Accessing pluripotent materials through tempering of dynamic covalent polymer networks.

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Inspired by this concept, we report synthetic polymers that act as a single "pluripotent" feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.

Doubly Threaded Slide-Ring Polycatenane Networks.

Crosslinking in polymer networks leads to intrinsic structural inhomogeneities that result in brittle materials. Replacing fixed covalent crosslinks with mobile ones in mechanically interlocked polymers (MIPs), such as in slide-ring networks (SRNs) in which interlocked crosslinks are formed when polymer chains are threaded through crosslinked rings, can lead to tougher, more robust networks. An alternative class of MIPs is the polycatenane network (PCN), in which the covalent crosslinks are replaced with interlocked rings that introduce the unusual catenane's mobility elements (elongation, rotation, and twisting) as connections between polymer chains. A slide-ring polycatenane network (SR-PCN), with doubly threaded rings embedded as crosslinks in a covalent network, combines the mobility features of both the SRNs and PCNs, where the catenated ring crosslinks can slide along the polymer backbone between the two limits of network bonding (covalent and interlocked). This work explores using a metal ion-templated doubly threaded pseudo[3]rotaxane (P3R) crosslinker, combined with a covalent crosslinker and a chain extender, to access such networks. A catalyst-free nitrile-oxide/alkyne cycloaddition polymerization was used to vary the ratio of P3R and covalent crosslinker to yield a series of SR-PCNs that vary in the amount of interlocked crosslinking units. Studies on their mechanical properties show that metal ions fix the rings in the network, leading to similar behavior as the covalent PEG gels. Removal of the metal ion frees the rings resulting in a high-frequency transition attributed to the additional relaxation of polymer chains through the catenated rings while also increasing the rate of poroelastic draining at longer timescales.

Designing Stress-Adaptive Dense Suspensions Using Dynamic Covalent Chemistry.

The non-Newtonian behaviors of dense suspensions are central to their use in technological and industrial applications and arise from a network of particle-particle contacts that dynamically adapt to imposed shear. Reported herein are studies aimed at exploring how dynamic covalent chemistry between particles and the polymeric solvent can be used to tailor such stress-adaptive contact networks, leading to their unusual rheological behaviors. Specifically, a room temperature dynamic thia-Michael bond is employed to rationally tune the equilibrium constant (K eq) of the polymeric solvent to the particle interface. It is demonstrated that low K eq leads to shear thinning, while high K eq produces antithixotropy, a rare phenomenon where the viscosity increases with shearing time. It is proposed that an increase in K eq increases the polymer graft density at the particle surface and that antithixotropy primarily arises from partial debonding of the polymeric graft/solvent from the particle surface and the formation of polymer bridges between particles. Thus, the implementation of dynamic covalent chemistry provides a new molecular handle with which to tailor the macroscopic rheology of suspensions by introducing programmable time dependence. These studies open the door to energy-absorbing materials that not only sense mechanical inputs and adjust their dissipation as a function of time or shear rate but also can switch between these two modalities on demand.

Relative effects of polymer composition and sample preparation on glass dynamics.

Modern design of common adhesives, composites and polymeric parts makes use of polymer glasses that are stiff enough to maintain their shape under a high stress while still having a ductile behavior after the yield point. Typically, material compositions are tuned with co-monomers, polymer blends, plasticizers, or other additives to arrive at a tradeoff between the elastic modulus and toughness. In contrast, strong changes to the mechanics of a glass are possible by changing only the molecular packing during vitrification or even deep in the glassy state. For example, physical aging or processing techniques such as physical vapor deposition increase the density, embrittle the material, and increase elastic modulus. Here, we use molecular simulations, validated by positron annihilation lifetime spectroscopy (PALS) and quasi-elastic neutron scattering, to understand the free volume distribution and the resulting dynamics of glassy co-polymers where the composition is systemically varied between polar 5-norbornene-2-methanol (NBOH) and non-polar ethylidene norbornene (ENB) monomers. In these polymer glasses, we analyze the structural features of the unoccupied volume using clustering analysis, where the clustering is parameterized to reproduce experimental measurements of the same features from PALS. Further, we analyze the dynamics, quantified by the Debye-Waller factor, and compare the results with softer, lower density states. Our findings indicate that faster structural relaxations and potentially improved ductility are possible through changes to the geometric structure and fraction of the free volume, and that the resulting changes to the glass dynamics are comparable to large changes in the monomer composition.

