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At least 73 records · Page 4

Fully Recyclable Polycarbonates from Simple, Bio-Derived Building Blocks

Plastic buildup and accumulation in the environment are an increasingly large problem facing civilization. Petroleum-based plastics can exist for hundreds to thousands of years in the environment, destroying habitats and polluting water. Environmentally conscious replacements for plastics are urgently needed. In this publication, we present a biobased alternative to petroleum-based polycarbonates. Using a diol monomer derived from glycerol and glycerol products, we have synthesized aliphatic polycarbonates with comparable physical properties to petroleum-based incumbents. The polymer can be quantitatively depolymerized using warm methanol to recover the monomer which can be repolymerized multiple times, or alternatively, the monomer, which is inherently nontoxic, can slowly break apart to the original components. This provides two end-of-life options for this material recycle or decomposition under environmental conditions to benign building blocks, thus providing a potential pathway to avoid environmental and bioaccumulation of plastics. We also demonstrate the ability to selectively recover the monomer from a simulated mixed-plastic waste environment; the monomer recovered this way functions identically to the virgin monomer after purification. This work represents an important step in the progress toward environmentally conscious polymer design with multiple end-of-life options.

36 MATERIALS SCIENCE↗

Counterintuitive Compatibilization of Poly(-Valerolactone) and Poly(L-Lactic Acid) by Statistical Copolymers toward Compostable and Recyclable Packaging

Poly(δ-valerolactone) (PVL) and poly(l-lactic acid) (PLLA) are bioderivable, compostable, and chemically recyclable plastics with synergistic properties for addressing plastic waste accumulation in receiving environments. Though recyclable-by-design polymers often fall short of competing with incumbent materials, blending affords a means to leverage individual component strengths toward ideal tunable properties. Polymer blends are often immiscible, but a range of methodologies are available to promote mixing. Here, we report on the compatibilization of 9 immiscible PVL and PLLA blends with three different compatibilization agents: thermoplastic starch, synthesized PVL-co-PLLA statistical copolymers (SCPs), and synthesized PVL-b-PLLA block-type copolymers. Resulting degrees of compatibilization are observed through scanning electron microscopy, corroborated by thermal and mechanical analyses monitoring performance as a function of microdomain size. Small-angle and wide-angle X-ray scattering experiments are conducted to observe the influence of compatibilizers on individual crystalline phases to further elucidate material behavior. Molecular dynamics simulations provide key insights into the interfacial interactions between homopolymers and compatibilizers. Finally, a suite of end-of-life avenues is established by biodegradation in industrial composting conditions, chemical recycling by deconstruction to hydroxymethyl esters, and direct chemical depolymerization to lactone precursors in mixed feed. Overall, we highlight several promising blends and the counterintuitive SCP compatibilization phenomenon toward high-performance, sustainable materials.

Compatibilization, copolymer compatibilizer, bio-b↗

Predicting homopolymer and copolymer solubility through machine learning

In this work, we report the development of multiple new machine learning (ML) models to accurately predict homopolymer/copolymer solubility over a diverse set of polymers & solvents, using explainable AI to provide polymer design recommendations.

Stubbs, Christopher D. [Department of Chemistry, C↗

Effect of penetrant–polymer interactions and shape on the motion of molecular penetrants in dense polymer networks

The diffusion of dilute molecular penetrants within polymers plays a crucial role in the advancement of material engineering for applications such as coatings and membrane separations. The potential of highly cross-linked polymer networks in these applications stems from their capacity to adjust the size and shape selectivity through subtle changes in network structures. In this paper, we use molecular dynamics simulation to understand the role of penetrant shape (aspect ratios) and its interaction with polymer networks on its diffusivity. We characterize both local penetrant hopping and the long-time diffusive motion for penetrants and consider different aspect ratios and penetrant–network interaction strengths at a variety of cross-link densities and temperatures. The shape affects the coupling of penetrant motion to the cross-link density- and temperature-dependent structural relaxation of networks and also affects the way a penetrant experiences the confinement from the network meshes. The attractive interaction between the penetrant and network primarily affects the former since only the system of dilute limit is of present interest. These results offer fundamental insights into the intricate interplay between penetrant characteristics and polymer network properties and also suggest future directions for manipulating polymer design to enhance the separation efficiency.

Chemistry↗

Polymerized small molecular acceptor based all-polymer solar cells with an efficiency of 16.16% via tuning polymer blend morphology by molecular design

All-polymer solar cells (all-PSCs) based on polymerized small molecular acceptors (PSMAs) have made significant progress recently. Here, we synthesize two A-DA’D-A small molecule acceptor based PSMAs of PS-Se with benzo[c][1,2,5]thiadiazole A’-core and PN-Se with benzotriazole A’-core, for the studies of the effect of molecular structure on the photovoltaic performance of the PSMAs. The two PSMAs possess broad absorption with PN-Se showing more red-shifted absorption than PS-Se and suitable electronic energy levels for the application as polymer acceptors in the all-PSCs with PBDB-T as polymer donor. Cryogenic transmission electron microscopy visualizes the aggregation behavior of the PBDB-T donor and the PSMA in their solutions. In addition, a bicontinuous-interpenetrating network in the PBDB-T:PN-Se blend film with aggregation size of 10~20 nm is clearly observed by the photoinduced force microscopy. The desirable morphology of the PBDB-T:PN-Se active layer leads its all-PSC showing higher power conversion efficiency of 16.16%.

