This study introduces an efficient strategy for synthesizing polyhydroxyurethane-based multicomponent hydrogels with enhanced rheological properties. In a single-step process, 3D materials composed of Polymer 1 (PHU) and Polymer 2 (PVA or gelatin) were produced. Polymer 1, a crosslinked polyhydroxyurethane (PHU), grew within a colloidal solution of Polymer 2, forming an interconnected network. The synthesis of Polymer 1 utilized a Non-Isocyanate Polyurethane (NIPU) methodology based on the aminolysis of bis(cyclic carbonate) (bisCC) monomers derived from 1-thioglycerol and 1,2-dithioglycerol (monomers A and E, respectively). This method, applied for the first time in Semi-Interpenetrating Network (SIPN) formation, demonstrated exceptional orthogonality since the functional groups in Polymer 2 do not interfere with Polymer 1 formation. Optimizing PHU formation involved a 20-trial methodology, identifying influential variables such as polymer concentration, temperature, solvent (an aprotic and a protic solvent), and the organo-catalyst used [a thiourea derivative (TU) and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU)]. The highest molecular weights were achieved under near-bulk polymerization conditions using TU-protic and DBU-aprotic as catalyst-solvent combinations. Monomer E-based PHU exhibited higher Mw¯ than monomer A-based PHU (34.1 kDa and 16.4 kDa, respectively). Applying the enhanced methodology to prepare 10 multicomponent hydrogels using PVA or gelatin as the polymer scaffold revealed superior rheological properties in PVA-based hydrogels, exhibiting solid-like gel behavior. Incorporating monomer E enhanced mechanical properties and elasticity (with loss tangent values of 0.09 and 0.14). SEM images unveiled distinct microstructures, including a sponge-like pattern in certain PVA-based hydrogels when monomer A was chosen, indicating the formation of highly superporous interpenetrated materials. In summary, this innovative approach presents a versatile methodology for obtaining advanced hydrogel-based systems with potential applications in various biomedical fields.

Non-isocyanate polyurethanes (NIPUs) based on biobased polyamines and polycarbonates are a sustainable alternative to conventional polyurethanes (PU). This article discloses a novel method to control the crosslinking density of fully biobased isocyanate-free polyurethanes, synthesized from triglycerides carbonated previously in scCO2 and different diamines, such as ethylenediamine (EDA), hexamethylenediamine (HMDA) and PriamineTM-1075 (derived from a dimerized fatty acid). As capping substances, water or bioalcohols are used in such a way that the crosslinking density can be adjusted to suit the requirements of the intended application. An optimization of the NIPU synthesis procedure is firstly carried out, establishing the polymerization kinetics and proposing optimal conditions set for the synthesis of the NIPUs. Then, the influence of the partial blocking of the active polymerization sites of the carbonated soybean oil (CSBO), using monofunctional amines, on the physical properties of the NIPUS is explored. Finally, the synthesis of fully biobased NIPUs with a targeted crosslinking density is achieved using hybrid NIPUs, employing partially carbonated oil and H2O or ethanol as blockers to achieve the desired physical properties in a very precise manner.

Polyurethanes (PUs) are a significant group of polymeric materials that, due to their outstanding mechanical, chemical, and physical properties, are used in a wide range of applications. Conventionally, PUs are obtained in polyaddition reactions between diisocyanates and polyols. Due to the toxicity of isocyanate raw materials and their synthesis method utilizing phosgene, new cleaner synthetic routes for polyurethanes without using isocyanates have attracted increasing attention in recent years. Among different attempts to replace the conventional process, polyaddition of cyclic carbonates (CCs) and polyfunctional amines seems to be the most promising way to obtain non-isocyanate polyurethanes (NIPUs) or, more precisely, polyhydroxyurethanes (PHUs), while primary and secondary -OH groups are being formed alongside urethane linkages. Such an approach eliminates hazardous chemical compounds from the synthesis and leads to the fabrication of polymeric materials with unique and tunable properties. The main advantages include better chemical, mechanical, and thermal resistance, and the process itself is invulnerable to moisture, which is an essential technological feature. NIPUs can be modified via copolymerization or used as matrices to fabricate polymer composites with different additives, similar to their conventional counterparts. Hence, non-isocyanate polyurethanes are a new class of environmentally friendly polymeric materials. Many papers on the matter above have been published, including both original research and extensive reviews. However, they do not provide collected information on NIPU composites fabrication and processing. Hence, this review describes the latest progress in non-isocyanate polyurethane synthesis, modification, and finally processing. While focusing primarily on the carbonate/amine route, methods of obtaining NIPU are described, and their properties are presented. Ways of incorporating various compounds into NIPU matrices are characterized by the role of PHU materials in copolymeric materials or as an additive. Finally, diverse processing methods of non-isocyanate polyurethanes are presented, including electrospinning or 3D printing.

