Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations.

For decades, self-blown polyurethane foams─found in an impressive range of materials─are produced by the toxic isocyanate chemistry and are difficult to recycle. Producing them in existing production plants by a rapid isocyanate-free self-blowing process from room temperature (RT) formulations is a long-lasting challenge. The recent water-induced self-blowing of nonisocyanate polyurethane (NIPU) formulations composed of a CO2-based tricyclic carbonate, diamine, water, and a catalyst successfully addressed the isocyanate issue, however failed to provide foams at RT. Herein, we elaborate a practical solution to empower the NIPU foam formation in record timeframes from RT formulations. We generate cascade exotherms by the addition of a highly reactive triamine and an epoxide to the formulation of the water-induced self-foaming process. These exotherms, combined to a fast cross-linking imparted by the triamine and epoxide, rapidly raise the temperature to the foaming threshold and deliver hybrid NIPU foams in 5 min with KOH as a catalyst. Careful selection of the monomers enables producing foams with a wide range of properties, as well as with an unprecedented high biobased content up to 90 wt %. Moreover, foams can be upcycled into polymer films by hot pressing, offering them a facile reuse scenario. This robust cheap process opens huge perspectives for greener foams of high biobased contents, expectedly responding to the sustainability demands of the foam sector. It is potentially compatible to the retrofitting of industrial foaming infrastructures, which is of paramount importance to accommodate existing foam production plants and address the huge foam market demands.

Water-Induced Self-Blown Non-Isocyanate Polyurethane Foams.

For 80 years, polyisocyanates and polyols were central building blocks for the industrial fabrication of polyurethane (PU) foams. By their partial hydrolysis, isocyanates release CO2 that expands the PU network. Substituting this toxic isocyanate-based chemistry by a more sustainable variant-that in situ forms CO2 by hydrolysis of a comonomer-is urgently needed for producing greener cellular materials. Herein, we report a facile, up-scalable process, potentially compatible to existing infrastructures, to rapidly prepare water-induced self-blown non-isocyanate polyurethane (NIPU) foams. We show that formulations composed of poly(cyclic carbonate)s and polyamines furnish rigid or flexible NIPU foams by partial hydrolysis of cyclic carbonates in the presence of a catalyst. By utilizing readily available low cost starting materials, this simple but robust process gives access to greener PU foams, expectedly responding to the sustainability demands of many sectors.

Introducing Polyhydroxyurethane Hydrogels and Coatings for Formaldehyde Capture.

Formaldehyde (FA) is a harmful chemical product largely used for producing resins found in our living spaces. Residual FA that leaches out the resin contributes to our indoor air pollution and causes some important health issues. Systems able to capture this volatile organic compound are highly desirable; however, traditional adsorbents are most often restricted to air filtration systems. Herein, we report novel waterborne coatings that are acting as a FA sponge for indoor air decontamination. These coatings, of the poly(hydroxyurethane) (PHU) type, rich in primary amine groups, are prepared by the polyaddition of a hydrosoluble dicyclic carbonate to a polyamine in water at room temperature under catalyst-free conditions. We highlight the importance of the choice of the polyamine on the curing rate of the formulation and on the FA capture ability of PHU. The excellent FA capturing ability of the best candidate is rationalized by investigating the action mode of the polyamine used to construct PHUs. With poly(vinyl amine), FA is covalently and permanently bound to PHU, with no release over time. The performance of the coating in FA abatement is impressive, with more than 90% of captured FA after one day of contact. The facility to prepare these transparent and colorless coatings from waterborne formulations gives access to new efficient indoor air depolluting solutions, potentially applicable to various surfaces of our living spaces (wall, ceiling, etc.).

Water-Borne Isocyanate-Free Polyurethane Hydrogels with Adaptable Functionality and Behavior.

Polyurethane hydrogels are attractive materials finding multiple applications in various sectors of prime importance; however, they are still prepared by the toxic isocyanate chemistry. Herein the facile and direct preparation in water at room temperature of a large palette of anionic, cationic, or neutral polyurethane hydrogels by a non-isocyanate route from readily available diamines and new hydrosoluble polymers bearing cyclic carbonates is reported. The latter are synthesized by free radical polymerization of glycerin carbonated methacrylate with water-soluble comonomers. The hydrogel formation is studied at different pH and its influence on the gel time and storage modulus is investigated. Reinforced hydrogels are also constructed by adding CaCl2 to the formulation that in-situ generates CaCO3 particles. Thermoresponsive hydrogels are also prepared from new thermoresponsive cyclic carbonate bearing polymers. This work demonstrates that a multitude of non-isocyanate polyurethane hydrogels are easily accessible under mild conditions without any catalyst, opening new perspectives in the field.

Atmospheric Plasma Deposition of Methacrylate Layers Containing Catechol/Quinone Groups: An Alternative to Polydopamine Bioconjugation for Biomedical Applications.

Bioconjugation of enzymes on coatings based on polydopamine (PDA) layers is an appealing approach to control biological responses on biomedical implant surfaces. As alternative to PDA wet deposition, a fast, solvent-free, and dynamic deposition approach based on atmospheric-pressure plasma dielectric barrier discharge process is considered to deposit on metallic surfaces acrylic-based interlayers containing highly chemically reactive catechol/quinone groups. A biomimetic approach based on covalent immobilization of Dispersin B, an enzyme with antibiofilm properties, shows the bioconjugation potential of the novel plasma polymer layers. The excellent antibiofilm activity against Staphylococcus epidermidis is comparable to the PDA-based layers prepared by wet chemical methods with slow deposition rates. A study of preosteoblastic MG-63 human cell line viability and adhesion properties on plasma polymer layers demonstrates early interaction required for biomedical applications.

Expanding the Scope of Controlled Radical Polymerization via Cobalt-Tellurium Radical Exchange Reaction.

Cobalt-mediated radical polymerization (CMRP) and tellurium-mediated radical polymerization (TERP) were combined for the first time, offering new perspectives in the precision design of macromolecular structures. In particular, the present work highlights the benefits of this strategy for the synthesis of novel poly(vinyl acetate)-based block copolymers. A range of well-defined poly(vinyl acetate)s (PVAc) were first produced via CMRP using the bis(acetylacetonato)cobalt(II) complex (Co(acac)2) as a regulating agent. Substitution of a methyltellanyl moiety for Co(acac)2 at the ω-chain end of the precursor was then achieved upon treatment with dimethylditelluride. In contrast to the PVAc prepared by TERP, the ones produced by sequential CMRP and Co/Te exchange reaction almost exclusively consist of regular head-to-tail-TeMe chain-end species that can be activated by TERP. Ultimately, a series of monomers problematic in Co(acac)2-mediated radical polymerization including N-isopropylacrylamide (NIPAM), 2-(dimethylamino)ethyl acrylate (ADAME), n-butyl acrylate (BA), isoprene (IP), and vinylimidazole (NVIm) were polymerized by TERP from the PVAc-TeMe macroinitiators leading to novel diblock copolymers that cannot be made by each technique used separately.