Modeling Brittle Fractures in Epoxy Nanocomposites Using Extended Finite Element and Cohesive Zone Surface Methods.

Linear elastic fracture modeling coupled with empirical material tensile data result in good quantitative agreement with the experimental determination of mode I fracture for both brittle and toughened epoxy nanocomposites. The nanocomposites are comprised of diglycidyl ether of bisphenol A cured with Jeffamine D-230 and some were filled with core-shell rubber nanoparticles of varying concentrations. The quasi-static single-edge notched bending (SENB) test is modeled using both the surface-based cohesive zone (CZS) and extended finite element methods (XFEM) implemented in the Abaqus software. For each material considered, the critical load predicted by the simulated SENB test is used to calculate the mode I fracture toughness. Damage initiates in these models when nodes at the simulated crack tip attain the experimentally measured yield stress. Prediction of fracture processes using a generalized truncated linear traction-separation law (TSL) was significantly improved by considering the case of a linear softening function. There are no adjustable parameters in the XFEM model. The CZS model requires only optimization of the element displacement at the fracture parameter. Thus, these continuum methods describe these materials in mode I fracture with a minimum number of independent parameters.

Supramolecular Salts for Additive Manufacturing of Polyimides.

Recent advances in vat photopolymerization (VP) additive manufacturing of fully aromatic polyimides employed photoreactive high-molecular-weight precursors dissolved at modest loadings (<20 wt %) in organic solvent. These earlier efforts revealed high isotropic shrinkage, approaching 52% on a linear basis while converting to the desired polyimide. To increase the polyimide precursor concentration and decrease shrinkage during VP processing of high-performance polyimides, photoreactive fully aromatic polyimide and thermoplastic polyetherimide (PEI) supramolecular salt precursors now serve as versatile alternatives. Both pyromellitic dianhydride-4,4'-oxydianiline (PMDA-ODA) and 4,4'-(4,4'-isopropylidene-diphenoxy)diphthalic anhydride-meta phenylene diamine (BPADA-mPD) supramolecular dicarboxylate-diammonium salts, termed polysalts, provided prerequisite rheological performance and photoreactivity for VP. Solutions (50 wt %) of both photoactive polysalts exhibited viscosities more than two orders of magnitude lower than previously reported polyimide precursor solutions for VP. In addition, VP of 50 wt % polysalt solutions yielded high resolution, self-supporting organogel structures. During thermal postprocessing to the desired fully aromatic polyimide and PEI, photocrosslinked polysalt organogels exhibited retention of part shape in concert with linear isotropic shrinkage of only 26%, the lowest reported value using organogel strategies for VP of fully aromatic polyimides. Furthermore, the imidized structures exhibited comparable thermal and mechanical properties to analogous polyimides synthesized using classical methodologies for 2D films. The combination of facile synthesis and increased precursor concentrations designates polysalt polyimide precursors as a versatile platform for additive manufacturing of well-defined 3D polyimide structures.

Hebbian Learning on Small Data Enables Experimental Discovery of High Tg Polyimides.

We report a study combining computational design and experimental evaluation of polyimides with high glass transition temperatures: Tg between 220 °C and 500 °C. The computational approach is based on the recently introduced competitive learning algorithm, supervised self-organizing maps (SUSI), which we recast as an ensemble method, e-SUSI. We use e-SUSI to solve both unsupervised and supervised/semisupervised learning tasks capturing structure-property relationships of high-Tg polyimides historically studied at Almaden Research Center. Predictors trained on historical data were applied to the combinatorial library of novel polyimides and informed selection of the candidates for synthesis and characterization. In this manner, three new polyimides were prepared with Tg values 281 °C, 282 °C, and 331 °C. The measured values closely agree with the predicted values 273 °C, 311 °C, and 335 °C, respectively. We discuss specific reasons that make the proposed computational design strategy attractive in rapid, deliverable-driven efforts with limited, small-batch data sets.

The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C-N Cross-Coupling.

