Polyurethane (PU) coatings were prepared from commercial Bayhydrol (R) polyurethane dispersions using onecomponent (1 K) and two-component (2 K) formulations, processed either through aqueous dispersion or organic solvent routes. Hydroxyfunctional polycarbonate- and polyester-based dispersions (Bayhydrol (R) UXP 2750 and UXP 2698), a flexible anionic dispersion (Bayhydrol (R) UH 340/1), and an aliphatic polyisocyanate hardener (Desmodur (R) N3600) were employed to investigate the influence of formulation strategy and processing pathway on coating performance. The effect of NCO/OH ratio, film thickness, and application method (roll- and spray-coating) on crosslinking efficiency, thermal behavior, mechanical properties, surface energy, and adhesion was systematically evaluated. Swelling and extractables measurements revealed significant differences in network integrity between aqueous and solvent-based routes, highlighting the critical role of water-induced isocyanate consumption in 2 K systems. Thermal analyses showed that the prepared coatings exhibit glass transition temperatures ranging from -50 to 69 degrees C and thermal stability comparable to conventional polyurethane coatings. Mechanical testing demonstrated that coating rigidity and toughness are primarily governed by resin functionality and molecular weight, while surface energy and adhesion strongly depend on urethane content and crosslink density. This study establishes clear process-structure-property relationships for industrially relevant polyurethane coatings and provides practical guidelines for optimizing waterborne and solventborne PU formulations.

Aminolysis of cyclic carbonates is one of the most promising routes for synthesizing non-isocyanate polyurethanes (NIPUs), yielding polyhydroxyurethanes (PHU). However, extensive hydrogen bonding from vicinal hydroxyl groups has been reported to hinder polymerization, limiting achievable high molar mass PHUs. In this study, we investigated the role of hydrogen bonding by designing a multifunctional monomer that suppress hydroxyl groups via silane chemistry. This approach, validated in a model system, was applied to polymerization and yielded a functionalized polymer with properties markedly different from the control polymer. Molecular weight comparison was performed using size exclusion chromatography (SEC), and thermal properties were subsequently evaluated.

Radical frontal photopolymerization under UV irradiation was investigated using polyurethane dimethacrylate formulations to fabricate transparent centimeter-scale polymer networks. The effects of the photoinitiator Darocur 4265 and the thermal initiator Luperox 231 on front propagation were investigated by real-time FTIR spectroscopy, differential scanning calorimetry (DSC), and in situ temperature monitoring using embedded thermocouples. Under optimized conditions, formulations containing only 0.1 wt% Darocur 4265 enabled the propagation of a polymerization front through samples up to 9.5 cm long, reaching maximum temperatures of approximately 105 °C and front propagation rates up to 20 cm min-1. Reconstruction of the front position from thermocouple measurements revealed a progressive decrease in propagation rate with increasing distance, consistent with the combined effects of light attenuation, heat dissipation and vitrification. Although Luperox 231 increased the initial heating rate, it did not significantly modify the overall propagation mechanism. These results demonstrate that transparent centimeter-scale polyurethane dimethacrylate networks can be fabricated by radical frontal photopolymerization under continuous UV irradiation without the need for a thermal initiator. They further provide new mechanistic insight into the coupled roles of light transport, photopolymerization kinetics and heat transfer governing front propagation in thick photopolymerized systems.

Vanillin cyclocarbonate was prepared according to a new methodology and used to prepare bis-cyclocarbonates with adaptable chemical structures. The resulting building block were involved in the design of non-isocyanate polyhydroxyurethane (NIPHU) covalent adaptable networks (CAN) containing imine bonds suitable for coating applications. Material properties were fully investigated. Thermal, mechanical and self-healing properties, were linked to the aliphatic or aromatic structure of the starting bis-cyclocarbonates and exhibited a rapid bond exchange compared to classical NIPHU. Recyclability of these materials was also demonstrated.

