Gregory I. Peterson

We describe the preparation and characterization of photo- and mechanochromic 3D-printed structures using a commercial fused filament fabrication printer. Three spiropyran-containing poly(ε-caprolactone) (PCL) polymers were each filamentized and used to print single- and multicomponent tensile testing specimens that would be difficult, if not impossible, to prepare using traditional manufacturing techniques. It was determined that the filament production and printing process did not degrade the

Self-immolative polymers (SIPs) are unique macromolecules that are able to react to multiple types of environmental influences by giving amplified response outputs. When triggering moieties installed at SIP chain ends are activated by their corresponding stimuli, a spontaneous head-to-tail depolymerization ensues, often involving multitopic release of small molecules. SIP designs have evolved a high degree of modularity in each of their functional components, enabling a broad range of utility an

Shape memory materials have emerged as an important class of materials in medicine due to their ability to change shape in response to a specific stimulus, enabling the simplification of medical procedures, use of minimally invasive techniques, and access to new treatment modalities. Shape memory polymers, in particular, are well suited for such applications given their excellent shape memory performance, tunable materials properties, minimal toxicity, and potential for biodegradation and resorp

We describe an efficient method to produce objects comprising spatially controlled and graded cross-link densities using vat photopolymerization additive manufacturing (AM). Using a commercially available diacrylate-based photoresin, 3D printer, and digital light processing (DLP) projector, we projected grayscale images to print objects in which the varied light intensity was correlated to controlled cross-link densities and associated mechanical properties. Cylinder and bar test specimens were

The influence of ball-mill grinding process parameters and polymer properties on the mechanochemical degradation of amorphous polymers was explored. For process parameters, the grinding frequency was found to have the greatest impact on the degradation rates of polystyrene (PS), with ca. 17 times difference in rate constants between the lowest and the highest frequencies studied. For polymer properties, molecular weight and molecular weight dispersity were shown to both influence degradation rat

Metathesis cyclopolymerization (CP) of α,ω-diynes is a powerful method to prepare functional polyacetylenes (PAs). PAs have long been studied due to their interesting electrical, optical, photonic, and magnetic properties which make them candidates for use in various advanced applications. Grubbs catalysts are widely used throughout synthetic chemistry, largely due to their accessibility, high reactivity, and tolerance to air, moisture, and many functional groups. Prior to our entrance into this

New polyphenylene-based dendronized polymers (denpols), exhibiting extended and rigid conformations, were prepared using ring-opening metathesis polymerization (ROMP). Their mechanochemical degradation was explored in ultrasound-induced elongational flow fields. Degradation rate constants were obtained for polyphenylene-based denpols, of varying generation, across a degree of polymerization (DP) range of ∼100-600. In general, it was found that larger side chains led to increased degradation rate

Polymer architecture is an important factor in polymer mechanochemistry. In this Feature Article, we summarize recent developments in utilizing polymer architecture to modulate mechanochemical reactions within polymers, or more specifically, the location and rates of bond scission events that lead to polymer fragmentation or mechanophore activation. Various well-defined architectures have been explored, including those of cyclic, intramolecularly cross-linked, dendritic, star, bottlebrush, and d

We explored the mechanochemical degradation of bottlebrush and dendronized polymers in solution (with ultrasonication, US) and solid states (with ball-mill grinding, BMG). Over 50 polymers were prepared with varying backbone length and arm architecture, composition, and size. With US, we found that bottlebrush and dendronized polymers exhibited consistent backbone scission behavior, which was related to their elongated conformations in solution. Considerably different behavior was observed with

Typical multimechanophore polymers (MMPs) are comprised of numerous mechanophores (force-responsive moieties) distributed throughout the backbone of linear polymers. We have developed a new MMP design based on graft polymers with mechanophores linking each arm to the backbone. By utilizing maleimide–anthracene cycloadducts, polymeric species containing anthracene were released from the parent polymer, enabling facile quantification of mechanophore activation. With pulsed ultrasound experiments,

Traditionally, most polymerizations rely on simple reactions such as alkene addition, ring-opening, and condensation because they are robust, highly efficient, and selective. These reactions, however, generally only yield a single new C-C or C-O bond during each propagation step. In recent years, novel macromolecules have been prepared with propagation steps that involve cascade reactions, enabling various combinations of bond making and breaking steps to form more complex repeat units. These po

The ultrasonic degradation of polynorbornene-g-polylactide and polynorbornene-g-polystyrene brush polymers was explored. First-order rate constants for backbone scission were obtained for brush polymers with varying arm lengths (ranging ca. 3–8 kDa) and backbone degrees of polymerization (ranging ca. 78–361). Master curves, in which the rate constant trends for all polymers converge, could be generated by accounting for the rate enhancement from the polymer being in an extended conformation and

The thermal shape memory behavior of a series of α-amino acid-based poly(ester urea)s has been explored. We demonstrate that these materials exhibit excellent shape memory performance in dual- and triple-shape thermomechanical testing. Significant activation of chain mobility above the <i>T</i>_g as well as a hydrogen bonding network provide the basis for shape transformations and recovery. Additionally, we tuned the shape memory properties of these materials with polymer blending, ena

The thermal shape memory behavior of poly(ester urea)s (PEUs) composed of varying α-amino acids and linear diols has been explored. The thermal, mechanical, and shape memory properties of PEUs are shown to be controlled by changing the amino acid and diol components of the polymer, without negatively affecting the shape memory performance of the polymer in most cases. These materials display triple-shape memory behavior and temperature memory properties due to a broad glass transition temperatur