Phosphorus-Containing Polyisocyanurate Elastomers for Flame Retardant Application

Polyurethane (PU) is one of the most common and versatile polymers in many applications especially in the construction and automotive industry where the improvement of thermal stability and flame retardancy is crucial. As polyisocyanaurate (PIR) is well known to have a high decomposition temperature and phosphorus motifs are usually used as flame retardants in polymers, the introduction of PIR and phosphorus motifs in polyurethanes can lead to PUs with high thermal stability and flame retardancy. We investigated a synthetic pathway to introduce polyisocyanurate (PIR) and phosphorus motifs in polyurethanes via co-trimerization of 4,4′-methylene diphenyl diisocyanate (4,4′-MDI) and monoisocyanate, which was synthesized from the reaction between diethyl (hydroxymethyl)phosphonate (DEHP) and 4,4′-MDI. The resulting PIR-DEHP prepolymer was used to prepare PIR-DEHP elastomers in both solvent and solvent-free conditions. The elastomer with polyester polyol and 15 wt % 1,4-butanediol in the polyol component showed high char formation (25.5 wt %) and 55% reduction in the total heat release (THR) relative to the reference elastomer without PIR and phosphorus content. It is expected that the use of the PIR-DEHP prepolymer can be extended to other applications, such as rigid PU foams and compact thermosets where the flame retardancy and bulk reaction conditions are required

Intramolecularly catalyzed dynamic polyester networks using neighboring carboxylic and sulfonic acid groups

Dynamic covalent bonds in a polymer network lead to plasticity, reshapability, and potential recyclability at elevated temperatures in combination with solvent-resistance and better dimensional stability at lower temperatures. Here we report a simple one-step procedure for the catalyst-free preparation and intramolecularly catalyzed stress-relaxation of dynamic polyester networks. The procedure is based on the coupling of branched OH-end functional polyesters (functionality ≥ 3) by pyromellitic dianhydride (PMDA) or 2,5-bis(methoxy-carbonyl) benzenesulfonic acid resulting in ester linkages with, respectively, a COOH or a SO3H group in a position ortho to the ester bond. This approach leads to an efficient external catalyst-free dynamic polyester network, in which the topology rearrangements occur via a dissociative mechanism involving anhydrides. The SO3H-containing network is particularly interesting, as it shows the fastest stress relaxation and does not suffer from unwanted additional transesterification reactions, as was observed in the COOH-containing network.</p

Synthesis of polyisocyanurate prepolymer and the resulting flexible elastomers with tunable mechanical properties

Polyurethane (PU) is used in a wide range of applications due to its diverse chemical and physical properties. To meet the increasing demands on thermal and mechanical properties of PU materials, polyisocyanurates(PIRs) have been introduced in PU materials as crosslinkers and due to their high decomposition temperature. We prepared a liquid PIR prepolymer with high PIR content by co-trimerization of 4,4’-methylene diphenyl diisocyanate (4,4’-MDI) and mono-isocyanates. The mono-isocyanate was synthesizedvia reaction between a 4,4’-MDI and a 2-ethyl-1-hexanol. The PIR prepolymer obtained was further reacted with long chain polyols and chain extenders in both solvent and solvent-free conditions, leading to PIR elastomers that exhibited good thermal stability with high char formation, and improvedmechanical properties with much higher Young’s modulus. This work demonstrates that the liquid PIR prepolymer can potentially be used in various large-scale industrial applications

Solvent-Free Preparation of Thermally Stable Poly(urethane-imide) Elastomers

Polyurethanes (PUs) are widely used in many applications due to their versatile chemical and physical properties. To meet the increasing demands on PU with respect to intrinsic mechanical and thermal properties, they can be modified with thermally stable aromatic imide structures to form poly(urethane imide) (PUI). However, the preparation of PUI materials has been limited by the need for strong polar solvents, which hinder their industrial scale development. In this work, we prepared imide-containing isocyanate-terminated prepolymers via the reaction of polymeric aromatic or aliphatic isocyanates and pyromellitic dianhydride in completely solvent-free conditions. The subsequent PUI elastomers made from these prepolymers exhibited enhanced char formation and stiffness in comparison to the reference elastomers without imide structures, among which the aromatic PUI elastomer shows improved flame retardancy according to the initial cone calorimetry measurement. This work demonstrates the potential use of imide prepolymers in other PU applications where high thermal stability and flame retardancy are required. The solvent-free synthesis also paves a way for the large-scale production of PUI materials

Fluorescent Visualization of Bond Breaking in Polymer Glasses

Mechanofluorescent polymer probes were used to visualize stresses and bond scission in polystyrene and polycarbonate. Sonication of polystyrene probes with a molar mass of 1.1 × 105 g·mol-1 in solution resulted in 30% activation after 1 h, while shorter probes showed lower activation percentages. Single-asperity sliding friction tests were performed on mechanophore-containing polystyrene and polycarbonate films. Polystyrene showed clearly visible crack formation with a correlated pattern in the friction force, penetration depth, and fluorescent activation of the mechanophore. Significant mechanophore activation in polystyrene was observed for an applied normal load of 100 mN, whereas in polycarbonate, activation only occurred at a normal load higher than 400 mN. The different degrees of activation correlate well with the toughness of polycarbonate compared to polystyrene.</p