This study presents the photochemical crosslinking of a partially biobased, semi-aromatic unsaturated polyester. Firstly, a polyester was synthesized from the condensation of diethyl 2,6-pyridinedicarboxylate, a biobased monomer derived from bacteria, and cis-2-butene-1,4-diol. Polyesters with molar masses up to 20,700 g/mol were obtained, with glass transition temperatures (Tg) reaching 51 degrees C. Secondly, photocrosslinked coatings were prepared by addition of a photosensitive thiol derivative of coumarin: 7-mercapto-4-methyl coumarin (0,1 eq / unsaturation). The resulting system was irradiated with a polychromatic lamp for one hour at 30 degrees C, allowing a thiol-ene reaction and a concomitant [2 + 2] cycloaddition. The resulting coatings were apolar (23 %), hard (Konig hardness 222 +/- 1 s), well crosslinked (swelling rate of 0.11 +/- 0.05) and exhibited a Tg of 74 degrees C.

This work aimed to develop an original, biobased, semi-aromatic and UV crosslinked unsaturated polyester, synthesized from a pyridine dicarboxylic acid derivative and an unsaturated aliphatic fatty acid derivative having 18 carbon atoms. A prepolymer with a number average molar mass of 1700 g/mol was synthesized and characterized by FTIR and NMR. This liquid prepolymer was then crosslinked under UV using a biobased compound, 7-mercapto-4-methyl coumarin (MMC), in two concomitant steps: the photografting of MMC onto the prepolymer by thiol-ene addition, and the photodimerization of MMC. The optimized conditions for the photochemical reaction were determined by evaluating the influence of formulation composition (thiol/fatty double bonds ratio from 0.1/1 to 1/1), temperature and irradiation time. In the end, relatively soft coatings (Konig hardness: 14.8 +/- 0.8 s, Tg =-34 degrees C) were produced after 1 h under UV irradiation at 30 degrees C with 0.1 equivalent of MMC.

Using a three steps procedure a water soluble cationic bis-cyclocarbonate was prepared. Aminolysis was attempted in water but was not successful because of rapid hydrolysis of the starting cyclocarbonate in these basic conditions. Non-isocyanate polyurethanes (linear and crosslinked) were then prepared in acetonitrile with high yields. The resulting materials exhibited good thermal properties (T-deg > 230 degree celsius) and Tg > 60 degree celsius. The presence of the cationic moiety led to hydrophilic materials with swelling rate of 45% and a plastification effect was observed with Tg decreasing down to -28 degree celsius. Further, considering ammonium characteristics, antibacterial properties were assessed. Surface adhesion test showed a 99,9% inhibition towards gram-positive and gramnegative bacteria for the polyurethane thermoset. Acute toxicity was evaluated on the bis-cyclocarbonate oligomer confirming its innocuity in the studied concentration range.

Herein we report an easily accessible supramolecular polymer readily made from polyvinyl butyral (PVB) by cross-linking with non-covalent self-complementary ureido-pyrimidinone (UPy) dimers. The resulting materials exhibit multifunctional properties, not only self-healing and shape memory, but also enhanced thermo-mechanical resistance. The UPy content, which represents the quadruple hydrogen bonding density, shows an important influence on tuning polymer performances. Moderate UPy content (2.5 mol.%) is important to impart the optimal comprehensive properties. Both infrared analyses and dynamic mechanical analyses indicate that the quadruple hydrogen bonding is stable up to 120 degrees C, thus enabling the healing process. The healing efficiency highly depends on the glass transition temperature (T-g) of the final polymer, itself being controlled by the UPy content. A 100% healing efficiency can be achieved at 120 degrees C when the UPy content is controlled up to 2.5 mol. %. Meanwhile, around 90% healing efficiency was achieved in water at 60 degrees C for all materials. All samples exhibit shape memory properties without obvious dependence on the UPy content. This work illustrates that the physical cross-linking, formed by non-covalent hydrogen bonding, cannot only provide a practical strategy to obtain multi-responsive shape memory polymers with self-healing feature but also offers the possibility to tune the polymer thermal and mechanical properties.

