Search NASA⌕ Search
Home/Archive/DOE OSTI

DOE OSTI · 3030317

One Step Block-like Copolymers from an Upcycled Monomer Using Ring-Opening Metathesis Polymerization

Foster, Jeffrey C. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000290978680)·Dishner, Isaiah T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000273339182)·Zheng, Jackie [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)]·Bocharova, Vera [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000342703866)·Kertesz, Vilmos [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000301865797)·Saito, Tomonori [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000245367530)
View original source ↗Read source document ↗Export metadata ↓

Abstract

Block-like copolymers can be readily synthesized in one step using monomers with widely separated reactivity ratios. Here, we show that trans,trans,trans-1,5,9-cyclododecatriene (CDT), produced from polybutadiene via cyclodepolymerization (CDP), undergoes gradient copolymerization via ring-opening metathesis polymerization (ROMP) with a selected norbornene monomer to produce a block-like copolymer that exhibits bulk nanophase separation and excellent thermomechanical performance. These data highlight a new ROMP copolymerization system with a sharp compositional drift and introduce a simple pathway to convert waste plastic into a valuable building block for high-value thermoplastic materials.

Explore related subjects

block copolymergradient copolymerplastic waste valorizationpolymer materialsring-opening metathesis polymerization

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Foster, Jeffrey C. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000290978680), Dishner, Isaiah T. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000273339182), Zheng, Jackie [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)], Bocharova, Vera [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000342703866), Kertesz, Vilmos [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000301865797), Saito, Tomonori [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000245367530). 2025-12-18. One Step Block-like Copolymers from an Upcycled Monomer Using Ring-Opening Metathesis Polymerization. https://doi.org/10.1021/acspolymersau.5c00157

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related reports

DOE OSTI2025

Facile One-Pot Block Copolymer-Mediated Solvothermal Approach for Synthesis of High-Entropy Alloy with Enhanced OER Activity

Herein, we introduce a straightforward synthesis approach for highly active dendritic multimetallic high-entropy alloy (DMHEA@PtIrPdAgRu) nanoparticles with sufficient entropic mixing, featuring uniform distribution of five noble group metals (Pt, Ir, Pd, Ag, and Ru) via a block copolymer-mediated one-pot solvothermal reduction method for oxygen evolution reaction (OER). In this synthesis, N,N -dimethylformamide (DMF) is used as a reductant as well as solvent and core–shell-corona-type (poly(styrene)- block -poly(vinylpyridine)- block -poly(ethylene oxide)) (PS-PVP-PEO) block copolymer as a structure directing agent. The cooperative effect between the copolymer architecture and the reducing environment of DMF promoted a confined nucleation mechanism for forming a single-phase dendritic structure HEA with high compositional uniformity, thereby mitigating phase segregation, a common challenge in the synthesis of multimetallic nanoparticles. This prepared DMHEA@PtIrPdAgRu catalyst exhibits a low overpotential of 490 mV to attain a high current density of 100 mA cm –2 with a Tafel slope of 442 mV dec –1 for oxygen evolution. The superior OER performance is attributed to the synergistic cooperation among its active and coordinated metal centers as well as the incorporation of corrosion-resistant metal like platinum.

block copolymer↗
DOE OSTI2021

Understanding kinetics of defect annihilation in chemoepitaxy-directed self-assembly.

Directed self-assembly (DSA) of block copolymers (BCP) has attracted considerable interest from the semiconductor industry because it can achieve semiconductor-relevant structures with a relatively simple process and low cost. However, the self-assembling structures can become kinetically trapped into defective states, which greatly impedes the implementation of DSA in high-volume manufacturing. Understanding the kinetics of defect annihilation is crucial to optimizing the process and eventually eliminating defects in DSA. Such kinetic experiments, however, are not commonly available in academic laboratories. To address this challenge, we perform a kinetic study of chemoepitaxy DSA in a 300 mm wafer fab, where the complete defectivity information at various annealing conditions can be readily captured. Through extensive statistical analysis, we reveal the statistical model of defect annihilation in DSA for the first time. The annihilation kinetics can be well described by a power law model, indicating that all dislocations can be removed by sufficiently long annealing time. We further develop image analysis algorithms to analyze the distribution of dislocation size and configurations and discover that the distribution stays relatively constant over time. The defect distribution is determined by the role of the guiding stripe, which is found to stabilize the defects. Although this study is based on polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA), we anticipate that these findings can be readily applied to other BCP platforms as well.

block copolymer↗