Predicting the Plateau Modulus from Molecular Parameters of Conjugated Polymers.

The relationship between Kuhn length l k , Kuhn monomer volume v 0, and plateau modulus G N 0, initially proposed by Graessley and Edwards for flexible polymers, and extended by Everaers, has a large gap in experimental data between the flexible and stiff regimes. This gap prevents the prediction of mechanical properties from the chain structure for any polymer in this region. Given the chain architecture, including a semiflexible backbone and side chains, conjugated polymers are an ideal class of material to study this crossover region. Using small angle neutron scattering, oscillatory shear rheology, and the freely rotating chain model, we have shown that 12 polymers with aromatic backbones populate a large part of this gap. We also have shown that a few of these polymers exhibit nematic ordering, which lowers G N 0. When fully isotropic, these polymers follow a relationship between l k , v 0, and G N 0, with a simple crossover proposed in terms of the number of Kuhn segments in an entanglement strand N e.

Carbon Nanotube Composites with Bottlebrush Elastomers for Compliant Electrodes.

Wearable electronics and biointerfacing technology require materials that are both compliant and conductive. The typical design strategy exploits polymer composites containing conductive particles, but the addition of a hard filler generally leads to a substantial increase in modulus that is not well-matched to biological tissue. Here, we report a new class of supersoft, conductive composites comprising carbon nanotubes (CNT) embedded in bottlebrush polymer networks. By virtue of the bottlebrush polymer architecture, these materials are several orders of magnitude softer than comparable composites in the literature involving linear polymer networks. For example, a CNT content of 0.25 wt % yields a shear modulus of 66 kPa while maintaining a typical conductivity for a CNT composite (ca. 10-2 S/m). An added benefit of this bottlebrush matrix chemistry is the presence of dynamic polyester bonds that facilitate thermal (re)processing. This unique strategy of designing soft composites provides new opportunities to tailor the structure and properties of sustainable advanced materials.

Room temperature 3D printing of super-soft and solvent-free elastomers.

Super-soft elastomers derived from bottlebrush polymers show promise as advanced materials for biomimetic tissue and device applications, but current processing strategies are restricted to simple molding. Here, we introduce a design concept that enables the three-dimensional (3D) printing of super-soft and solvent-free bottlebrush elastomers at room temperature. The key advance is a class of inks comprising statistical bottlebrush polymers that self-assemble into well-ordered body-centered cubic sphere phases. These soft solids undergo sharp and reversible yielding at 20°C in response to shear with a yield stress that can be tuned by manipulating the length scale of microphase separation. The addition of a soluble photocrosslinker allows complete ultraviolet curing after extrusion to form super-soft elastomers with near-perfect recoverable elasticity well beyond the yield strain. These structure-property design rules create exciting opportunities to tailor the performance of 3D-printed elastomers in ways that are not possible with current materials and processes.

Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials.

We introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side chains were cross-linked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress-relaxation rates at elevated temperatures (160-180 °C) due to dynamic ester cross-links that undergo transesterification with residual hydroxy groups. Varying the cross-linker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10-100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.

Glass transition temperature from the chemical structure of conjugated polymers.

The glass transition temperature (Tg) is a key property that dictates the applicability of conjugated polymers. The Tg demarks the transition into a brittle glassy state, making its accurate prediction for conjugated polymers crucial for the design of soft, stretchable, or flexible electronics. Here we show that a single adjustable parameter can be used to build a relationship between the Tg and the molecular structure of 32 semiflexible (mostly conjugated) polymers that differ drastically in aromatic backbone and alkyl side chain chemistry. An effective mobility value, ζ, is calculated using an assigned atomic mobility value within each repeat unit. The only adjustable parameter in the calculation of ζ is the ratio of mobility between conjugated and non-conjugated atoms. We show that ζ correlates strongly to the Tg, and that this simple method predicts the Tg with a root-mean-square error of 13 °C for conjugated polymers with alkyl side chains.

Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers.

All conjugated polymers examined to date exhibit significant cumulative lattice disorder, although the origin of this disorder remains unclear. Using atomistic molecular dynamics (MD) simulations, the detailed structures for single crystals of a commonly studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) are obtained. It is shown that thermal fluctuations of thiophene rings lead to cumulative disorder of the lattice with an effective paracrystallinity of about 0.05 in the π-π stacking direction. The thermal-fluctuation-induced lattice disorder can in turn limit the apparent coherence length that can be observed in diffraction experiments. Calculating mobilities from simulated crystal structures demonstrates that thermal-fluctuation-induced lattice disorder even enhances charge transport in P3HT. The mean inter-chain charge transfer integral is enhanced with increasing cumulative lattice disorder, which in turn leads to pathways for fast charge transport through crystals.