Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Hybrid Monomer Design Synergizing Property Trade‐offs in Developing Polymers for Circularity and Performance

Journal Article · · Angewandte Chemie

Abstract

Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability to monomer for a circular plastics economy and desirable performance that can rival or even exceed today's non‐recyclable or hard‐to‐recycle petroleum‐based incumbents. However, within a traditional monomer framework it is challenging to optimize, concurrently , contrasting polymerizability/depolymerizability and recyclability/performance properties. Here, we highlight the emerging hybrid monomer design strategy to develop intrinsically circular polymers with tunable performance properties, aiming to unify desired, but otherwise conflicting, properties in a single monomer. Conceptually, this design hybridizes parent monomer pairs of contrasting, mismatching, or matching properties into offspring monomers that not only unify the above‐described conflicting properties but also radically alter the resultant polymer properties far beyond the limits of what either parent homopolymers or their copolymers can achieve.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1973293
Alternate ID(s):
OSTI ID: 1983509
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 31 Vol. 135; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (117)

Thermodynamics and Kinetics of Ring-Opening Polymerization book January 2009
Dynamic Covalent Polymer Networks: from Old Chemistry to Modern Day Innovations journal February 2017
Toward Stimuli‐Responsive Dynamic Thermosets through Continuous Development and Improvements in Covalent Adaptable Networks (CANs) journal February 2020
Completely Recyclable Monomers and Polycarbonate: Approach to Sustainable Polymers journal March 2017
Plastics of the Future? The Impact of Biodegradable Polymers on the Environment and on Society journal November 2018
Beyond Mechanical Recycling: Giving New Life to Plastic Waste journal June 2020
Biodegradable Polyhydroxyalkanoates by Stereoselective Copolymerization of Racemic Diolides: Stereocontrol and Polyolefin‐Like Properties journal March 2020
Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers journal October 2021
O‐to‐S Substitution Enables Dovetailing Conflicting Cyclizability, Polymerizability, and Recyclability: Dithiolactone vs. Dilactone journal September 2021
Efficient and Selective Chemical Recycling of CO 2 ‐Based Alicyclic Polycarbonates via Catalytic Pyrolysis journal July 2022
Functionalizable and Chemically Recyclable Thermoplastics from Chemoselective Ring‐Opening Polymerization of Bio‐renewable Bifunctional α‐Methylene‐δ‐valerolactone journal June 2022
Highly Selective Preparation and Depolymerization of Chemically Recyclable Poly(cyclopentene carbonate) Enabled by Organoboron Catalysts journal October 2022
Biodegradable High‐Density Polyethylene‐like Material journal December 2022
Learning Nature: Recyclable Monomers and Polymers journal June 2018
Emerging Trends in Closed‐Loop Recycling Polymers: Monomer Design and Catalytic Bulk Depolymerization journal February 2023
Endowing Polythioester Vitrimer with Intrinsic Crystallinity and Chemical Recyclability journal March 2023
Recyclable Vinyl‐Functionalized Polyesters via Chemoselective Organopolymerization of Bifunctional α‐Methylene‐δ‐Valerolactone journal May 2019
Mechanical Recycling of Packaging Plastics: A Review journal September 2020
Polyolefin Innovations toward Circularity and Sustainable Alternatives journal July 2022
Radical-initiated homo- and copolymerization of α-methylene-γ-butyrolactone journal October 1982
Toward Infinitely Recyclable Plastics Derived from Renewable Cyclic Esters journal February 2019
Geminal Dimethyl Substitution Enables Controlled Polymerization of Penicillamine-Derived β-Thiolactones and Reversed Depolymerization journal July 2020
Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties journal March 2021
Design principles for intrinsically circular polymers with tunable properties journal November 2021
Controlled radical depolymerization of chlorine-capped PMMA via reversible activation of the terminal group by ruthenium catalyst journal November 2019
Malleable and Recyclable Thermosets: The Next Generation of Plastics journal December 2019
Synthesis and degradation behavior of poly(ethyl cyanoacrylate) journal July 2008
Comments on the depolymerization of polycarbonates derived from epoxides and carbon dioxide: A mini review journal March 2018
Multiscale SAXS/WAXD characterisation of the deformation mechanisms of electrospun PCL scaffolds journal August 2020
