Megan L. Robertson

Tough Blends of Polylactide and Castor Oil

Poly(l-lactide) (PLLA) is a renewable resource polymer derived from plant sugars with several commercial applications. Broader implementation of the material is limited due to its inherent brittleness. We show that the addition of 5 wt % castor oil to PLLA significantly enhances the overall tensile toughness with minimal reductions in the modulus and no plasticization of the PLLA matrix. In addition, we used poly(ricinoleic acid)-PLLA diblock copolymers, synthesized entirely from renewable resources, as compatibilizers for the PLLA/castor oil blends. Ricinoleic acid, the majority fatty acid comprising castor oil, was polymerized through a lipase-catalyzed condensation reaction. The resulting polymers contained a hydroxyl end-group that was subsequently used to initiate the ring-opening polymerization of l-lactide. The binary PLLA/castor oil blend exhibited a tensile toughness seven times greater than neat PLLA. The addition of block copolymer allowed for control over the morphology of the blends, and even further improvement in the tensile toughness was realized-an order of magnitude larger than that of neat PLLA.

Biorenewable Tough Blends of Polylactide and Acrylated Epoxidized Soybean Oil Compatibilized by a Polylactide Star Polymer

Polylactide (PLA), a commercially available thermoplastic derived from plant sugars, finds applications in consumer products, disposable packaging, and textiles, among others. The widespread application of this material is limited by its brittleness, as evidenced by low tensile elongation at break, impact strength, and fracture toughness. Herein, a multifunctional vegetable oil, acrylated epoxidized soybean oil (AESO), was investigated as a biodegradable, renewable additive to improve the toughness of PLA. AESO was found to be a highly reactive oil, providing a dispersed phase with tunable properties in which the acrylate groups underwent cross-linking at the elevated temperatures required for processing the blends. Additionally, the presence of hydroxyl groups on AESO provided two routes for compatibilization of PLA/AESO blends: (1) reactive compatibilization through the transesterification of AESO and PLA and (2) synthesis of a PLA star polymer with an AESO core. The morphological, thermal, and mechanic...

Phase inversion in polylactide/soybean oil blends compatibilized by poly(isoprene-b-lactide) block copolymers.

Renewable composites were prepared by melt blending of polylactide and soybean oil. The blend morphology was tuned by the addition of poly(isoprene-b-lactide) block copolymers. Due to the extreme difference in the viscosities of soybean oil and polylactide, a critical block copolymer composition was found to induce a phase inversion point at which the minor soybean oil phase became the matrix surrounding polylactide particles. This transition was due to the thermodynamic interactions between the block copolymer and the two phases and shear forces acting on the mixture during blending. The size of the soybean oil droplets in the polylactide matrix was also highly dependent on the block copolymer composition. In binary polylactide/soybean oil blends, there was a limiting concentration of soybean oil that could be incorporated into the polylactide matrix (6% of the total blend weight), which could be increased up to 20% by the addition of block copolymers.

The future of plastics recycling

Chemical advances are increasing the proportion of polymer waste that can be recycled The environmental consequences of plastic solid waste are visible in the ever-increasing levels of global plastic pollution both on land and in the oceans. But although there are important economic and environmental incentives for plastics recycling, end-of-life treatment options for plastic solid waste are in practice quite limited. Presorting of plastics before recycling is costly and time-intensive, recycling requires large amounts of energy and often leads to low-quality polymers, and current technologies cannot be applied to many polymeric materials. Recent research points the way toward chemical recycling methods with lower energy requirements, compatibilization of mixed plastic wastes to avoid the need for sorting, and expanding recycling technologies to traditionally nonrecyclable polymers.

Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils

Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between polystyrene and short-chain polyacrylates (n ≤ 10). To our knowledge, this is the first study to explore the thermodynamic interactions between polystyrene and long-chain poly(n-alkyl acrylates) with n > 10. This work lays the groundwork for the development of multicomponent structured systems (i.e., blends and copolymers) in this class of sustainable materials.

Synthesis, Characterization, and Cross-Linking Strategy of a Quercetin-Based Epoxidized Monomer as a Naturally-Derived Replacement for BPA in Epoxy Resins.

The natural polyphenolic compound quercetin was functionalized and cross-linked to afford a robust epoxy network. Quercetin was selectively methylated and functionalized with glycidyl ether moieties using a microwave-assisted reaction on a gram scale to afford the desired monomer (Q). This quercetin-derived monomer was treated with nadic methyl anhydride (NMA) to obtain a cross-linked network (Q-NMA). The thermal and mechanical properties of this naturally derived network were compared to those of a conventional diglycidyl ether bisphenol A-derived counterpart (DGEBA-NMA). Q-NMA had similar thermal properties [i.e., glass transition (Tg ) and decomposition (Td ) temperatures] and comparable mechanical properties (i.e., Youngs Modulus, storage modulus) to that of DGEBA-NMA. However, it had a lower tensile strength and higher flexural modulus at elevated temperatures. The application of naturally derived, sustainable compounds for the replacement of commercially available petrochemical-based epoxies is of great interest to reduce the environmental impact of these materials. Q-NMA is an attractive candidate for the replacement of bisphenol A-based epoxies in various specialty engineering applications.

Tuning Bacterial Attachment and Detachment via the Thickness and Dispersity of a pH-Responsive Polymer Brush

We investigated the effect of two brush parameters, thickness and dispersity in the molecular weight distribution, on the adhesion of bacteria to pH-responsive poly(acrylic acid) (PAA) brushes synthesized using surface-initiated atom transfer radical polymerization. The attachment and detachment of Staphylococcus epidermidis to PAA brushes at pH 4 and pH 9, respectively, were examined with confocal microscopy. An optimal range of brush thickness, 13-18 nm, was identified for minimizing bacterial adhesion on PAA brushes at pH 4, and bacterial attachment did not depend on the brush dispersity. Increasing either the brush thickness or dispersity detached bacteria from the brushes when the pH was increased from 4 to 9. Bacterial detachment likely arose from an enhanced actuation effect in thick or high-dispersity brushes, as PAA brushes change conformation from collapsed to extended states when the pH is increased from 4 to 9. These results suggest that manipulating the molecular weight distribution provides a route to separately tune the attachment and detachment of bacteria.

Dispersity control in atom transfer radical polymerizations through addition of phenylhydrazine

Molar mass dispersity in polymers affects a wide range of important material properties, yet there are few synthetic methods that systematically generate unimodal distributions with specifically tailored dispersities. Here, we describe a general method for tuning the dispersity of polymers synthesized via atom transfer radical polymerization (ATRP). Addition of varying amounts of phenylhydrazine (PH) to the ATRP of tert-butyl acrylate led to significant deviations in the reaction kinetics, yielding poly(tert-butyl acrylate) with dispersities Đ = 1.08–1.80. ATRP reactions in the presence of the reducing agent tin(II) 2-ethylhexanoate, under otherwise comparable reaction conditions, did not drive similar increases in dispersity. We therefore deduced that PH does not function primarily as a reducing agent in these syntheses. Nuclear magnetic resonance analyses revealed the incorporation of aromatic polymer end-groups upon PH addition, suggesting that the ATRP-active halide termini of the growing polymer chains underwent irreversible nucleophilic substitution reactions with PH that led to chain termination. A kinetic model including this irreversible chain termination by PH was in excellent agreement with experimentally measured reaction kinetics. To demonstrate the generality of this approach, we conducted ATRP syntheses of polystyrene in the presence of PH to achieve dispersities of Đ = 1.07–2.30. This study suggests that PH addition is an effective, facile, and flexible method of dispersity control in polymers synthesized by ATRP.