14 SOLAR ENERGY↗

From p- to n-Type Mixed Conduction in Isoindigo-Based Polymers through Molecular Design

Organic mixed ionic and electronic conductors are of significant interest for bioelectronic applications. Here, we use three different isoindigoid building blocks to obtain polymeric mixed conductors with vastly different structural and electronic properties which can be further fine-tuned through the choice of comonomer unit. We show how careful design of the isoindigoid scaffold can afford highly planar polymer structures with high degrees of electronic delocalization, while subtle structural modifications can control the dominant charge carrier (hole or electron) when probed in organic electrochemical transistors. We employ a combination of experimental and computational techniques to probe electrochemical, structural and mixed ionic and electronic properties of the polymer series which in turn allows us to derive important structure-property relations for this promising class of materials in the context of organic bioelectronics. Ultimately, we use these findings to outline robust molecular design strategies for isoindigo-based mixed conductors that can support efficient p-type, n-type and ambipolar transistor operation in an aqueous environment.

36 MATERIALS SCIENCE↗

Toward a Circular Bioeconomy: Designing Microbes and Polymers for Biodegradation

Polymer production is rapidly increasing, but there are no large-scale technologies available to effectively mitigate the massive accumulation of these recalcitrant materials. One potential solution is the development of a carbon-neutral polymer life cycle, where microorganisms convert plant biomass to chemicals, which are used to synthesize biodegradable materials that ultimately contribute to the growth of new plants. Realizing a circular carbon life cycle requires the integration of knowledge across microbiology, bioengineering, materials science, and organic chemistry, which itself has hindered large-scale industrial advances. This review addresses the biodegradation status of common synthetic polymers, identifying novel microbes and enzymes capable of metabolizing these recalcitrant materials and engineering approaches to enhance their biodegradation pathways. Design considerations for the next generation of biodegradable polymers are also reviewed, and finally, opportunities to apply findings from lignocellulosic biodegradation to the design and biodegradation of similarly recalcitrant synthetic polymers are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Tuning the Mechanical and Electric Properties of Conjugated Polymer Semiconductors: Side–Chain Design Based on Asymmetric Benzodithiophene Building Blocks

Understanding molecular design rules for stretchable polymer semiconductors is important for enabling next generation stretchable electronic circuits. To simultaneously improve both electrical properties and mechanical stretchability, a design strategy is reported in introducing conjugated rigid fused-rings with bulky side groups in semiconducting polymers. In this work, the understanding of this design concept is improved by systematically investigating the effect of different types of bulky side groups asymmetrically substituted on conjugated polymer semiconductor backbones. Specifically, four types of side groups are investigated, including naphthalene (NaPh), biphenyl (PhPh), thienylphenyl (ThPh), and alkylphenyl (C4Ph), asymmetrically substituted on benzodithiophene units, namely asy-BDT. With the four types of side groups installed on BDT-containing conjugated polymers in an asymmetrical fashion, it is observed that they reduced the polymer chain aggregation and film crystallinity, hence improving the film stretchability. Furthermore, the fully conjugated polymer back-bone allows maintenance of good charge carrier mobilities. Specifically, polymer PDPP-C4Ph (with C4Ph side groups) shows the highest mobility in the fully stretchable transistor and maintained its mobility even after being subjected to hundreds of stretching-releasing cycles at 25% strain. Altogether, the results provide anunderstanding of the use of asymmetrically substituted fused-ring conjugated polymer structures to tune mechanical and charge transport properties.

36 MATERIALS SCIENCE↗

Immune-compatible designs of semiconducting polymers for bioelectronics with suppressed foreign-body response

One of the greatest obstacles to achieving implantable electronics with long-term functionality and minimized inflammatory reactions is the immune-mediated foreign-body response (FBR). Recently, semiconducting polymers with mixed electron–ion conductivity have been demonstrated as promising candidates to achieve direct electrical interfacing on bio-tissues. However, there is limited understanding of their immune compatibility in vivo, and strategies for minimizing the FBR through molecular design remain underexplored. Here we introduce a set of molecular design strategies for enhancing the immune compatibility of semiconducting polymers. Specifically, we show that selenophene, when incorporated in the backbone, can mitigate the FBR by suppressing macrophage activation. In addition, side-chain functionalization with immunomodulatory groups decreases the FBR further by downregulating the expression of inflammatory biomarkers. Together, our synthesized polymers achieve suppression of the FBR by as much as 68% (as indicated by the collagen density). In the meantime, these immune-compatible designs still provide a high charge-carrier mobility of around 1 cm 2 V −1 s −1 . In conclusion, we anticipate that such immune-compatible design principles can be translated to a variety of conjugated polymers to suppress the FBR for implantable applications.

