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Recent advancements in polymer science and manufacturing technologies triggered new developments of porous materials used for mitigating heat losses, such as thermal insulating polymeric foams. The major bottleneck in the optimization of these products, however, remains the absence of analytical methods able to scrutinize their large design space reasonably quickly and cost-effectively. This manuscript targets the paucity of data for polymeric foams by illustrating, at a proof-of-principle level, that several well-established analytical methods including optical microscopy, pycnometry, dielectric spectroscopy, thermogravimetric analysis, and nuclear magnetic resonance can be exploited for an extensive, yet logistically efficient, characterization of these materials. The purpose of this study is thus introducing an experimental platform for the characterization of market foam products and for the development of new polymeric foams with pore sizes that are particularly relevant for industrial and residential thermal insulation. Since this work introduces several new methodologies, it may be used as a guide for both laboratory users and specialists in the field, who may further improve the herein proposed experimental concepts., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Catalin Gainaru reports financial support was provided by US Department of Energy. S. Shrestha reports financial support was provided by US Department of Energy. A. Tamraparni reports financial support was provided by US Department of Energy. D. Howard reports financial support was provided by US Department of Energy. T. Saito reports financial support was provided by US Department of Energy. D. Hun reports financial support was provided by US Department of Energy. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 Published by Elsevier Ltd.)

Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO 2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO 2 -facilitated recyclability without sacrificing performance. The presence of CO 2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO 2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability., (© 2024. The Author(s).)

Elastomers play a vital role in many forthcoming advanced technologies in which their adhesive properties determine materials' interface performance. Despite great success in improving the adhesive properties of elastomers, permanent adhesives tend to stick to the surfaces prematurely or result in poor contact depending on the installation method. Thus, elastomers with on-demand adhesion that is not limited to being triggered by UV light or heat, which may not be practical for scenarios that do not allow an additional external source, provide a solution to various challenges in conventional adhesive elastomers. Herein, we report a novel, ready-to-use, ultra high-strength, ductile adhesive elastomer with an on-demand adhesion feature that can be easily triggered by a compression force. The precursor is mainly composed of a capsule-separated, two-component curing system. After a force-trigger and curing process, the ductile adhesive elastomer exhibits a peel strength and a lap shear strength of 1.2 × 10 4 N m -1 and 7.8 × 10 3 kPa, respectively, which exceed the reported values for advanced ductile adhesive elastomers. The ultra-high adhesion force is attributed to the excellent surface contact of the liquid-like precursor and to the high elastic modulus of the cured elastomer that is reinforced by a two-phase design. Incorporation of such on-demand adhesion into an elastomer enables a controlled delay between installation and curing so that these can take place under their individual ideal conditions, effectively reducing the energy cost, preventing failures, and improving installation processes.

Elastic vitrimers, i.e., elastic polymers with associative dynamic covalent bonds, can afford elastomers with recyclability while maintaining their thermal and chemical stability. Herein, we report a series of boronic ester-based vitrimers with tunable mechanical properties and recyclability by varying the substitute groups of boronic acid in polymer networks. The dynamic polymer networks are formed by reacting diol-containing tetra-arm poly(amidoamine) with boronic acid-terminated tetra-arm poly(ethylene glycol), which possesses different substituents adjacent to boronic acid moieties. Varying the substituent adjacent to the boronic ester unit will significantly affect the binding strength of the boronic ester, therefore affecting their dynamics and mechanical performance. The electron-withdrawing substituents noticeably suppress the dynamics of boronic ester exchange and increase the activation energy and relaxation time while enhancing the mechanical strength of the resulting elastic vitrimers. On the other hand, the presence of electron-rich substituent affords relatively reduced glass transition temperature ( T g ), faster relaxation, and prominent recyclability and malleability at lower temperatures. The developed pathway will guide the rational design of elastomers with well-tunable dynamics and processabilities., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Despite intensive research on sustainable elastomers, achieving elastic vitrimers with significantly improved mechanical properties and recyclability remains a scientific challenge. Herein, inspired by the classical elasticity theory, we present a design principle for ultra-tough and highly recyclable elastic vitrimers with a defined network constructed by chemically crosslinking the pre-synthesized disulfide-containing polydimethylsiloxane (PDMS) chains with tetra-arm polyethylene glycol (PEG). The defined network is achieved by the reduced dangling short chains and the relatively uniform molecular weight of network strands. Such elastic vitrimers with the defined network, i.e., PDMS-disulfide-D, exhibit significantly improved mechanical performance than random analogous, previously reported PDMS vitrimers, and even commercial silicone-based thermosets. Moreover, unlike the vitrimers with random network that show obvious loss in mechanical properties after recycling, those with the defined network enable excellent thermal recyclability. The PDMS-disulfide-D also deliver comparable electrochemical signals if utilized as substrates for electromyography sensors after the recycling. The multiple relaxation processes are revealed via a unique physical approach. Multiple techniques are also applied to unravel the microscopic mechanism of the excellent mechanical performance and recyclability of such defined network., (© 2023 Wiley-VCH GmbH.)

