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Structure Development in Cross-Linked, Soybean Oil-based Waterborne Polyurethanes

Development of waterborne polyurethanes (WPU) using bio-based sources represents a step towards sustainable materials science and industry. We synthesized bio-based cationic water-dispersed crosslinked polyurethanes from high oleic soybean oil (HOSO) polyol, isophorone diisocyanate, and methyldiethanol amine, with varying ionic group contents after neutralization with acetic acid. Our primary objective was to analyze how crosslinking affects the dispersion process and film properties in multifunctional systems. The synthesis-structure-property relationship is elucidated through comprehensive analyses of the products at different stages of the synthesis. The dispersion of the WPU particles in water must occur prior to gelation during the final preparation, leading to incomplete conversion and the formation of imperfect networks. Insight into the synthesis process and polymer structure was gained by simulating polymer network parameters. Morphological analyses using synchrotron-based X-ray scattering and atomic force microscopy revealed a hierarchical structure within the WPU films. Importantly, all the films prepared in this study, without using coalescence agents, have low water absorption and high water contact angles, demonstrating their potential for textile and leather coatings and other applications.

bio-based polymers

Robust Self-Healing Adhesives Based on Dynamic Urethane Exchange Reactions

Thermoset polyurethanes (PUs) have been successfully reprocessed as covalent adaptable networks (CANs) by catalyzing carbamate exchange. Here we extend bond exchange beyond the internal network cross-links to create a dynamic urethane adhesive. Interfacing PU CANs to substrates with nucleophilic functional groups creates adhesives capable of reversible transcarbamoylation with the substrate, which has not been demonstrated previously by CAN adhesives. Two types of thermoset PU films were synthesized, one containing the green carbamate exchange catalyst Zr(tmhd)4 and the other containing no catalyst. Although otherwise identical in chemical and network properties, as indicated by FT-IR spectroscopy and dynamic mechanical thermal analysis (DMTA), the film containing catalyst showed dynamic bond exchange behavior through stress relaxation analysis. When evaluated as an adhesive, the CAN film exhibited self-healing properties and retained its adhesive strength for five cycles, which is attributed to reversible covalent bonding to the glass substrate. Furthermore, this work expands industrially relevant CANs to structural adhesives and demonstrates their potential value in an application that presently employs PUs as single-use materials.

adhesive

Synthesis, Properties, and Metathesis Activity of Polyurethane Thermoplastics and Thermosets from a Renewable Polysesquiterpene Diol

Polyurethanes (PUs) are the sixth most commonly utilized plastic class, yet ∼80% of commodity material is landfilled or incinerated at the end of life. Disposal of thermosets is particularly problematic as cross-linking prevents the repurposing of disposed material. Thus, there is considerable interest in the development of PUs derived from inexpensive feedstocks that can be inherently chemically deconstructed. Ring opening metathesis polymerization (ROMP) of the naturally occurring sesquiterpene β-caryophyllene in the presence of dihydroxy chain terminators afforded the polyol hydroxy-terminated polycaryophyllene (HTPCR). Incorporation of HTPCR into PUs through reaction with polyisocyanates produced polymers with thermal and rheological properties comparable to commodity materials. The feasibility of chemical degradation of both thermoplastic and thermoset materials was also demonstrated through ruthenium-mediated metathesis, utilizing the metathesis-active olefins within the repeat caryophyllene monomer unit. Overall, this work highlights the value of biorenewable, chemically reprocessable polysesquiterpenes in the PU space.

materials

Tissue simulating gel for medical research

A tissue simulating gel and a method for preparing the tissue simulating gel are disclosed. The tissue simulating gel is prepared by a process using water, gelatin, ethylene gylcol, and a cross-linking agent. In order to closely approximate the characteristics of the type of tissue being simulated, other material has been added to change the electrical, sound conducting, and wave scattering properties of the tissue simulating gel. The result of the entire process is a formulation that will not melt at the elevated temperatures involved in hyperthermia medical research. Furthermore, the tissue simulating gel will not support mold or bacterial growth, is of a sufficient mechanical strength to maintain a desired shape without a supporting shell, and is non-hardening and non-drying. Substances were injected into the tissue simulating gel prior to the setting-up thereof just as they could be injected into actual tissue, and the tissue simulating gel is translucent so as to permit visual inspection of its interior. A polyurethane spray often used for coating circuit boards can be applied to the surface of the tissue simulating gel to give a texture similar to human skin, making the tissue simulating gel easier to handle and contributing to its longevity.

Companion, John A.

Tissue simulating gel for medical research

A tissue simulating gel and a method for preparing the tissue simulating gel are disclosed. The tissue simulating gel is prepared by a process using water, gelatin, ethylene glycol, and a cross-linking agent. In order to closely approximate the characteristics of the type of tissue being simulated, other material has been added to change the electrical, sound conducting, and wave scattering properties of the tissue simulating gel. The result of the entire process is a formulation that will not melt at the elevated temperatures involved in hyperthermia medical research. Furthermore, the tissue simulating gel will not support mold or bacterial growth, is of a sufficient mechanical strength to maintain a desired shape without a supporting shell, and is non-hardening and non-drying. Substances have been injected into the tissue simulating gel prior to the setting-up thereof just as they could be injected into actual tissue, and the tissue simulating gel is translucent so as to permit visual inspection of its interior. A polyurethane spray often used for coating circuit boards can be applied to the surface of the tissue simulating gel to give a texture similar to human skin, making the tissue simulating gel easier to handle and contributing to its longevity.

Companion, John A.

Inline Electrical Connector Mate/Demate Pliers

Military and aerospace industries use Mil-Spec type electrical connections on bulkhead panels that require inline access for mate and demate operations. These connectors are usually in tight proximity to other connectors, or recessed within panels. The pliers described here have been designed to work in such tight spaces, and consist of a mirrored set of parallel handles, two cross links, two return springs, and replaceable polyurethane-coated end effectors. The polyurethane eliminates metal-to-metal contact and provides a high-friction surface between the jaw and the connector. Operationally, the user would slide the pliers over the connector shell until the molded polyurethane lip makes contact with the connector shell edge. Then, by squeezing the handles, the end effector jaws grip the connector shell, allowing the connector to be easily disconnected by rotating the pliers. Mating the connector occurs by reversing the prescribed procedure, except the connector shell is placed into the jaws by hand. The molded lip within the jaw allows the user to apply additional force for difficult-to-mate connectors. Handle design has been carefully examined to maximize comfort, limit weight, incorporate tether locations, and improve ergonomics. They have been designed with an off-axis offset for wiring harness clearance, while placing the connector axis of rotation close to the user s axis of wrist rotation. This was done to eliminate fatigue during multiple connector panel servicing. To limit handle opening width, with user ergonomics in mind, the pliers were designed using a parallel jaw mechanism. A cross-link mechanism was used to complete this task, while ensuring smooth operation.

Yutko, Brian

Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

Leventis, Nicholas