Fractography of poly(: N -isopropylacrylamide) hydrogel networks crosslinked with mechanofluorophores using confocal laser scanning microscopy

Due to their soft and brittle nature, the mechanical characterization of polymer hydrogels is a difficult task employing traditional testing equipment. Here, we endowed poly(N-isopropyl acrylamide) (PNIPAAm) hydrogel networks with Diels-Alder adducts of π-extended anthracenes as mechanofluorophore crosslinkers. After swelling the networks with varying amounts of water and subjecting them to force, we visualized the subsequent fluorescence caused by covalent bond scission with confocal laser scanning microscopy (CLSM) and related the intensities to the macroscopic fracture mechanics and the elastic moduli recorded with traditional uniaxial compression. The sensitivity of the mechanofluorophores allowed the analysis of low levels of mechanical stress produced via a hand-induced needle-puncturing process and, thus, is an alternative to conventional force application methods. The detection and precise localization of covalent bond scission via CLSM helps elucidating the interrelationship between molecular structure and the macroscopic properties of chemically crosslinked polymeric hydrogels. We believe that this micro-scale mechanophore-assisted fractography can establish a new paradigm for the mechanical analysis of soft matter in fields covering traditional polymer and life sciences. © 2019 The Royal Society of Chemistry

Benzene Tetraamide:A Covalent Supramolecular Dual Motif in Dynamic Covalent Polymer Networks

In dynamic polyamide networks, 1,2,4,5-benzene tetraamide (B4A) units act simultaneously as a dynamic covalent cross-linker and as supramolecular stacking motif. This results in materials with a rubbery plateau modulus that is about 20 times higher than that of a corresponding reference network in which the supramolecular interaction is suppressed. In branched polyamides with the same B4A dynamic motif, hydrogen bonding and stacking lead to strong and reversible supramolecular networks, whereas a branched polyamide with the nonstacking reference linker is a viscous liquid under the same conditions. Wide-angle X-ray scattering and variable-temperature infrared experiments confirm that covalent cross-linking and stacking cooperatively contribute to the dynamics of the network. Stress relaxation in the reference network is dominated by a single mode related to the dynamic covalent chemistry, whereas relaxation in the B4A network has additional modes assigned to the stacking dynamics.</p

Hepatic Spheroid Formation on Carbohydrate-Functionalized Supramolecular Hydrogels

Two synthetic supramolecular hydrogels, formed from bis-urea amphiphiles containing lactobionic acid (LBA) and maltobionic acid (MBA) bioactive ligands, are applied as cell culture matrices in vitro. Their fibrillary and dynamic nature mimics essential features of the extracellular matrix (ECM). The carbohydrate amphiphiles self-assemble into long supramolecular fibers in water, and hydrogels are formed by physical entanglement of fibers through bundling. Gels of both amphiphiles exhibit good self-healing behavior, but remarkably different stiffnesses. They display excellent bioactive properties in hepatic cell cultures. Both carbohydrate ligands used are proposed to bind to asialoglycoprotein receptors (ASGPRs) in hepatic cells, thus inducing spheroid formation when seeding hepatic HepG2 cells on both supramolecular hydrogels. Ligand nature, ligand density, and hydrogel stiffness influence cell migration and spheroid size and number. The results illustrate the potential of self-assembled, carbohydrate-functionalized hydrogels as matrices for liver tissue engineering.</p

Dynamic covalent networks with tunable dynamicity by mixing acylsemicarbazides and thioacylsemicarbazides

Dynamic covalent networks (DCNs) use chemical bonds that break and reform at appropriate processing conditions to allow reconfiguration of the networks. Recently, the acylsemicarbazide (ASC) motif has been added to the repertoire of such dynamic covalent bonds, which is capable of hydrogen bonding as well as dynamic bond exchange. In this study, we show that its sulfur congener, thioacylsemicarbazide (TASC), also acts as a dynamic covalent bond, but exchanges at a slower rate than the ASC moiety. In addition, siloxane-based DCNs comprising either ASC or TASC motifs or a varying composition of both show tunable relaxation dynamics, which slow down with an increasing amount of TASC motifs. The reduction in stress relaxation goes hand in hand with a reduction of creep in the network and can be tuned by the ASC/TASC ratio. All networks are readily processed using compression molding and dissolve when treated with excess hydrazide in solution. The ability to control network properties and creep in dynamic covalent polymeric networks by small changes in the molecular structure of the dynamic bond allows a generalized synthetic approach while accommodating a wide temperature window for application.</p

Tracking Local Mechanical Impact in Heterogeneous Polymers with Direct Optical Imaging

Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane—a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small‐molecule organometallic mechano‐responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft‐matter systems for which global characterization techniques fall short of providing molecular‐level insight