Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.     

Elevation of modulus and elongation of semicrystalline polyurethanes

Polyurethanes were synthesized based on an amorphous polyester polyol, and different chain extenders, comparing the universally accepted symmetric chain extender (1,4‐butanediol) with an asymmetric (1,2‐propanediol) chain extender. The effect of incorporating a crystalline polyester polyol polyhexamethylene adipate (PHMA) was investigated. The resulting morphologies and tensile properties are dramatically different. Based on the thermal and infrared data obtained, the sample with the symmetric chain extender exhibits a phase‐separated morphology, which can change as a function of time and temperature. Conversely, the polyurethane with the asymmetric chain extender has a phase mixed morphology that remains stable under the same experimental conditions. Incorporating crystalline PHMA resulted in a substantial change in the mechanical properties of the materials, especially for the copolymer comprising asymmetric chain extender. The rate of crystallization and the degree of crystallization achieved depended on the type of chain extender used. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018     

Actuation design for high‐performance shape memory polyurethanes

A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (M_c) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000M_c with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479     

Statistical and experimental investigation on low density microcellular foaming of PLA-TPU/cellulose nano-fiber bio-nanocomposites

This study dedicates to foaming of biocompatible blends of polylactic acid and thermoplastic polyurethane reinforced with bio-degradable cellulose nanofibers. This research primarily was associated with fabrication of PLA-TPU nanocomposites using a low weight fraction of cellulose nanofibers as a biodegradable reinforcement. Microstructural and mechanical properties of fabricated nanocomposites were examined and diffractometry was utilized to verify formation of percolated nanocomposites. Microcellular foaming was then performed with CO₂ as a blowing agent. Central composite design was applied in designing the experiments to evaluate the effects of main operating variables consisting of saturation pressure and time, heating time and foaming temperature. The results demonstrated that high saturation pressure and time promoted low cell diameters (below 5 μm) and high cell densities (above 10⁹ cell/cm³) due to the grown degree of crystallinity and higher PLA-TPU miscibility. Accordingly, adding TPU and CNF to the matrix create high crystalline foamed samples decorated with low bulk density.     

Stress–Strain Dependence of Segmented Polyurethanes and Polyurethane Ureas

The stress–strain dependences of segmented elastomers based on polyetherurethanes, polyesterurethane ureas, and polybutadieneurethane ureas were investigated. These dependences were adequately described using the generalized approach proposed earlier by the authors for amorphous elastomers. The experimental data obtained for four series of samples with chemical cross-linking confirmed an applicability of this approach for segmented elastomers. Unlike amorphous elastomers, the effective network density value was affected not only by the density of the chemical network, but the contribution of the network formed by the hard domains also needs be taken into account.     

Oxygen Barrier Properties of Waterborne Polyurethane/Silica Hybrids

The oxygen barrier properties of films obtained from waterborne polyurethane/silica hybrid dispersions were analyzed. Two different types of polyurethanes were used, based on poly(propylene glycol) and poly(1,4-butylene adipate). Three different strategies were followed in the preparation of the hybrid dispersions. In the first type of materials (series 1), the inorganic part came exclusively from the covalent incorporation of trifunctional silane groups into the polymeric chains. The other two series contained, in addition to the trifunctional silane groups, tetrafunctional silane groups either physically blended (series 2) or “in situ” generated (series 3). Materials of series 1 showed an increase of the oxygen permeability coefficient with the silane content. However, the other two types of materials presented just the opposite dependence. In this latter case, the systems containing “in situ” generated silica (series 3) presented higher permeability coefficient values, probably because of the steric hindrance imposed by the polyurethane that gave rise to silica networks containing silanol groups and free volume holes. Moreover, lower permeability coefficient values were obtained when larger size particles were added. This fact could mean that the polyurethane/silica interface effects were not totally hindered even when the organic/inorganic phases were covalently bonded.     

Properties of Absorbent Acrylic Foam Prepared Based on the Method of High Internal Phase Emulsion

Acrylate and methacrylate monomers absorbent acrylate foams were prepared based on the method of high internal phase emulsion (HIPE). The influence of reaction conditions on liquid absorption by acrylate foams was studied. The reaction conditions included monomer ratio, cross-linker amount, initiator amount, emulsifier amount, emulsion concentration, emulsification temperature, and the curing time. The reaction conditions were determined to achieve the best liquid absorption by acrylate foams. Acrylate foams were analyzed with Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results showed that when the monomer ratio was 9:1, cross-linking agent was 30% of monomer amount, initiator amount was 4% of the reactants amount, emulsifier amount was 8% of the reactants amount, the ratio of aqueous phase to oil phase was 32:1, emulsification temperature was 75°C, and curing time was 1.5 h, we could prepare the acrylate foam material with the best liquid absorption. Reaction of monomer and cross-linking agent was confirmed by FTIR analysis. The pore sizes of acrylate foam were between 1 μm and 8 μm according to SEM analysis. This material was very suitable to absorb aqueous fluids.     

Study of Electrical Conductivity of Para-Toluene Sulfonic Acid Doped Polyaniline/Polyester-Based Polyurethane Blends in the S-Band Frequency Range

Conducting polymer blends were prepared using polyaniline doped with para- toluene sulfonic acid (PTSA-PANI) and a polyester polyol-based polyurethane (PU). The morphological, thermal and dielectric properties of the PTSA-PANI/PU blends in the frequency range of 1–5 GHz (S band) were investigated. It was found that the morphology of the samples was affected by the PTSA-PANI loading, resulting in the formation of agglomerates and pathways when above 10 wt%. The thermal stability of the composites was improved with increased PTSA-PANI loading. The electrical conductivity percolation threshold was obtained at 2.5% of PTSA-PANI loading and the electrical conductivity reached the value of 0.13 S/m at a PTSA-PANI loading of 30 wt%. The obtained results for the PTSA-PANI/PU blends prepared indicate a high potential for their successful use in electrical and electromagnetic applications.     

Effect of a Nanoclay on the Mechanical,Thermal and Flame Retardant Properties of Rigid Polyurethane Foam

Water blown rigid polyurethane foams (PUF) with organoclay/organically modified nanoclay (ONC) were prepared and their properties such as density, mechanical, morphological, insulation, thermal and flame retardant properties were studied. In this investigation, the ONC content was varied from 1 to 10 parts per hundred of polyol (php) by weight. It was observed that the compressive strength of ONC filled PUF increased up to 3 php of ONC loading and then it decreased. Wide angle X-ray diffraction and transmission electron microscopy studies indicated the exfoliated dispersion of ONC in PUF. The thermal conductivity of ONC filled PUF decreases up to 5 php and then increases. The glass transition temperature (Tg) of PUF decreases on loading of ONC. The TGA analysis shows that there is slight increase in degradation temperature with increase in ONC loading. The flame retardant properties (LOI and flame spread rate) are improved slightly on addition (3 php) of ONC filled PUF.