Cavitation-Mediated Fracture Energy Dissipation in Polylactide at Rubbery Soybean Oil-Based Block Copolymer Interfaces Formed via Reactive Extrusion.

Here, we spearhead a new approach to biopolymer impact modification that demonstrates superior performance while maintaining greater than 99% compostability. Using soybean-based monomers, a virtually untapped resource in terms of commercial volume and overall cost, a series of hyperbranched block copolymers were synthesized and melt-processed with poly(l-lactide) (PLA) to yield impact resistant all-polymer composites. Although PLA impact modification has been treated extensively, to date, the only practical solutions have relied on non-compostable petroleum-based rubbers. This study illustrates the activity of energy dissipation mechanisms such as cavitation, classically relegated to well-entangled petroleum-based rubbers, in poorly entangled hyperbranched soybean-based rubbers. Furthermore, we present a complete study of the mechanical performance and morphology of these impact modified PLA composites. The significance of combining deformation theory with a scalable green alternative to petroleum-based rubbers opens up a potential avenue for cheap compostable engineering thermoplastics.

Polystyrene-block-Polydimethylsiloxane as a Potential Silica Substitute for Polysiloxane Reinforcement.

Here we report microphase-separated poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) as a reinforcing filler in PDMS thermosets that overcomes the long-standing problem of aging in the processing of silica-reinforced silicone. Surprisingly, PS-b-PDMS reinforced composites display comparable mechanical performance to silica-modified analogs, even though the modulus of PS is much smaller than that of silica and there is no evidence of percolation with respect to the rigid PS domains. We have found that a few unique characteristics contribute to the reinforcing performance of PS-b-PDMS. The strong self-assembly behavior promotes batch-to-batch repeatability by having well-dispersed fillers. The structure and size of the fillers depend on the loading and characteristics of both filler and matrix, along with the shear effect. The reinforcing effect of PS-b-PDMS is mostly brought by the entanglements between the corona layer of the filler and the matrix, rather than the hydrodynamic reinforcement of the PS phase.

Gel Point Suppression in RAFT Polymerization of Pure Acrylic Cross-Linker Derived from Soybean Oil.

Here we report the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylated epoxidized soybean oil (AESO), a cross-linker molecule, to high conversion (>50%) and molecular weight (>100 kDa) without macrogelation. Surprisingly, gelation is suppressed in this system far beyond the expectations predicated both on Flory-Stockmeyer theory and multiple other studies of RAFT polymerization featuring cross-linking moieties. By varying AESO and initiator concentrations, we show how intra- versus intermolecular cross-linking compete, yielding a trade-off between the degree of intramolecular linkages and conversion at gel point. We measured polymer chain characteristics, including molecular weight, chain dimensions, polydispersity, and intrinsic viscosity, using multidetector gel permeation chromatography and NMR to track polymerization kinetics. We show that not only the time and conversion at macrogelation, but also the chain architecture, is largely affected by these reaction conditions. At maximal AESO concentration, the gel point approaches that predicted by the Flory-Stockmeyer theory, and increases in an exponential fashion as the AESO concentration decreases. In the most dilute solutions, macrogelation cannot be detected throughout the entire reaction. Instead, cyclization/intramolecular cross-linking reactions dominate, leading to microgelation. This work is important, especially in that it demonstrates that thermoplastic rubbers could be produced based on multifunctional renewable feedstocks.

Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar.

Biorefineries aim to convert biomass into a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps. In this work, a route that combines bio- and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L(-1) in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94 % yield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.

The battle for the "green" polymer. Different approaches for biopolymer synthesis: bioadvantaged vs. bioreplacement.

Biopolymers have been used throughout history; however, in the last two centuries they have seen a decrease in their utilization as the proliferation of inexpensive and mass-produced materials from petrochemical feedstocks quickly became better-suited to meeting society's needs. In recent years, high petroleum prices and the concern of society to adopt greener and cleaner products has led to an increased interest in biorenewable polymers and the use of sustainable technologies to produce them. Industrial and academic researchers alike have targeted several routes for producing these renewable materials. In this perspective, we compare and contrast two distinct approaches to the economical realization of these materials. One mentality that has emerged we term "bioreplacement", in which the fields of synthetic biology and catalysis collaborate to coax petrochemical monomers from sugars and lignocellulosic feedstocks that can subsequently be used in precisely the same ways to produce precisely the same polymers as we know today. For example, the metabolic engineering of bacteria is currently being explored as a viable route to common monomers such as butadiene, isoprene, styrene, acrylic acid, and sebacic acid, amongst others. Another motif that has recently gained traction may be referred to as the "bioadvantage" strategy, where the multifunctional "monomers" given to us by nature are combined in novel ways using novel chemistries to yield new polymers with new properties; for these materials to compete with their petroleum-based counterparts, they must add some advantage, for example less cost. For instance, acrylated epoxidized soybean oil readily undergoes polymerization to thermosets and recently, thermoplastic rubbers. Additionally, many plants produce pre-polymeric or polymeric materials that require little or no post modification to extract and make use of these compounds.