Environmental and health hazard ranking and assessment of plastic polymers based on chemical composition journal August 2011
Future Directions for Sustainable Polymers journal May 2019
Mechanical and chemical recycling of solid plastic waste journal November 2017
Synthesis and Postpolymerization Modification of One-Pot ω-Pentadecalactone Block-like Copolymers journal October 2015
Dynamic Covalent Polymer Networks: A Molecular Platform for Designing Functions beyond Chemical Recycling and Self-Healing journal January 2021
Catalysis as an Enabling Science for Sustainable Polymers journal October 2017
Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration journal June 2021
Roles of Conformational Flexibility in the Crystallization of Stereoirregular Polymers journal June 2021
Influence of Tacticity on the Crystal Structures of Hydrogenated Ring-Opened Poly(norbornene)s journal August 2021
Toughening Biodegradable Isotactic Poly(3-hydroxybutyrate) via Stereoselective Copolymerization of a Diolide and Lactones journal October 2021
Closed-Loop Recyclable Aliphatic Poly(ester-amide)s with Tunable Mechanical Properties journal May 2022
Depolymerization of Polymethacrylates by Iron ATRP journal November 2022
Current Challenges and Perspectives in CO2-Based Polymers journal February 2023
Aliphatic Polyester Block Polymer Design journal March 2016
50th Anniversary Perspective : There Is a Great Future in Sustainable Polymers journal May 2017
“Nonstrained” γ-Butyrolactone-Based Copolyesters: Copolymerization Characteristics and Composition-Dependent (Thermal, Eutectic, Cocrystallization, and Degradation) Properties journal October 2017
Synthesis and Controlled Organobase-Catalyzed Ring-Opening Polymerization of Morpholine-2,5-Dione Derivatives and Monomer Recovery by Acid-Catalyzed Degradation of the Polymers journal May 2019
Chemical Synthesis of CO2-Based Polymers with Enhanced Thermal Stability and Unexpected Recyclability from Biosourced Monomers journal June 2021
A Thermodynamic Roadmap for the Grafting-through Polymerization of PDMS11MA journal August 2020
100th Anniversary of Macromolecular Science Viewpoint: Toward Catalytic Chemical Recycling of Waste (and Future) Plastics journal October 2020
Modulating Polymerization Thermodynamics of Thiolactones Through Substituent and Heteroatom Incorporation journal July 2022
Ring-Opening Polymerization of a Bicyclic Lactone: Polyesters Derived from Norcamphor with Complete Chemical Recyclability journal September 2022
Investigating the Effect of End-Group, Molecular Weight, and Solvents on the Catalyst-Free Depolymerization of RAFT Polymers: Possibility to Reverse the Polymerization of Heat-Sensitive Polymers journal September 2022
Photoassisted Radical Depolymerization journal December 2022
Dependence of Copolymer Sequencing Based on Lactone Ring Size and ε-Substitution journal February 2016
Zinc-Mediated Allylation-Lactonization One-Pot Reaction to Methylene Butyrolactones: Renewable Monomers for Sustainable Acrylic Polymers with Closed-Loop Recyclability journal April 2022
Crystals and Crystallinity in Polymeric Materials journal May 2006
Effects of Residual Zinc Compounds and Chain-End Structure on Thermal Degradation of Poly(ε-caprolactone) journal July 2004
Copolymerization. journal April 1950
gem -Disubstituent Effect:  Theoretical Basis and Synthetic Applications journal May 2005
Evaluation of strain in hydrocarbons. The strain in adamantane and its origin journal April 1970
Anionic ring-opening polymerization of thiolactones journal June 1968
Tuning the Release Rate of Acidic Degradation Products through Macromolecular Design of Caprolactone-Based Copolymers journal May 2007
Disulfide-Mediated Reversible Polymerization toward Intrinsically Dynamic Smart Materials journal January 2022
Understanding the Structure–Polymerization Thermodynamics Relationships of Fused-Ring Cyclooctenes for Developing Chemically Recyclable Polymers journal January 2022
Closing the “One Monomer–Two Polymers–One Monomer” Loop via Orthogonal (De)polymerization of a Lactone/Olefin Hybrid journal January 2022
Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability journal March 2022
Reversing RAFT Polymerization: Near-Quantitative Monomer Generation Via a Catalyst-Free Depolymerization Approach journal February 2022
Solid-State Chemical Recycling of Polycarbonates to Epoxides and Carbon Dioxide Using a Heterodinuclear Mg(II)Co(II) Catalyst journal September 2022
Chemical Recycling of Polyethylene by Tandem Catalytic Conversion to Propylene journal September 2022
Tough while Recyclable Plastics Enabled by Monothiodilactone Monomers journal January 2023