Li, Nan [University of Chicago, IL (United States)↗

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗

Intramolecular structure and dynamics in computationally designed peptide-based polymers displaying tunable chain stiffness

Here, polymers assembled using computationally designed coiled coil bundlemers display tunable stiffness via control of interbundlemer covalent connectivity as confirmed using small-angle neutron scattering. Neutron spin echo spectroscopy reveals that rigid rod polymers show a decay rate Γ~Q 2 (Q is the scattering vector) expected of straight cylinders. Semirigid polymers assembled using bundlemers linked via 4-armed organic linker show flexible segmental dynamics at mid-Q and Γ~Q 2 behavior at high Q. The results give insight into linker flexibility-dependent interbundlemer dynamics in the hybrid polymers.

36 MATERIALS SCIENCE↗

Perspectives on Polyolefin Catalysis in Microfluidics for High-Throughput Screening: A Minireview

Polyolefins are the largest produced plastics in the world which traditionally employ continuous stirred tank reactors and fluidized bed reactors for commercial production. The operating condition, reaction kinetics, and molecular interactions inside the reactor strongly affect the polyolefin properties, which require stringent process control in conventional procedures. Understanding the catalytic pathway, behavior of polymer particles and effect of reactor conditions are essential for designing specific polymer properties, namely the molecular weight, chain length, polydispersity, etc. Microfluidics can play a significant role in designing polymers tailored to the user needs. Smaller channel dimensions help obtain uniform reaction conditions over the length of the microfluidic reactor in a controlled environment. With real-time monitoring techniques in microfluidics, even single particle growth of polymer can be studied to understand the parameters affecting the polymer properties. High throughput microfluidics can help catalyst screening in a short duration with less consumption of reagents generating less waste. When supplemented with efficient machine learning algorithms, automated high throughput microfluidics has the potential to rapidly optimize the process and develop new knowledge even with a limited data set. When trained on data sets generated using microfluidic experiments that are designed efficiently with working knowledge of the process, machine learning algorithms can provide the relationship between the multivariable parameters space and polymer properties, which is not possible with the traditional statistical methods and interpolation techniques. Here, the rise in the utilization of microfluidics, with the advancement of machine learning algorithms, for polyolefin catalysis, highlights the importance of microfluidics for catalyst discovery, parameter optimization, and understanding reaction pathway for producing polymers with specific properties for specialized applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗

Designing clay-polymer nanocomposite sorbents for water treatment: A review and meta-analysis of the past decade

Clay-polymer nanocomposites (CPNs) have been studied for two decades as sorbents for water pollutants, but their applicability remains limited. Our aim in this review is to present the latest progress in CPN research using a meta-analysis approach and identify key steps necessary to bridge the gap between basic research and CPN application. Based on results extracted from 99 research articles on CPNs and 8 review articles on other widely studies sorbents, CPNs had higher adsorption capacities for several inorganic and organic pollutant classes (including heavy metals, oxyanions, and dyes, n = 308 observations). We applied principal component analysis, analysis of variance, and multiple linear regressions to test how CPN and pollutant properties correlated with Langmuir adsorption model coefficients. While adsorption was, surprisingly, not influenced by mineral properties, it was influenced by CPN fabrication method, polymer functional groups, and pollutant properties. For example, among the pollutant classes, heavy metals had the highest adsorption capacity but the lowest adsorption affinity. Conversely, dyes had high adsorption affinities, as reflected by the linear correlation between adsorption affinity and pollutant molecular weight. Scaling from ‘basic research’ to ‘technological application’ requires testing CPN performance in real water, application in columns, comparison to commercial sorbents, regeneration, and cost evaluation. However, our survey indicates that of the 158 observations, only 20 compared the CPN's performance to that of a commercial sorbent. We anticipate that this review will promote the design of smart and functional CPNs, which can then evolve into an effective water treatment technology.

42 ENGINEERING↗

Specific molecular design of polycarboxylate polymers exhibiting optimal compatibility with clay contaminants in concrete

Highlights: • Allyl ether-based PCEs with short side chain length and low side chain density presented superior clay resistance. • PCEs with medium side chain density exhibited best clay robustness when compared at the absolute dosed quantities. • The proportion of PCE being intercalated into the layered structure of clay was quantified. It is widely recognized that the dispersing ability of polycarboxylate superplasticizers (PCEs) could be hindered due to the presence of clay contaminants in concrete. In this study, a series of allyl ether-based polycarboxylate superplasticizers possessing short polyethylene glycol side chains was successfully synthesized and probed for their clay tolerance. The resulting PCE polymers were characterized via Size Exclusion Chromatography (SEC) to obtain their molecular properties. Thereafter, their dispersing ability was probed in the absence and presence of sodium bentonite. Allyl ether-based polycarboxylate (APEG) polymers possessing short side chains were found to exhibit enhanced clay resistance as compared to that of conventional MPEG PCEs holding long pendant chains. The mode of interaction between APEG PCEs and bentonite was investigated via sorption and XRD measurements. The data revealed that APEG PCEs possessing a lower side chain density intercalate less into the interlayer space of bentonite than those exhibiting higher side chain density.

36 MATERIALS SCIENCE↗