Recyclable Cross-Linked Polyethylene from Self-Condensing Telechelic Polyethylene by Combining Olefin Metathesis, Hydrogenation, and Transesterification.

Cross-linked polyethylene (PEX) is a high-performance thermoset with improved thermomechanical properties compared to its parent linear polymer, polyethylene (PE). The covalent bonds linking PEX, however, prevent efficient recycling or reprocessing, which represents a critical liability with respect to addressing the current global plastic waste crisis. Existing strategies to impart recyclability into PEX rely largely on radical chemistries, which are difficult to control and lead to side reactions.

PLA Block Polymers: Versatile Materials for a Sustainable Future.

Block polymers present an almost endless realm of possibilities to develop functional materials for myriad applications. The established self-assembly of block polymers allows researchers to access properties that are inaccessible in homopolymers. However, there is a need to develop more sustainable options than the current commodity block polymers.

Strong Hydrogen Bonds Sustain Even-Odd Effects in Poly(ester amide)s with Long Alkyl Chain Length in the Backbone.

The number of methylene groups between strongly interacting functional groups within polymer repeating units induces even-odd effects on thermal and mechanical properties. However, detailed studies correlating the even-odd effect with structural changes are still lacking. In this work, we establish correlations between the structure and thermal properties of poly(ester amide)s containing long alkyl chain lengths.

Alkyl-Substituted Polycaprolactone Poly(urethane-urea)s as Mechanically Competitive and Chemically Recyclable Materials.

We report the mechanical performance and chemical recycling advantages of implementing alkyl-substituted poly(ε-caprolactones) (PCLs) as soft segments in thermoplastic poly(urethane-urea) (TPUU) materials. Poly(4-methylcaprolactone) (P4MCL) and poly(4-propylcaprolactone) (P4PrCL) were prepared, reacted with isophorone diisocyanate, and chain-extended with water to form TPUUs. The resulting materials' tensile properties were similar or superior to a commercially available polyester thermoplastic poly(urethane) and had superior elastic recovery properties compared to a PCL analogue due to the noncrystalline nature of P4MCL and P4PrCL.

Regio- and Stereoregular EVOH Copolymers from ROMP as Designer Barrier Materials.

This work aimed to decrease the water permeability ( ) while simultaneously maintaining low oxygen permeability ( ) in ethylene vinyl alcohol (EVOH)-based copolymers by introducing high levels of backbone regioregularity and stereoregularity. Both regioregular atactic and isotactic EVOH samples with 75 mol % ethylene were prepared by a ring-opening metathesis polymerization (ROMP)-hydrogenation-deprotection approach and then compared to commercial EVOH(44) (containing 44 mol % ethylene) as a low standard with poor water barrier characteristics (i.e.

Preparation and Characterization of H-Shaped Polylactide.

An H-polymer has an architecture that consists of four branches symmetrically attached to the ends of a polymer backbone, similar in shape to the letter "H". Here, a renewable H-polymer efficiently synthesized using only ring-opening transesterification is demonstrated. The strategy relies on a tetrafunctional poly(±-lactide) macroinitiator, from which four poly(±-lactide) branches are grown simultaneously.

Cross-Linked Polyolefins through Tandem ROMP/Hydrogenation.

Cross-linked polyolefins have important advantages over their thermoplastic analogues, particularly improved impact strength and abrasion resistance, as well as increased chemical and thermal stability; however, most strategies for their production involve postpolymerization cross-linking of polyolefin chains. Here, a tandem ring-opening metathesis polymerization (ROMP)/hydrogenation approach is presented. Cyclooctene (COE)--dicyclopentadiene (DCPD) networks are first synthesized using ROMP, after which the dispersed Ru metathesis catalyst is activated for hydrogenation through the addition of hydrogen gas.

Chemically Recyclable Linear and Branched Polyethylenes Synthesized from Stoichiometrically Self-Balanced Telechelic Polyethylenes.