Catalytic Chemical Recycling of Post-Consumer Polyethylene journal December 2022
The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways journal October 2016
4-Hydroxyproline-Derived Sustainable Polythioesters: Controlled Ring-Opening Polymerization, Complete Recyclability, and Facile Functionalization journal March 2019
Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets journal September 2019
Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s journal October 2019
Olefin metathesis of cyclohexene journal April 1986
Synthesis and homopolymerization kinetics of α-methylene-δ-valerolactone, an exo-methylene cyclic monomer with a nonplanar ring system spanning the radical center journal August 1983
Hydrogenated Ring-Opened Polynorbornene:  A Highly Crystalline Atactic Polymer journal February 2005
An Efficient Method To Depolymerize Polyamide Plastics:  A New Use of Ionic Liquids journal June 2007
Classify plastic waste as hazardous journal February 2013
Sustainable polymers from renewable resources journal December 2016
Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone journal November 2015
Tailored silyl ether monomers enable backbone-degradable polynorbornene-based linear, bottlebrush and star copolymers through ROMP journal October 2019
A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization journal November 2021
A circular polyester platform based on simple gem-disubstituted valerolactones journal November 2022
Strategies to reduce the global carbon footprint of plastics journal April 2019
Chemical recycling of waste plastics for new materials production journal June 2017
Chemical recycling to monomer for an ideal, circular polymer economy journal April 2020
Closed-loop recycling of polyethylene-like materials journal February 2021
Cleavable comonomers enable degradable, recyclable thermoset plastics journal July 2020
Critical advances and future opportunities in upcycling commodity polymers journal March 2022
Plastic futures and their CO2 emissions journal December 2022
Growing environmental footprint of plastics driven by coal combustion journal December 2021
Catalytic upcycling of high-density polyethylene via a processive mechanism journal October 2020
Chemical and biological catalysis for plastics recycling and upcycling journal July 2021
Chemically recyclable polymers: a circular economy approach to sustainability journal January 2017
Synthesis and mechanistic investigations of pH-responsive cationic poly(aminoester)s journal January 2020
High chemical recyclability of vinyl lactone acrylic bioplastics journal January 2020
Closed-loop chemical recycling of thermosetting polymers and their applications: a review journal January 2022
Closed-loop chemical recycling of poly(ε-caprolactone) by tuning reaction parameters journal January 2022
A sustainable approach for the synthesis of recyclable cyclic CO2-based polycarbonates journal January 2022
Production, use, and fate of all plastics ever made journal July 2017
High-performance pan-tactic polythioesters with intrinsic crystallinity and chemical recyclability journal August 2020
Closed-loop recyclable plastics from poly(ethyl cyanoacrylate) journal March 2023
Microplastics in the seas journal July 2014
The promise of plastics from plants journal November 2017
A synthetic polymer system with repeatable chemical recyclability journal April 2018
Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures journal November 2019
Predicted growth in plastic waste exceeds efforts to mitigate plastic pollution journal September 2020
Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization journal October 2020
Mixed plastics waste valorization through tandem chemical oxidation and biological funneling journal October 2022
Catalytic deconstruction of waste polyethylene with ethylene to form propylene journal September 2022
Plastics in the Marine Environment journal January 2017
First Example of Cationic Ring-Opening Polymerization of γ-Thionobutyrolactone journal March 2005
4-Hydroxy- l -Proline as a General Platform for Stereoregular Aliphatic Polyesters: Controlled Ring-Opening Polymerization, Facile Functionalization, and Site-Specific Bioconjugation journal October 2020
Chemoselective Polymerization of Fully Biorenewable α-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters journal January 2021
Degradable and Recyclable Polymers by Reversible Deactivation Radical Polymerization journal July 2022

Similar Records

Hybrid Monomer Design Synergizing Property Trade‐offs in Developing Polymers for Circularity and Performance
Journal Article · Wed May 10 00:00:00 EDT 2023 · Angewandte Chemie (International Edition) · OSTI ID:1973308

Related Subjects