Plastic represents an essential material in our society; however, a major imbalance between their high production and end-of-life management is leading to unrecovered energy, economic hardship, and a high carbon footprint. The adoption of plastic recycling has been limited, mainly due to the difficulty of recycling mixed plastics. Here, we report a versatile organocatalyst for selective glycolysis of diverse consumer plastics and their mixed waste streams into valuable chemicals. The developed organocatalyst selectively deconstructs condensation polymers at a specific temperature, and additives or other polymers such as polyolefin or cellulose can be readily separated from the mixed plastics, providing a chemical recycling path for many existing mixed plastics today. The Life Cycle Assessment indicates that the production of various condensation polymers from the deconstructed monomers will result in a significant reduction in greenhouse gas emissions and energy input, opening a new paradigm of plastic circularity toward a net-zero carbon society.

The overall performance of polymer composites depends on not only the intrinsic properties of the polymer matrix and inorganic filler but also the quality of interfacial adhesion. Although many reported approaches have been focused on the chemical treatment for improving interfacial adhesion, the examination of ultimate mechanical performance and long-term properties of polymer composites has been rarely investigated. Herein, we report carbon fiber (CF)/epoxy composites with improved interfacial adhesion by covalent bonding between CFs and the epoxy matrix. This leads to the improved ultimate mechanical properties and enhanced thermal aging performance. Raman mapping demonstrates the formation of an interphase region derived from the covalent bonding between CFs and the epoxy matrix, which enables the uniform fiber distribution and eliminates phase separation during thermal cycling. The covalent attachment of the CF to the epoxy matrix suppresses its migration during temperature fluctuations, preserving the mechanical performance of resulting composites under the thermal aging process. Furthermore, the finite elemental analysis reveals the effectiveness of the chemical treatment of CFs in improving the interfacial strength and toughness of silane-treated CF/epoxy composites. The insight into the mechanical improvement of CF/epoxy composites suggests the high potential of surface modification of inorganic fillers toward polymer composites with tunable properties for different applications.

To investigate the utility of acrylic monomers from various plant oils in adhesives manufacturing, 25-45 wt. % of high oleic soybean oil-based monomer (HOSBM) was copolymerized in a miniemulsion with commercially applied butyl acrylate (BA), methyl methacrylate (MMA), or styrene (St). The compositions of the resulting ternary latex copolymers were varied in terms of both "soft" (HOSBM, BA) and "rigid" (MMA or St) macromolecular fragments, while total monomer conversion and molecular weight of copolymers were determined after synthesis. For most latexes, results indicated the presence of lower and higher molecular weight fractions, which is beneficial for the material adhesive performance. To correlate surface properties and adhesive performance of HOSBM-based copolymer latexes, contact angle hysteresis (using water as a contact liquid) for each latex-substrate pair was first determined. The data showed that plant oil-based latexes exhibit a clear ability to spread and adhere once applied on the surface of materials differing by polarities, such as semicrystalline polyethylene terephthalate (PET), polypropylene (PP), bleached paperboard (uncoated), and tops coated with a clay mineral paperboard. The effectiveness of plant oil-based ternary latexes as adhesives was demonstrated on PET to PP and coated to uncoated paperboard substrates. As a result, the latexes with high biobased content developed in this study provide promising adhesive performance, causing substrate failure instead of cohesive/adhesive break in many experiments.

