The effective management of plastic waste streams to prevent plastic land and water pollution is a growing problem that is also one of the most important challenges in polymer science today. Polymer materials that are stable over their lifetime and can also be cheaply recycled or repurposed as desired could more easily be diverted from waste streams. However, this is difficult for most commodity plastics. It is especially difficult to conceive this with intractable, cross-linked polymers such as rubbers. In this work, we explore the utility of microencapsulated Grubbs’ catalysts for the in-situ depolymerization and reprocessing of polybutadiene (PB) rubber. Second-generation Hoveyda-Grubbs catalyst (HG2) contained within glassy thermoplastic microspheres can be dispersed in PB rubber below the microsphere’s glass transition temperature (Tg) without adverse depolymerization, evidenced by rubber with and without these microspheres obtaining similar shear storage moduli of ≈16 and ≈28 kPa, respectively. The thermoplastic’s Tg can be used to tune the depolymerization temperature, via release of HG2 into the rubber matrix. For example, using poly(lactic acid) (PLA) vs polysulfone results in an 85 and 162 °C depolymerization temperature, respectively. Liquefaction of rubber to a mixture of small molecules and oligomers is demonstrated using a 0.01 mol % catalyst loading using PLA as the encapsulant. At that same catalyst loading, depolymerization occurs to a greater extent in comparison to two ex-situ approaches, including a conventional solvent-assisted method, where it occurs at roughly twice the extent at each given catalyst loading. In addition, depolymerization of the microsphere-loaded rubbers was demonstrated for samples stored under nitrogen for 23 days. Lastly, we show that the depolymerized products can be reprocessed back into solid rubber with a shear storage modulus of ≈32 kPa. Thus, we envision that this approach could be used to recycle and reuse cross-linked rubbers at the end of their product lifetime.
Frontal polymerization involves the propagation of a thermally driven polymerization wave through a monomer solution to rapidly generate high-performance polymeric materials with little energy input. The balance between latent catalyst activation and sufficient reactivity to sustain a front can be difficult to achieve and often results in systems with poor storage lives. This is of particular concern for frontal ring-opening metathesis polymerization (FROMP) where gelation occurs within a single day of resin preparation due to the highly reactive nature of Grubbs-type catalysts. In this report we demonstrate the use of encapsulated catalysts to provide remarkable latency to frontal polymerization systems, specifically using the highly active dicyclopentadiene monomer system. Negligible differences were observed in the frontal velocities or thermomechanical properties of the resulting polymeric materials. FROMP systems with encapsulated catalyst particles are shown with storage lives exceeding 12 months and front rates that increase over a well-characterized 2 month period. Moreover, the modularity of this encapsulation method is demonstrated by encapsulating a platinum catalyst for the frontal polymerization of silicones by using hydrosilylation chemistry.
Solid state nuclear magnetic resonance (NMR) spectroscopy and small-to wide-angle X-ray scattering (SWAXS) methods were used to characterize the heterogeneous dynamics and polymer domain structure in rubber modified thermoset materials containing the diglycidyl ether of bisphenol A (DGEBA) epoxy resin and a mixture of Jeffamine reactive rubber and 4,4-diaminodicyclohexylmethane (PACM) amine curing agent. The polymer chain dynamics and morphologies as a function of the PACM/Jeffamine ratio were determined. Using dipolar-filtered NMR experiments, the resulting networks are shown to be composed of mobile and rigid regions that are separated on nanometer length scales, along with a dynamically immobilized interface region. Proton NMR spin diffusion experiments measured the dimensions of the mobile phase to range between 9 and 66 nm and varied with the relative PACM concentration. Solid state 13C magic angle spinning NMR experiments show that the highly mobile phase is composed entirely of the dynamically flexible polyether chains of the Jeffamine rubber, the immobilized interface region is a mixture of DGEBA, PACM, and the Jeffamine rubber, with the PACM cross-linked to DGEBA predominantly residing in the rigid phase. The SWAXS results showed compositional nanophase separation spanning the 11–77 nm range. These measurements of the nanoscale compositional and dynamic heterogeneity provide molecular level insight into the very broad and controllable glass transition temperature distributions observed for these highly cross-linked polymer networks.