Predominantly non-furanic commercial humins were used to prepare humin-based non-isocyanate polyurethane (NIPU) resins for wood panel adhesives. Pure humin-based NIPU resins and tannin-humin NIPU resins were prepared, the latter to upgrade the humins\' performance. Species in the raw humins and species formed in the NIPU resins were identified by Matrix Assisted Laser Desorption Ionization Time of Flight (MALDI ToF) spectrometry and Fourier Transform Infrared (FTIR). Humins, fulvic acid and derivatives, humic acid and its fragments, some lignans present and furanic oligomers present formed NIPU linkages. Thermomechanical analysis (TMA) showed that as with other biomaterials-based NIPU resins, all these resins also showed two temperature peaks of curing, the first around 130 °C and the second around 220 °C. A decrease in the Modulus of Elasticity (MOE) between the two indicated that the first curing period corresponded to linear growth of the oligomers forming a physical entanglement network. This then disentangled, and the second corresponded to the formation of a chemical cross-linked network. This second peak was more evident for the tannin-humin NIPU resins. All the laboratory particleboard made and tested either bonded with pure humins or with tannin-humin NIPU adhesives satisfied well the internal bond strength requirements of the relevant standard for interior grade panels. The tannin-humin adhesives performed clearly better than the pure humins one.

A partially biobased self-blowing and self-hardening polyurethane foam from glucose-based non-isocyanate polyurethanes (g-NIPU) was prepared by reaction of glucose with dimethyl carbonate and hexamethylene diamine. However, these foam types generally require a high foaming temperature. In this paper, a self-blowing foam based on g-NIPU was prepared at room temperature by using maleic acid as an initiator and glutaraldehyde as a crosslinker. Water absorption, compression resistance, and fire resistance were tested. Scanning electron microscopy (SEM) was used to observe the foam cells structure. Middle infrared (ATR FT-MIR) and Matrix Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) mass spectrometry were used to help to analyze the reactions during the foaming process. The results obtained showed that self- blowing rigid foams have good compression, this being directly proportional to the foam density. Increasing the amount of glutaraldehyde or reducing maleic acid thickens the cell walls and increases the density of the foams. MALDI-TOF analysis showed that g-NIPU reacts with both maleic acid and glutaraldehyde. The foams presented poor fire resistance indicating that, as for isocyanate based polyurethane foams, addition of a fire retardant would be necessary.

Mostly biosourced non-isocyanate polyurethanes (NIPU) were prepared from mono- and disaccharides, namely glucose and sucrose, reacted with dimethyl carbonate and hexamethylene diamine. The main aim of this research was to show that NIPU can be prepared from mono- and disaccharides, this just being an initial exploratory work and its sole main aim. The oligomers obtained were detected by MALDI-ToF, CP-MAS 13C NMR, and FTIR spectrometries. The glucose-derived NIPU were shown to harden at a markedly lower temperature than the sucrose-derived ones and to be easier to handle and spread. The NIPU obtained were applied as wood and steel surface coatings and tested by the sessile drop test (on wood) and cross-cut test (on steel) with encouraging results. The glucose NIPU gave good surface coating results already at 103 °C, while the sucrose NIPU yielded good results only at a markedly higher temperature of hardening. The NIPU saccharide resins were also tested as thermosetting wood joint adhesives with the glucose NIPU yielding very encouraging results.