Palladium-catalyzed amination reactions using soluble organic bases have provided a solution to the many issues associated with heterogeneous reaction conditions. Still, homogeneous C-N cross-coupling approaches cannot yet employ bases as weak and economical as trialkylamines. Furthermore, organic base-mediated methods have not been developed for Ni(0/II) catalysis, despite some advantages of such systems over those employing Pd-based catalysts. We designed a new air-stable and easily prepared Ni(II) precatalyst bearing an electron-deficient bidentate phosphine ligand that enables the cross-coupling of aryl triflates with aryl amines using triethylamine (TEA) as base. The method is tolerant of sterically congested coupling partners, as well as those bearing base- and nucleophile-sensitive functional groups. With the aid of density functional theory (DFT) calculations, we determined that the electron-deficient auxiliary ligands decrease both the pKa of the Ni-bound amine and the barrier to reductive elimination from the resultant Ni(II)-amido complex. Moreover, we determined that the preclusion of Lewis acid-base complexation between the Ni catalyst and the base, due to steric factors, is important for avoiding catalyst inhibition.

Nickel-Mediated Cross-Coupling of Boronic Acids and Phthalimides for the Synthesis of Ortho-Substituted Benzamides.

The decarbonylative coupling of phthalimides with aryl boronic acids provides ready access to a broad range of ortho-substituted benzamides. This nickel-mediated methodology extends reactivity from previously described air-sensitive diorganozinc reagents of limited availability to easily handled and widely commercially available boronic acids. The decarbonylative coupling is tolerant of a broad range of functional groups and demonstrates little sensitivity to steric factors on either of the coupling partners.

Pd-Catalyzed C-N Coupling Reactions Facilitated by Organic Bases: Mechanistic Investigation Leads to Enhanced Reactivity in the Arylation of Weakly Binding Amines.

The ability to use soluble organic amine bases in Pd-catalyzed C-N cross-coupling reactions has provided a long-awaited solution to the many issues associated with employing traditional, heterogeneous reaction conditions. However, little is known about the precise function of these bases in the catalytic cycle and about the effect of variations in base structure on catalyst reactivity. We used 19F NMR to analyze the kinetic behavior of C-N coupling reactions facilitated by different organic bases. In the case of aniline coupling reactions employing DBU, the resting state was a DBU-bound oxidative addition complex, LPd(DBU)(Ar)X, and the reaction was found to be inhibited by base. In general, however, depending on the binding properties of the chosen organic base, increased concentration of the base can have a positive or negative influence on the reaction rate. Furthermore, the electronic nature of the aryl triflate employed in the reaction directly affects the reaction rate. The fastest reaction rates were observed with electronically neutral aryl triflates, while the slowest were observed with highly electron-rich and -deficient substrates. We propose a model in which the turnover-limiting step of the catalytic cycle depends on the relative nucleophilicity of the base compared to that of the amine. This hypothesis guided the discovery of new reaction conditions for the coupling of weakly binding amines, including secondary aryl amines, which were unreactive nucleophiles in our original protocol.

Breaking the Base Barrier: An Electron-Deficient Palladium Catalyst Enables the Use of a Common Soluble Base in C-N Coupling.

Due to the low intrinsic acidity of amines, palladium-catalyzed C-N cross-coupling has been plagued continuously by the necessity to employ strong, inorganic, or insoluble bases. To surmount the many practical obstacles associated with these reagents, we utilized a commercially available dialkyl triarylmonophosphine-supported palladium catalyst that facilitates a broad range of C-N coupling reactions in the presence of weak, soluble bases. The mild and general reaction conditions show extraordinary tolerance for even highly base-sensitive functional groups. Additionally, insightful heteronuclear NMR studies using 15N-labeled amine complexes provide evidence for the key acidifying effect of the cationic palladium center.

Rhodium-Catalyzed Interconversion of Quinolinyl Ketones with Boronic Acids via C-C Bond Activation.

A rhodium-catalyzed cross-coupling of aryl and aliphatic quinolinyl ketones with boronic acids has been developed. Proceeding via quinoline-directed carbon-carbon σ bond activation, the transformation demonstrates tolerance of a range of functional groups on both the ketone and aryl boronic acid substrates, providing good to excellent yields of the new ketones, particularly those containing electron-withdrawing substituents. Catalyst reactivity is dependent on quinolinyl ketone substrates, with alkyl ketones requiring Rh(PPh3)3Cl instead of the more reactive [Rh(C2H4)2Cl]2. With the use of K2CO3 as an additive, methyl boronic acid is also a competent substrate, giving rise to an unprecedented methylation technique.