High-density polyethylene (HDPE) is a widely used commercial plastic due to its excellent mechanical properties, chemical resistance, and water vapor barrier properties. However, less than 10% of HDPE is mechanically recycled, and the chemical recycling of HDPE is challenging due to the inherent strength of the carbon-carbon backbone bonds. Here, we report chemically recyclable linear and branched HDPE with sparse backbone ester groups synthesized from the transesterification of telechelic polyethylene macromonomers.

Tough polycyclooctene nanoporous membranes from etchable block copolymers.

Porous materials with pore dimensions of the nanometer length scale are useful as nanoporous membranes. ABA triblock copolymers are convenient precursors to such nanoporous materials if the end blocks are easily degradable (, polylactide or PLA), leaving nanoporous polymeric membranes (NPMs) if in thin film form. The membrane properties are dependent on midblock monomer structure, triblock copolymer composition, overall molar mass, and polymer processing conditions.

Dynamic Aliphatic Polyester Elastomers Crosslinked with Aliphatic Dianhydrides.

Chemically crosslinked elastomers are a class of polymeric materials with properties that render them useful as adhesives, sealants, and in other engineering applications. Poly(γ-methyl-ε-caprolactone) (PγMCL) is a hydrolytically degradable and compostable aliphatic polyester that can be biosourced and exhibits competitive mechanical properties to traditional elastomers when chemically crosslinked. A typical limitation of chemically crosslinked elastomers is that they cannot be reprocessed; however, the incorporation of dynamic covalent bonds can allow for bonds to reversibly break and reform under an external stimulus, usually heat.

High Performance Star Block Aliphatic Polyester Thermoplastic Elastomers Using PDLA--PLLA Stereoblock Hard Domains.

Star block (ABC) terpolymers consisting of a rubbery poly(γ-methyl-ε-caprolactone) (PγMCL) (C) core and hard poly(l-lactide) (PLLA) (B) and poly(d-lactide) (PDLA) (A) end-blocks with varying PDLA to PLLA block ratios were explored as high-performance, sustainable, aliphatic polyester thermoplastic elastomers (APTPEs). The stereocomplexation of the PDLA/PLLA blocks within the hard domains provided the APTPEs with enhanced thermal stability and an increased resistance to permanent deformation compared to nonstereocomplex analogs. Variations in the PDLA:PLLA block ratio yielded tunable mechanical properties likely due to differences in the extent and location of stereocomplex crystallite formation as a result of architectural constraints.

Tuning the crystallization and thermal properties of polyesters by introducing functional groups that induce intermolecular interactions.

The performance of sustainable polymers can be modified and enhanced by incorporating functional groups in the backbone of the polymer chain that increases intermolecular interactions, thus impacting the thermal properties of the material. However, in-depth studies on the role of intermolecular interactions on the crystallization of these polymers are still needed. This work aims to ascertain whether incorporating functional groups able to induce intermolecular interactions can be used as a suitable systematic strategy to modify the polymer thermal properties and crystallization kinetics.

Effect of Poloxamer Binding on the Elasticity and Toughness of Model Lipid Bilayers.

Poloxamers, also known by their trade name, Pluronics, are known to mitigate damage to cellular membranes. However, the mechanism underlying this protection is still unclear. We investigated the effect of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of giant unilamellar vesicles, composed of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine, using micropipette aspiration (MPA).

Molecular homing and retention of muscle membrane stabilizing copolymers by non-invasive optical imaging in vivo.

First-in-class membrane stabilizer Poloxamer 188 (P188) has been shown to confer membrane protection in an extensive range of clinical conditions; however, elements of the systemic distribution and localization of P188 at the organ, tissue, and muscle fiber levels have not yet been elucidated. Here we used non-invasive fluorescence imaging to directly visualize and track the distribution and localization of P188 . The results demonstrated that the Alx647 probe did not alter the fundamental properties of P188 to protect biological membranes.

Dihydroxy Polyethylene Additives for Compatibilization and Mechanical Recycling of Polyethylene Terephthalate/Polyethylene Mixed Plastic Waste.