Once limited to chain-growth polymerizations, fine control over polymerization-induced phase separation (PIPS) has recently been demonstrated in rubber-toughened thermoset materials formed through step-growth polymerizations. The domain length scales of these thermoset materials can be elegantly tuned by utilizing a binary mixture of curing agents (CAs) that individually yield disparate morphologies. Importantly, varying the composition of the binary mixture affects characteristics of the materials such as glass transition temperature and tensile behavior. Here, we establish a full phase diagram of PIPS in a rubber-toughened epoxy system tuned by a binary CA mixture to provide a robust framework of phase behaviour. X-Ray scattering in situ and post-PIPS is employed to elucidate the PIPS mechanism whereby an initial polymerization-induced compositional fluctuation causes nanoscale phase separation of rubber and epoxy components prior to local chain crosslinking and potential macrophase separation. We further demonstrate the universality of this approach by alternatively employing binary epoxy or binary rubber mixtures to achieve broad variations in morphology and glass transitions.
The development of chemistry is reported to implement selective dual-wavelength olefin metathesis polymerization for continuous additive manufacturing (AM). A resin formulation based on dicyclopentadiene is produced using a latent olefin metathesis catalyst, various photosensitizers (PSs) and photobase generators (PBGs) to achieve efficient initiation at one wavelength (e.g., blue light) and fast catalyst decomposition and polymerization deactivation at a second (e.g., UV-light). This process enables 2D stereolithographic (SLA) printing, either using photomasks or patterned, collimated light. Importantly, the same process is readily adapted for 3D continuous AM, with printing rates of 36 mm h–1 for patterned light and up to 180 mm h–1 using un-patterned, high intensity light.
Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate the morphology at these length scales are unsuitable for a majority of thermoset materials typically formed through step-growth mechanisms. By varying the composition of a binary curing agent mixture in a classic rubber-toughened epoxy thermoset, where the two curing agents are selected based on disparate compatibility with the rubber, we demonstrate facile tunability over morphology through a single compositional parameter. Indeed, this method yields morphologies spanning the nano-scale to the macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. We further demonstrate a profound connection between chain dynamics and microstructure in these materials, with the tunable morphology enabling exquisite variations in glass transition. In addition, previously unattainable control over tensile mechanical properties is realized, including atypical increase of elongation at failure while maintaining the modulus and ultimate strength.
This communication describes a novel series of linear and crosslinked polyurethanes (PUs) and their selective depolymerization under mild conditions. Two unique polyols are synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis (RCM) to five- and six-membered cycloalkenes. These polyols are co-polymerized with toluene diisocyanate to generate linear PUs and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked PUs. The polyol design is such that the RCM reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs’ catalyst under ambient conditions, the PUs are rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enable further re-polymerization by traditional strategies for polymerization of double bonds. It is anticipated that this general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.
Sandia Materials Science Investment Area contributed to the SARS-CoV-2 virus and COVID-19 disease which represent the most significant pandemic threat in over 100 years. We completed a series of 7, short duration projects to provide innovative materials science research and development in analytical techniques to aid the neutralization of COVID-19 on multiple surfaces, approaches to rapidly decontaminate personal protective equipment, and pareto assessment of construction materials for manufacturing personal protective equipment. The developed capabilities and processes through this research can help US medical personnel, government installations and assets, first responders, state and local governments, and multiple federal agencies address the COVID-19 Pandemic.
