Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets.

The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct and irreconcilable. Yet, the past two decades have seen extensive development of materials that bridge this gap through incorporation of dynamic crosslinks, enabling them to behave as both robust networks and moldable plastics. Although their potential utility is significant, the growth of covalent adaptable networks (CANs) has obscured the line between "thermoplastic" and "thermoset" and erected a conceptual barrier to the growing number of new researchers entering this discipline. This Perspective aims to both outline the fundamental theory of CANs and provide a critical assessment of their current status. We emphasize throughout that the unique properties of CANs emerge from the network chemistry, and particularly highlight the role that the crosslink exchange mechanism (i.e., dissociative exchange or associative exchange) plays in the resultant material properties under processing conditions. Predominant focus will be on thermally induced dynamic behavior, as the majority of presently employed exchange chemistries rely on thermal stimulus, and it is simple to apply to bulk materials. Lastly, this Perspective aims to identify current issues and address possible solutions for better fundamental understanding within this field.

Photocrosslinkable Polymeric Bicontinuous Microemulsions.

We present an approach to photocrosslink bicontinuous microemulsions derived from ternary blends of poly(methoxyethyl acrylate) (PM, Mn = 4200 g/mol), poly(hexyl methacrylate-co-coumarin methacrylate) (PHC, Mn = 6800 g/mol), and PM-b-PHC diblock polymer (Mn = 19,400 g/mol) in a phase-selective manner, enabling structural characterization at an unprecedented level of detail. This strategy utilizes the [2 + 2] photodimerization reaction of coumarin derivatives to covalently crosslink blends without the use of harsh reagents or disruptive thermal treatment, thus preserving the intricate network structure throughout curing. The resulting crosslinked bicontinuous microemulsions exhibited rubbery behavior at elevated temperatures, achieving an elastic shear modulus of nearly 1 MPa at 70 °C, owing to the presence of the three-dimensional co-continuous network morphology. The dimensional stabilization afforded by crosslinking further allowed the microstructure to be directly imaged by scanning electron microscopy and atomic force microscopy. Contrary to recent theoretical findings, the BµE appears in a wide temperature and compositional window, suggesting that it is a robust feature of these blends. As a proof of concept demonstrating both the utility of bicontinuous microemulsion-derived materials and versatility of this strategy toward broader applications in energy storage and transport, the uncrosslinked portion of a cured blend was extracted by washing and replaced with an ionic liquid; the resultant heterogeneous solid electrolyte exhibited a room-temperature conductivity of 2 mS/cm, approximately one-quarter that of the pure ionic liquid.

Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers.

A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order-disorder transition temperature (TODT) significantly. Additionally, the effective Flory-Huggins interaction parameter (χeff) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. We therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.

Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization.

As many physical properties of polymers scale with molecular weight, the ability to achieve polymers of nearly inaccessibly high molecular weight provides an opportunity to probe the upper size limit of macromolecular phenomena. Yet many of the most stimulating macromolecular designs remain out of reach of current ultrahigh molecular weight (UHMW) polymer synthetic approaches. Herein, we show that UHMW polymers of diverse composition can be achieved by irradiation of thiocarbonylthio photoiniferters with long-wave ultraviolet or visible light in concentrated organic solution. This facile photopolymerization strategy is general to acrylic-, acrylamido-, methacrylic-, and styrenic-based monomers, enabling the synthesis of well-defined macromolecules with molecular weights in excess of 106 g/mol. The high chain-end fidelity afforded by photoiniferter polymerization conditions facilitated the design of UHMW amphiphilic block copolymers, which were found to self-assemble into micellar morphologies up to 200 nm in diameter.

Influence of an immune-modulatory feed supplement on performance and immune function of beef cows and calves preweaning.

The ability to positively alter immune and stress response with nutritional compounds is of great interest and importance to the beef industry. There is a proprietary product (OmniGen-AF [OG]; Phibro Animal Health, Quincy, IL) reported to have performance-enhancing benefits by altering animal response to stress and immune challenges. The objective of this 2-yr research project was to study the effect of supplementing OG to beef cows and their calves on breeding and growth performance. One hundred and twelve multiparous beef cows and 48 primiparous cows were randomly assigned to treatment in year 1; control (CON, no OG; n = 56 multiparous and 24 primiparous) or treatment (OG fed at 8.8 g/100 kg body weight [BW]; n = 56 multiparous and 24 primiparous). Multiparous cows (mean ± SD = 6.4 ± 0.4 yr; BW = 589 ± 9.2 kg; body condition score [BCS] 6.2 ± 0.07) were used in both years of the experiment and primiparous cows (mean ± SD = 2.1 ± 0.04 yr of age, weighed 400 ± 7.5 kg, and BSC of 5.6 ± 0.06) were only used in the first year of the experiment. CON and OG supplements were offered over two production cycles beginning in December approximately 60 d prior to projected calving through pre-breeding in May of each year. Calves from treatment cows were offered treatments in a creep supplement limited to a daily rate of 1% as-fed of BW prorated for 3-d/wk feeding from mid-July through weaning with OG offered at 8.8 g/100 kg BW. Primiparous cow's BW, BCS, and calf performance were not affected by treatment (P ≥ 0.15) in year 1. BW of multiparous OG cows tended (P = 0.10) to be heavier at weaning in year 1 and was greater (P = 0.05) at the onset of the experiment in year 2. Body condition of OG cows was greater (P ≤ 0.02) at weaning in both years 1 and 2, as well as at the onset of the experiment in year 2. Calves fed OG from the mature cows gained more (P = 0.05) BW during the creep feeding period than CON. Core body temperatures of OG heifers measured during the late summer with intravaginal temperature data loggers tended (P ≤ 0.10) to be less at 1400 and 1700 hours and were less (P = 0.05) at 1800 hours than CON heifers. Feeding OG did not result in changes (P = 0.25) in serum titer response to the BVD virus of calves during year 2. The results of the current experiment indicate feeding OG to beef cows and calves can result in improvement in BCS of cows, enhance weight gain of calves preweaning, and reduce heat loads in heifer calves during the late summer.