaluate them as potential sealants and adhesives, and they are end‐capped with moisture curing agents and left to cure at ambient conditions (22 °C and 20–30% humidity) with the curing processes monitored rheologically. The chemical stability of the novel partially sustainable hybrid PHUs (HPHUs) in pure water is investigated to check the viability of applying them outdoors. Only SBC or MBC‐PDMS HPHUs are found to be hydrophobic with water contact angles of 105° and 109°, respectively, but they are brittle. Small and wide‐angle X‐ray scattering of these water‐resistant films show that they are potentially composed of three different phases due to microphase separation: the PDMS matrix, a hard segments phase, and a third phase mixing the PDMS diamine end‐segments and some dissolved hard segments.

Hydrophobicity of hybrid polyhydroxyurethane (HPHU), via sol/gel curing of a PHU made from diglycerol dicarbonate (DGC) and a poly­(propylene glycol) (PPG)-based diamine, is increased by reacting the carbonate-terminated PHU with diamines based on poly­(dimethylsiloxane) (PDMS) and the fatty acid-derived Priamine 1074. The modified PHUs were end-capped with silane moisture-curing agents, and swelling of the HPHUs was studied in water and other solvents over 1 week. These films exhibited a drop in the water swelling index (4%) compared to the original poly­(DGC-PPG) HPHUs (75%). The PDMS-modified HPHU has a dominant PDMS phase, due to its comparatively longer chain length relative to the PHU, thereby increasing water repellency. Besides an increase in hydrophobicity, the Priamine 1074-modified HPHU revealed a higher storage modulus that is at least 12 times higher than that of the original films. Consequently, Priamine 1074 is regarded as a promising biobased reactive additive when formulating hydrophobic PHU resins.

Variants of the partially hydrolytically degradable cationic macromonomer polycaprolactone choline iodide ester methacrylate (PCL 2 ChMA) have been synthesized to assess the effects of structure on the performance of the resulting polymers in the flocculation of mature fine tailings (MFT) that are a byproduct of bitumen extraction from oil sands. Neither the substitution of PCL with poly(lactic acid) (PLA) units or replacement of the methacrylate functionality with acrylate greatly affected the ability of the resulting cationic flocculants to settle and separate the sediments in diluted MFT suspensions, as the synthesized polymers have similar structures and charge densities. The higher degradation rates of the PLA-based materials, however, led to faster compaction of the MFT sediment, as quantified by the amount of water released from the flocculated materials over time. Over 50% compaction was observed in MFT samples ranging between 2 and 20 wt % held for either 5 days at 50 °C or for 12 weeks at room temperature, whereas no significant amount of water was released from sediment flocculated with a comparable nondegradable cationic polymer or with high molecular-weight nonionic poly(acrylamide). The results demonstrate the potential of these LA-based cationic degradable polymers for dewatering of oil sands MFT or other flocculated sediments.