A promising process to design non-isocyanate polyurethane (NIPU) foams has been developed. The transurethane polycondensation reaction between fatty biscarbamates, fatty diols, and diamines was used to synthesize a biobased aminotelechelic NIPU oligomer. The prepared oligomer (hard phase) was mixed with an amino-telechelic polydimethylsiloxane (PDMS, soft phase) and then reacted with a biosourced tri-epoxide molecule as crosslinking agent, in the presence of water/ethanol mixtures as physical blowing agents. The crosslinking reaction was followed by Fourier transform infrared spectroscopy (FTIR) and rheometry. The foams can be obtained in less than 2 hours at 95 & DEG;C. The prepared foams exhibited cell diameters ranging from 130 to 3090 & mu;m, as well as densities ranging from 55 to 950 kg/m3. Their thermal stability thresholds were above 300 & DEG;C. They displayed glass transition temperature values ranging from -20 to -18 & DEG;C, and low values of the Young modulus ranging from 2.0 & BULL;103 to 5.7 & BULL;103 Pa. The hysteresis loss, the recovery time, and the firmness of these foams were dependent on the PDMS content and/or the morphological parameters.

The radical induced cationic frontal polymerization (RICFP) was used for the first time to elaborate epoxy foam from a mixture of a polyglycerol polyglycidyl ether (Denacol & REG; EX-512) and 3,4-epoxycyclohexylmethyl-3 & PRIME;,4 & PRIME;epoxycyclohexane carboxylate (CE) in 9/1 wt ratio. The initiating system was composed of 3.5 wt% of p(octyloxyphenyl) phenyl iodonium hexafluoroantimonate (I-Sb) used as acid photogenerator, and 5 wt% of 1,1,2,2-tetraphenyl ethanediol (TPED) acted as thermal radical initiator. Only 19 s of UV irradiation were necessary to generate a propagation velocity of the polymerization front of 24.0 cm/min. A maximum temperature of 201 degrees C was measured at the polymerization front. In the presence of 1 wt% of xylene playing the rule of physical foaming agent, the matrix was expanded by a factor 5. The prepared foams exhibited cell diameters ranging from 1.4 to 2.2 mm and an apparent density of 220 kg/m3.

The synthesis of functionalized polymyrcene, from bio-based myrcene and from carbon dioxide, is performed, thanks to the unique features of microflow systems.

A new process for the preparation of non-isocyanate polyurethane (NIPU) flexible foams has been implemented. Biobased amino-telechelic NIPU oligomers were prepared by an organo-catalyzed transurethane poly-condensation reaction of fatty biscarbamates with fatty diols and diamines. The obtained oligomers were reacted with a biobased multi-epoxide molecule as crosslinking agent, in the presence of a poly(hydromethylsiloxane) or its copolymer as foaming agent and surfactant. The crosslinking and foaming reactions were monitored by rheometric, volumetric and FTIR studies. The foams can be obtained in < 30 min at 100 degrees C or in 14.5 h at room temperature. The prepared foams displayed cell diameters in the range of 210 to 430 mu m associated with densities in the range of 130 to 400 kg/m(3). They also exhibited thermal stabilities above 300 degrees C, as well as a soft character attested by negative Tg values ranging from -10 to-28 degrees C, and low values of the Young modulus varying from 1.0 x 10(4) Pa to 6.3 x 10(4) Pa. The recovery time, hysteresis loss and the firmness of these foams were found to be dependent on their chemical structures.

A strategy aiming to decrease the amount of isocyanate in the PU industries without changing their current facilities is proposed. Hydroxyl terminated non-isocyanate polyurethane (NIPU) oligomers (H-Ol) with controlled molecular weights and chemical structures have been prepared as precursors. They were prepared by transurethane polycondensation between bis(methylcarbamate) (BMC), hydroxyterminated poly(tetramethyleneoxide) (PTMO) and butanediol at several molar ratios. H-Ol were then reacted with a polyisocyanurate as crosslinking agent to afford several partially NIPU coatings. Polyurethanes based on the PTMO polyols and the polyisocyanurate were also prepared as controls to highlight the importance of the urethane function in the H-OlI. The influence of the chemical structures on the thermal and mechanical properties of the final coatings has been investigated. The prepared coatings displayed thermal stabilities above 200 degrees C, Young modulus ranging from 3 to 64 MPa, tensile strength values from 0.9 to 17 MPa and elongation at break varying from 25 to 530%. H-Ol with the highest urethane content gave a coating with the best adhesion properties on a metal surface. All the obtained properties were within the characteristic range of two commercial PU reference coatings.