This study demonstrated that polymerization behavior of plant oil-based acrylic monomers (POBMs) synthesized in one-step transesterification reaction from naturally rich in oleic acid olive, canola, and high-oleic soybean oils is associated with a varying mass fraction of polyunsaturated fatty acid fragments (linoleic (C18:2) and linolenic (C18:3) acid esters) in plant oil. Using miniemulsion polymerization, a range of stable copolymer latexes was synthesized from 60 wt.% of each POBM and styrene to determine the impact of POBM chemical composition (polyunsaturation) on thermal and mechanical properties of the resulted polymeric materials. The unique composition of each plant oil serves as an experimental tool to determine the effect of polyunsaturated fatty acid fragments on POBM polymerization behavior and thermomechanical properties of crosslinked films made from POBM-based latexes. The obtained results show that increasing polyunsaturation in the copolymers results in an enhanced crosslink density of the latex polymer network which essentially impacts the mechanical properties of the films (both Young's modulus and toughness). Maximum toughness was observed for crosslinked latex films made from 50 wt.% of each POBM in the monomer feed.

In recent years, polymer chemistry has experienced an intensive development of a new field regarding the synthesis of aliphatic and aromatic biobased monomers obtained from renewable plant sources. A one-step process for the synthesis of new vinyl monomers by the reaction of direct transesterification of plant oil triglycerides with N -(hydroxyethyl)acrylamide has been recently invented to yield plant oil-based monomers (POBMs). The features of the POBM chemical structure, containing both a polar (hydrophilic) fragment capable of electrostatic interactions, and hydrophobic acyl fatty acid moieties (C 15 -C 17 ) capable of van der Waals interactions, ensures the participation of the POBMs fragments of polymers in intermolecular interactions before and during polymerization. The use of the POBMs with different unsaturations in copolymerization reactions with conventional vinyl monomers allows for obtaining copolymers with enhanced hydrophobicity, provides a mechanism of internal plasticization and control of crosslinking degree. Synthesized latexes and latex polymers are promising candidates for the formation of hydrophobic polymer coatings with controlled physical and mechanical properties through the targeted control of the content of different POBM units with different degrees of unsaturation in the latex polymers.

Vinyl monomers from soybean, sunflower, linseed, and olive oils were copolymerized with styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) to determine the reactivity of biobased monomers in radical copolymerization, as well as their feasibility in emulsion processes for the synthesis of biobased latexes. Radical copolymerization of plant-oil-based monomers is described with the classical Mayo-Lewis equation. Using emulsion (or miniemulsion) polymerization with MMA or VAc, stable aqueous polymer dispersions with latex particles measuring 80-160 nm and containing 3-35 wt % of biobased monomer units were successfully synthesized. The number-average molecular weight of the latex copolymers (20 000-150 000) decreases by increasing the degree of unsaturation in monomers and their content in the reaction feed. The presence of plant-oil-based fragments changes the T g of resulting copolymers from 105 to 79 °C in copolymerization with MMA and from 30 to 11 °C in copolymerization with Vac. As a result, biobased units provide considerable flexibility (elongation at break of about 250%) and improve the toughness of the normally rigid and brittle poly(MMA). Even a small amount (2-5%) of biobased fragments incorporated into the structure of poly(VAc) significantly improves water resistance and provides hydrophobicity to the resulting polymer latex films. The obtained results clearly indicate that the vinyl monomers from plant oils can be considered as good candidates for internal plasticization of polymeric materials through reducing intermolecular interactions in copolymers., Competing Interests: The authors declare no competing financial interest.