Polymer blend compatibilization is an attractive solution for mechanical recycling of mixed plastic waste because it can result in tough blends. In this work, hydroxy-telechelic polyethylene (HOPEOH) reactive additives were used to compatibilize blends of polyethylene terephthalate (PET) and linear low-density polyethylene (LLDPE). HOPEOH additives were synthesized with molar masses of 1-20 kg/mol by ring-opening metathesis polymerization of cyclooctene followed by catalytic hydrogenation.

Polymeric Microcapsules as Robust Mimics of Emulsion Liquid Membranes for Selective Ion Separations.

Selective ion separations are increasingly needed to combat water scarcity, recover resources from wastewater, and enable the efficient recycling of electronics waste. Emulsion liquid membranes (ELMs) have received interest due to rapid kinetics, high selectivities, and low solvent requirements but are too unstable for industrial usage. We demonstrate that polymeric microcapsules can serve as robust, solvent-free mimics of ELMs.

Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene.

Hydroxy-telechelic polyalkenamers have long been synthesized using ring-opening metathesis polymerization (ROMP) in the presence of an acyclic olefin chain-transfer agent (CTA); however, this route typically requires protected diols in the CTA due to the challenge of alcohol-mediated degradation of ruthenium metathesis catalysts that can not only deactivate the catalysts, but also compromise the CTA. We demonstrate the synthesis and implementation of a new hydroxyl-containing CTA in which extended methylene spacers isolate the olefin and alcohol moieties to mitigate decomposition pathways. This CTA enabled the direct ROMP synthesis of hydroxy-telechelic polycyclooctene with controlled chain lengths dictated by the initial ratio of monomer to CTA.

Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations.

Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (), the side-chain degree of polymerization (), and the backbone degree of polymerization (), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to and are controlled by the macromonomer degree of polymerization () and the initial fraction of the macromonomer in the feed (), respectively.

The role of intermolecular interactions on melt memory and thermal fractionation of semicrystalline polymers.

The origin of melt memory effects associated with semicrystalline polymers and the physical parameters involved in this process have been widely studied in the literature. However, a comprehensive understanding of the role of intermolecular interactions on melt memory is still being developed. For this purpose, we have considered aliphatic polyesters and we have incorporated amide and additional ester groups.

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena.

Lipid Membrane Binding and Cell Protection Efficacy of Poly(1,2-butylene oxide)--poly(ethylene oxide) Copolymers.

Poloxamers consisting of poly(ethylene oxide) (PEO) and poly(propylene oxide) segments can protect cell membranes against various forms of stress. We investigated the role of the hydrophobic block chemistry on polymer/membrane binding and cell membrane protection by comparing a series of poly(butylene oxide)--PEO (PBO--PEO) copolymers to poloxamer analogues, using a combination of pulsed-field-gradient (PFG) NMR experiments and a lactate dehydrogenase (LDH) cell assay. We found that the more hydrophobic PBO--PEO copolymers bound more significantly to model liposomes composed of 1-palmitol-2-oleoyl-glycero-3-phosphocholine (POPC) compared to poly(propylene oxide) (PPO)/PEO copolymers.

Enhanced Polyester Degradation through Transesterification with Salicylates.

Polyesters constitute nearly 10% of the global plastic market, but most are essentially non-degradable under ambient conditions or in engineered environments. A range of degradable polyesters have been developed as more sustainable alternatives; however, limitations of practical degradability and scalability have hindered their viability. Here, we utilized transesterification approaches, including polymerization-transesterification, between a salicylate and a polyester to incorporate salicylate units into commercial polyester backbones.

Synthesis, Microstructure, and Properties of High-Molar-Mass Polyglycolide Copolymers with Isolated Methyl Defects.

An efficient, fast, and reliable method for the synthesis of high-molar-mass polyglycolide (PGA) in bulk using bismuth (III) subsalicylate through ring-opening transesterification polymerization is described. The difference between the crystallization ( ≈ 180 °C)/degradation ( ≈ 245 °C) temperatures and the melting temperature ( ≈ 222 °C) significantly affects the ability to melt-process PGA homopolymer. To expand these windows, the effect of copolymer microstructure differences through incorporation of methyl groups in pairs using lactide or isolated using methyl glycolide (≤10% methyl) as comonomers on the thermal, mechanical, and barrier properties were studied.