N-[2-(acryloyloxy)ethyl]-N,N-dimethyl-N-butylammonium iodide was successfully photo-polymerized from native and thiolated PDMS surface, in the presence of benzophenone. The directly and indirectly grafted surfaces exhibited quaternary ammonium densities of about 1015 and 1017 N+.cm−2, respectively, and very high hydrophilicity compared to non-grafted surfaces. The live and dead tests performed by fluorescence microscopy revealed an effective contact bactericidal effect of this surface against Escherichia coli and Staphylococcus epidermidis.

Vinylbenzyl dimethylbutylammonium chloride was successfully grafted and photo-polymerized from a PDMS surface, in presence of benzophenone. The obtained surface exhibited quaternary ammonium density above 10(17) charge/cm(2) and very high hydmphilicity compared to ungrafted surfaces. Bacterial enumeration and fluorescence microscopy revealed an efficient contact killing of this surface against Escherichia coli, Staphylococcus aureus and Staphylococcus epidermidis.

This paper reports the development in aqueous solution of mixed micelles of tunable cloud point temperature through blending in various proportions of two copolymers of different chemical natures. For that purpose, a lipid-b-poly(2-isopropyl-2-oxazoline) (lipid-b-P(iPrOx)) copolymer, self-assembling into thermosensitive micelles that phase-separate above a cloud point temperature of 38 °C, was blended in various proportions with commercial C18-b-PEOx. The latter was constituted of a hydrophobic saturated C18 chain and a hydrophilic poly(ethylene oxide) (PEO) block with varying polymerization degrees (x) and does not have any thermosensitive properties on the studied temperature range for any value of x. The different blends were thoroughly characterized by light scattering and UV-visible spectroscopy, revealing that hybridization between both copolymers always occurred, independent of the PEO block length. The resulting mixed micelles present TCP values progressively increasing with the C18-b-PEOx proportion, from 38 to 61 °C. This study demonstrates the relevance of the blending approach to tune the phase separation of micellar systems by formulation rather than by more tedious synthetic efforts. Shifting TCP through this approach extends the range of temperature where lipid-b-P(iPrOx) can find an application.

The generation and reactivity of two model vinyl carbenoids from gem-dibromoalkenes 1 were studied in microflow systems. From substrate 1a (R = Ph, CF3), the lithium-bromine exchange could be simply performed within 30 ms at 20 °C with very good E-selectivity whereas the reaction was unselective under batch conditions, even at −78 °C. Moreover, the unstable carbenoid generated from 1b (R = Ph, H) could be trapped as the major product while only the Fritsch-Buttemberg-Wiechell rearrangement product was obtained in a flask under cryogenic conditions.

Cationic copolymerizations of different ketoketenes are conducted to explore the structure and properties of the afforded copolymers. Diethylketene (DEK) and diphenylketene (DPK) are both copolymerized with dimethylketene (DMK), via a cationic mechanism using the mixture AlCl3 / (CH3)3CCl as initiator. The experiments confirmed that two series of polyketones, containing a main DMK chain comprising few DEK or DPK units, are successfully obtained. The reactivity ratios are calculated. The structures and thermal performances of the obtained copolymers are discussed. An interesting DMK / DEK copolymer with a broad processing window was obtained (Tm = 164 °C, $${T}_{d}^{5\%}$$ = 259 °C).

Non-isocyanate polyurethane acrylate coatings (NIPUAs) were prepared by photocrosslinking of mixtures of an acrylate terminated NIPU oligomers (A-Ol) and reactive (meth-)acrylate diluents. A-Ol were prepared by a transurethane polycondensation pathway followed by an acrylation reaction of the resulting hydroxy chain-ends. The influence of the reactive diluent content and chemical structures on the thermal and mechanical properties of these coatings has been investigated. The obtained materials exhibited thermal stabilities above 255 degrees C, Young modulus ranging from 2.6 to 9.2 MPa, tensile strength from 2.69 to 25.5 MPa and elongation at break from 56 to 470%.