A series of networks is introduced with systematically varied network heterogeneity and high overall values of average glass transition temperature (Tg), based on polymerization of rigid acrylate and aromatic thiol monomers. The curing behavior, chain dynamics, and microstructure of these networks were investigated through a combination of dynamic mechanical analysis and infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and x-ray scattering, respectively. The maximum Tg achieved during cure can be related to the breadth of the mechanical loss tangent, as others have previously suggested, as well as the temperature dependence of the chain dynamics in the network as monitored by 1H NMR. In addition, the microstructures of the networks are characterized by periodic, fractal microgels with characteristic length scales of ca. 20–40 nm. Intriguingly, this structural motif persists in the more homogeneous networks exhibiting comparatively narrow glass transitions and chain dynamics, indicating that dynamically homogeneous networks can still exhibit significant compositional heterogeneity at the mesoscale.
NMR spectroscopy continues to provide important molecular level details of dynamics in different polymer materials, ranging from rubbers to highly crosslinked composites. It has been argued that thermoset polymers containing dynamic and chemical heterogeneities can be fully cured at temperatures well below the final glass transition temperature (Tg). In this paper, we described the use of static solid-state 1H NMR spectroscopy to measure the activation of different chain dynamics as a function of temperature. Near Tg, increasing polymer segmental chain fluctuations lead to dynamic averaging of the local homonuclear proton-proton (1H-1H) dipolar couplings, as reflected in the reduction of the NMR line shape second moment (M2) when motions are faster than the magnitude of the dipolar coupling. In general, for polymer systems, distributions in the dynamic correlation times are commonly expected. To help identify the limitations and pitfalls of M2 analyses, the impact of activation energy or, equivalently, correlation time distributions, on the analysis of 1H NMR M2 temperature variations is explored. It is shown by using normalized reference curves that the distributions in dynamic activation energies can be measured from the M2 temperature behavior. An example of the M2 analysis for a series of thermosetting polymers with systematically varied dynamic heterogeneity is presented and discussed.
Boronic acid-modified polymers (BAMPs) can interact with glycoproteins and other glycosylated compounds through covalent binding of the boronic acid moieties to saccharide residues. As a first step toward evaluating the utility of BAMPs as SARS-CoV-2 antiviral agents, this COVID-19 rapid response LDRD was intended to examine the effect of BAMPs on SARS-CoV-2 spike glycoprotein and its subsequent binding with ACE2 receptor protein. Multiple different approaches were attempted in order to determine whether BAMPs based on poly(ethylene glycol) and poly(ethylenimine) bind the spike protein, but failed to produce a definitive answer. However, two different enzyme-linked immunosorbent assays clearly showed no discernable effect of boronic acid in inhibiting spike-ACE2 binding.
Sandia National Laboratories currently has 27 COVID-related Laboratory Directed Research & Development (LDRD) projects focused on helping the nation during the pandemic. These LDRD projects cross many disciplines including bioscience, computing & information sciences, engineering science, materials science, nanodevices & microsystems, and radiation effects & high energy density science.
We report a novel approach whereby cross-linked polybutadiene (PB) networks can be depolymerized in situ based on thermally activated alkene metathesis. A commercially available latent Ru catalyst, HeatMet, was compared to the common second-generation Hoveyda-Grubbs catalyst, HG2, in the metathetic depolymerization of PB. HeatMet was found to possess exceptional stability and negligible activity toward PB under ambient conditions, in solution and in bulk. This enabled cross-linked networks to be prepared containing homogeneously distributed Ru catalyst. The dynamic mechanical properties of networks containing HeatMet and cross-linked using alcohol-isocyanate or thiol-ene chemistry were evaluated during cross-linking and post-cross-linking under isothermal and nonisothermal heating. In both cases, above minimum catalyst loadings ranging from 0.004 to 0.024 mol %, the networks exhibited rapid degelation into a soluble oil upon heating to 100 °C. At these temperatures, extensive depolymerization of the PB segments through ring-closing metathesis of 1,4/1,2 diads by the activated HeatMet introduced network defects in significantly greater proportion than the original number of cross-links. The in situ depolymerization of cross-linked PB networks through latent catalysis, as described here, may enable facile disposal and recycling of PB encapsulants and adhesives, among other applications.