Synthesis, Structure and Properties of Polyester Polyureas via a Non-Isocyanate Route with Good Combined Properties.

Polyureas have been widely applied in many fields, such as coatings, fibers, foams and dielectric materials. Traditionally, polyureas are prepared from isocyanates, which are highly toxic and harmful to humans and the environment. Synthesis of polyureas via non-isocyanate routes is green, environmentally friendly and sustainable. However, the application of non-isocyanate polyureas is quite restrained due to their brittleness as the result of the lack of a soft segment in their molecular blocks. To address this issue, we have prepared polyester polyureas via an isocyanate-free route and introduced polyester-based soft segments to improve their toughness and endow high impact resistance to the polyureas. In this paper, the soft segments of polyureas were synthesized by the esterification and polycondensation of dodecanedioic acid and 1,4-butanediol. Hard segments of polyureas were synthesized by melt polycondensation of urea and 1,10-diaminodecane without a catalyst or high pressure. A series of polyester polyureas were synthesized by the polycondensation of the soft and hard segments. These synthesized polyester-type polyureas exhibit excellent mechanical and thermal properties. Therefore, they have high potential to substitute traditional polyureas.

Biodegradable Polyurethane Derived from Hydroxylated Polylactide with Superior Mechanical Properties.

Developing biodegradable polyurethane (PU) materials as an alternative to non-degradable petroleum-based PU is a crucial and challenging task. This study utilized lactide as the starting material to synthesize polylactide polyols (PLA-OH). PLA-based polyurethanes (PLA-PUs) were successfully synthesized by introducing PLA-OH into the PU molecular chain. A higher content of PLA-OH in the soft segments resulted in a substantial improvement in the mechanical attributes of the PLA-PUs. This study found that the addition of PLA-OH content significantly improved the tensile stress of the PU from 5.35 MPa to 37.15 MPa and increased the maximum elongation to 820.8%. Additionally, the modulus and toughness of the resulting PLA-PU were also significantly improved with increasing PLA-OH content. Specifically, the PLA-PU with 40% PLA-OH exhibited a high modulus of 33.45 MPa and a toughness of 147.18 MJ m-3. PLA-PU films can be degraded to carbon dioxide and water after 6 months in the soil. This highlights the potential of synthesizing PLA-PU using biomass-renewable polylactide, which is important in green and sustainable chemistry.

The Influence of Diisocyanate Structure on Thermal Stability of Thermoplastic Polyurethane Elastomers Based on Diphenylmethane-Derivative Chain Extender with Sulfur Atoms.

The work is a continuation of the research on thermoplastic polyurethane (TPU) elastomers containing sulfur atoms which are incorporated into the polyurethane chain using aliphatic-aromatic chain extenders. These materials show some improved properties in relation to conventional ones, e.g., adhesion to metals, bacterial resistance and refractive index. The present study deals with the detailed characteristics of the process of thermal decomposition of TPU elastomers obtained from 2,2'-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 1,1'-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and poly(oxytetramethylene) diol of Mn = 2000 g/mol by thermogravimetric analysis coupled on-line with Fourier transform infrared spectroscopy. The analysis was performed under inert and oxidative conditions. All TPU elastomers were found to have a relatively good thermal stability, with those based on aromatic diisocyanate being at an advantage. In helium, they are stable up to 280-282 °C (from HDI) and 299-301 °C (from MDI), whereas in synthetic air up to 252-265 °C (from HDI) and 261-272 °C (from MDI), as measured by the temperature of 1% mass loss. Depending on the content of the hard segments and the tested atmosphere, the TPU elastomers decompose from one to four stages. From the analysis of the volatile decomposition products, it follows that the decomposition of both types of hard segments was accompanied by the evolution of carbonyl sulfide, carbon dioxide, water, sulfide dioxide, alcohols and aromatic compounds. For the hard segment derived from HDI, isocyanates, amines, and unsaturated compounds were also identified, while for the MDI-derived one, aldehydes were discovered. In turn, the polyether soft segment decomposed mainly into aliphatic ethers, aldehydes, and carbon monoxide.

Preparation and Properties of PED-TDI Polyurethane-Modified Silicone Coatings.

To explore the influence mechanisms of polyurethane soft segments on modified silicone coatings, a series of modified coatings was prepared by introducing different contents of hydroxypropyl-terminated polydimethylsiloxane (PDMS2200) into the soft segment of polyurethane. ATR-FTIR, NMR, CLSM, AFM, contact angle measurement, the tensile test, bacterial adhesion, and the benthic diatom adhesion test were used to investigate the structure, morphology, roughness, degree of microphase separation, surface energy, tensile properties, and antifouling properties of the modified coatings. The results show that PDMS2200 could aggravate the microphase separation of the modified coatings, increase the surface-free energy, and reduce its elastic modulus; when the microphase separation exceeded a certain degree, increasing PDMS2200 would decrease the tensile properties. The PED-TDI polyurethane-modified silicone coating prepared with the formula of PU-Si17 had the best tensile properties and antifouling properties among all modified coatings.

Effect of Different Soft Segment Contents on the Energy Storage Capacity and Photo-Thermal Performance of Polyurethane-Based/Graphene Oxide Composite Solid-Solid Phase Change Materials.

