Search Results (8)

Carbon dioxide-derived oligocarbonate diols (OCDs) represent a promising class of sustainable raw materials that can enhance the environmental profile of polyurethane (PUR) coatings without compromising their performance. In this work, six oligocarbonate diols, differing in chemical structure (aromatic, aliphatic, and cycloaliphatic), were employed as modifiers in solvent-based PUR coatings designed for wood substrates. The study evaluates the influence of OCD’s chemical nature on the mechanical and optical properties of the resulting coatings. The results demonstrate that the structure of the oligocarbonate diol plays a decisive role in determining coating performance. PUR systems containing aliphatic soft segments exhibited the most favorable mechanical response, particularly in terms of wear resistance, outperforming coatings modified with cycloaliphatic and aromatic OCDs—wear reduction ranged between 43% and 71%. In contrast, the highest hardness values (0.46 and 0.41) were observed for the coatings incorporating aromatic moieties, indicating increased rigidity associated with aromatic structures. Importantly, adhesion at the wood–coating interface remained excellent and unaffected by the type of OCD used (cross-cut class I or II), confirming the compatibility of all investigated formulations with wooden substrates. Overall, the findings clearly show that newly developed CO₂-based oligocarbonate diols are effective and versatile modifiers for polyurethane wood coatings, enabling the tuning of functional properties while supporting more sustainable coating technologies. Full article

Oligocarbonate diols (OCD) require tedious and time-consuming synthesis procedures. The most common ones use dimethyl carbonate or alkylene carbonate as starting materials. Considering the preparation of small batches of oligomerols with an atypical structure, this methodology is not convenient. Therefore, we developed a simple way to obtain OCDs and oligo(urethane-carbonate) diols (OUCDs) containing aliphatic, cycloaliphatic, aromatic or oxyethylene units based on commercially available OCDs (ETERNACOLL, UBE). The process was conducted in two stages combining transesterification/transurethanization and polycondensation reactions. It resulted in novel OCDs and OUCDs with an irregular structure. Their composition was characterized using FT-IR, NMR, and MALDI-TOF techniques. The hydroxyl values were determined by potentiometric titration. The numerical average molar masses of the oligomerols ranged from approx. 1000 to 3200 g/mol, making them attractive materials for the preparation of a variety of polyurethane products. Thanks to the presence of carbonate moieties that are resistant to hydrolytic and oxidative degradation, poly(carbonate-urethane)s could find applications as coatings, thermoplastic elastomers, and biomaterials. The influence of the structural variations of the oligomerols on the properties of polyurethanes is now under investigation. Full article

This study introduces a metal-free binary catalytic system for coupling CO₂ with cyclohexane oxide (CHO) under mild conditions, allowing for tunable product selectivity. Using trans-cyclohexane diol (trans-CHD) and phosphazene superbase (P₄) as catalysts, the system selectively produces cyclic carbonates and oligocarbonates at 1 bar CO₂ pressure and 80 °C. By adjusting the catalyst ratio, varying proportions of cis-cyclohexane carbonate (cis-CHC), trans-cyclohexane carbonate (trans-CHC), and oligocarbonate are achieved, with 51 mol% CHO conversion and respective selectivities of 36%, 31%, and 33%. The catalytic efficiency and precise control of product outcomes underscore this system’s potential. Full article

The luminescent properties of photocured aliphatic and aromatic network polycarbonate methacrylates, containing organic fluorescent dyad, have been studied. The dyad molecule includes two photosensitive fragments—tetraarylimidazole with a hydroxyl group and azomethinocoumarin—in each of which excited state intramolecular proton transfer (ESIPT) occurs, leading to the appearance of two emissions: blue (450 nm) and green (535 nm). It was established that the ratio of the intensities of these emissions depends very significantly on the excitation wavelength, as well as on the length, flexibility and polarity of the matrix oligomeric bridges. Full article