A series of polyurethane/graphene oxide (PU/GO) solid-solid phase change materials (SSPCMs) were synthesized by using GO as a light-absorbing filler and polyethylene glycol (PEG) as a phase change matrix. The effects of PEG content on the energy storage capacity, thermal stability and photo-thermal conversion performance of PU were investigated. The results show that the form-stability of PU/GO decreases while the phase change enthalpy and photo-thermal conversion efficiency of PU/GO increases with the increasing PEG content. The introduction of a very low content of GO can maintain comparable energy storage density and greatly improve light absorption by reasonably modulating the soft segment contents. The PU/GO composite with 92 wt% PEG has a phase change enthalpy of 138.12 J/g and a high photo-thermal conversion efficiency (87.6%). The composite solid-solid PCMs have great potential for effective energy storage and solar energy utilization.

Design and Synthesis of Bio-Inspired Polyurethane Films with High Performance.

In the present work, the synthesis of segmented polyurethanes functionalized with catechol moieties within the hard or the soft segment is presented. For this purpose, a synthetic route of a new catechol diol was designed. The direct insertion of this catechol-free derivative into the rigid phase led to segmented polyurethanes with low performance (σmax ≈ 4.5 MPa). Nevertheless, when the derivative was formally located within the soft segment, the mechanical properties of the corresponding functionalized polyurethane improved considerably (σmax ≈ 16.3 MPa), owing to a significant increase in the degree of polymerization. It is proposed that this difference in reactivity could probably be attributed to a hampering effect of this catecholic ring during the polyaddition reaction. To corroborate this hypothesis, a protection of the aromatic ring was carried out, blocking the hampering effect and avoiding secondary reactions. The polyurethane bearing the protected catechol showed the highest molecular weight and the highest stress at break described to date (σmax ≈ 66.1 MPa) for these kind of catechol-functionalized polyurethanes. Therefore, this new approach allows for the obtention of high-performance polyurethane films and can be applied in different sectors, benefiting from the molecular adhesion introduced by the catechol ring.

Sorption/Diffusion Contributions to the Gas Permeation Properties of Bi-Soft Segment Polyurethane/Polycaprolactone Membranes for Membrane Blood Oxygenators.

Due to their high hemocompatibility and gas permeation capacity, bi-soft segment polyurethane/polycaprolactone (PU/PCL) polymers are promising materials for use in membrane blood oxygenators. In this work, both nonporous symmetric and integral asymmetric PU/PCL membranes were synthesized, and the permeation properties of the atmospheric gases N2, O2, and CO2 through these membranes were experimentally determined using a new custom-built gas permeation apparatus. Permeate pressure vs. time curves were obtained at 37.0 °C and gas feed pressures up to 5 bar. Fluxes, permeances, and permeability coefficients were determined from the steady-state part of the curves, and the diffusion and sorption coefficients were estimated from the analysis of the transient state using the time-lag method. Independent measurements of the sorption coefficients of the three gases were performed, under equilibrium conditions, in order to validate the new setup and procedure. This work shows that the gas sorption in the PU/PCL polymers is the dominant factor for the permeation properties of the atmospheric gases in these membranes.

A biomimetic approach for designing stent-graft structures: Caterpillar cuticle as design model.

Stent-graft (SG) induced biomechanical mismatch at the aortic repair site forms the major reason behind postoperative hemodynamic complications. These complications arise from mismatched radial compliance and stiffness property of repair device relative to native aortic mechanics. The inability of an exoskeleton SG design (an externally stented rigid polyester graft) to achieve optimum balance between structural robustness and flexibility constrains its biomechanical performance limits. Therefore, a new SG design capable of dynamically controlling its stiffness and flexibility has been proposed in this study. The new design is adopted from the segmented hydroskeleton structure of a caterpillar cuticle and comprises of high performance polymeric filaments constructed in a segmented knit architecture. Initially, conceptual design models of caterpillar and SG were developed and later translated into an experimental SG prototype. The in-vitro biomechanical evaluation (compliance, bending moment, migration intensity, and viscoelasticity) revealed significantly better performance of hydroskeleton structure than a commercial SG device (Zenith(™) Flex SG) and woven Dacron(®) graft-prosthesis. Structural segmentation improved the biomechanical behaviour of new SG by inducing a three dimensional volumetric expansion property when the SG was subjected to hoop stresses. Interestingly, this behaviour matches the orthotropic elastic property of native aorta and hence proposes segmented hydroskeleton structures as promising design approach for future aortic repair devices.

The tensile properties of poly(ethylene oxide)-based segmented block copolymers in the dry and wet state.

The tensile properties of poly(ethylene oxide)-based segmented block copolymers were studied in the dry and wet state. The hard segments were made up of monodisperse crystallisable tetra-amide segments (T6T6T) comprising terephthalate (T) and hexamethylenediamine (6) groups. The length of the segments making up the soft phase was varied from 600 to 10,000 g/mol. The water absorption of the PEO-based copolymers was found to increase exponentially with the PEO concentration. The modulus and yield strength decreased with water absorption and this effect seemed to be mainly the result of a lowering hard segment content caused by their swelling with water. Upon wetting, the copolymers demonstrated an increased yield strain. Furthermore, the ultimate properties were sensitive to the hard segment content, the molecular weight of the copolymer and whether or not strain-hardening could take place. Upon wetting, the fracture stresses decreased whereas the fracture strains increased. The true fracture stresses of the wet samples were as high as those of the dry samples for reasonable amounts of absorbed water.