Porous polymer monolith materials of 2-mm thickness were obtained by visible light-induced radical polymerization of oligocarbonate dimethacrylate (OCM-2) in the presence of 1-butanol (10 to 70 wt %) as a porogenic additive. The pore characteristics and morphology of polymers were studied by mercury intrusion porosimetry and scanning electron microscopy. Monolithic polymers with both open and closed pores up to 100 nm in size are formed when the alcohol content in the initial composition is up to 20 wt %. The pore structure in such materials is a system of holes in the bulk of the polymer (hole-type pores). Open interconnected pores with a specific volume up to 2.22 cm³/g and modal pore size up to 10 microns are formed in the volume of the polymer with 1-butanol content of more than 30 wt %. Such porous monoliths are a structure of covalently bonded polymer globules (interparticle-type pores). The free space between the globules represents a system of open interconnected pores. In the transition region of 1-butanol concentrations (from 20 to 30 wt %), areas with both structures and intermediate frameworks, as well as honeycomb structures of polymer globules connected by bridges, are fixed on the polymer surface. It was found that the transition from one type of pore system to another is accompanied by a sharp change in the strength characteristics of the polymer. Approximation of experimental data using the sigmoid function made it possible to determine the concentration of the porogenic agent in the vicinity of which the percolation threshold is observed. Full article

The presented research focuses on the synthesis and structure–properties relationship of poly(carbonate-urea-urethane) (PCUU) systems including investigations on shape-memory effect capability. Furthermore, we approached the topic from a broader perspective by conducting extensive analysis of the relationship between the synthesized compounds and the results of computer simulations by means of the Monte Carlo method. For the first time, by using a unique simulation tool, the dynamic lattice liquid model (DLL), all steps of multi-step synthesis of these materials were covered by the simulations. Furthermore, broad thermal, mechanical, and thermomechanical characterization of synthesized PCUUs was performed, as well as determining the shape-memory properties. PCUUs exhibited good mechanical properties with a tensile strength above 20 MPa, elongation at break around 800%, and an exhibited shape-memory effect with shape fixity and shape recovery ratios above 94% and 99%, respectively. The dynamic lattice liquid model was employed to show the products and their molar mass distribution, as well as monomer conversion or the dispersity index for individual reaction steps. The results obtained in the following manuscript allow the planning of syntheses for the PCUUs of various structures, including crosslinked and soluble systems, which can provide a broad variety of applications of these materials, as well as a better understanding of the composition–properties relationship. Full article

Carbon dioxide is an important raw material in many industrial technologies, but it is also one of the greenhouse gases that has to be effectively removed from the environment. This contribution provides a brief overview of carbon dioxide-based polymers developed in the laboratories of the Faculty of Chemistry at Warsaw University of Technology. We present some simple and versatile synthetic approaches that can be used to prepare a library of oligocarbonate diols, polycarbonates, poly(ester-carbonates), poly(ether-carbonates) and various types of polyurethanes, including the newly emerging family of environmentally friendly non-isocyanate polyurethanes. The main synthesis strategy involves the reaction of CO₂ with oxiranes to form five-membered cyclic carbonates, which can be utilized as a source of carbonate bonds in polymeric materials obtained by the ester exchange reactions and/or step-growth polyaddition. We also show that cyclic carbonates are valuable starting materials in the synthesis of hyperbranched polymers and polymer networks. The properties of several CO₂-based polymers are presented and their potential application as biomaterials, smart materials, and absorbers with a high CO₂ capture capacity is discussed. Full article

Acyltransferases are enzymes that are capable of catalyzing the transesterification of non-activated esters in an aqueous environment and therefore represent interesting catalysts for applications in various fields. However, only a few acyltransferases have been identified so far, which can be explained by the lack of a simple, broadly applicable high-throughput assay for the identification of these enzymes from large libraries. Here, we present the development of such an assay that is based on the enzymatic formation of oligocarbonates from dimethyl carbonate and 1,6-hexanediol. In contrast to the monomers used as substrates, the oligomers are not soluble in the aqueous environment and form a precipitate which is used to detect enzyme activity by the naked eye, by absorbance or by fluorescence measurements. With activity detected and thus confirmed for the enzymes Est8 and MsAcT, the assay enabled the first identification of acyltransferases that act on carbonates. It will thus allow for the discovery of further efficient acyltransferases or of more efficient variants via enzyme engineering. Full article