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At least 163 records · Page 9

Repurposing Post-Consumer Polyethylene to Access Cross-Linked Polyethylene with Reprocessabilty, Recyclability, and Tunable Properties

Polyethylene (PE) is the most widely produced plastic but accumulation and resistance to degradation has significantly contributed to the plastic waste crisis. Upcycling has presented promising solutions to transform PE waste into value-added products. In this study, mixed post-consumer PE was successfully repurposed into reprocessable and chemically recyclable cross-linked polyethylene (XLPE). This process involved converting PE into telechelic oligomers, followed by repolymerization using a hybrid cross-linking system consisting of a dynamic cross-linker 2,4,6-triethoxy-1,3,5-triazine (TETA) and non-dynamic cross-linker tris(6-isocyanatohexyl)isocyanurate (Tri-HDI). In the resulting XLPE, TETA facilitated iterative reprocessing with minimal property degradation across cycles, whereas Tri-HDI helped preserve functional performance throughout service life. Compared to PE, XLPE exhibited enhanced mechanical properties, reduced creep deformation under application-relevant temperatures, and high temperature structural stability. Notably, copolymerizing PE oligomers with commercial macrodiols was employed to create composite XLPEs, enabling tuning material properties. After use, XLPE can be efficiently and selectively depolymerized under mild conditions, even when mixed with commercial insulator cables. This depolymerization allows for the recovery of the constituent building blocks, enabling purification and subsequent repolymerization for reuse. This approach demonstrates the potential of repurposing plastic waste into sustainable materials and fostering the development of a circular economy.

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMI↗

Self‐Healable Poly(ionic liquid) Copolymers Driven by Polar and Dipolar Forces

Abstract Commodity aliphatic and aromatic acrylic‐based copolymers self‐heal due to ubiquitouskey‐and‐lock,ring‐and‐lock, andfluorophilic‐σ‐lockvan der Waals (vdW) interactions. However, the role of these interactions in the presence of covalently copolymerized ionic liquid (IL) is not known. This study is driven by the hypothesis that covalently incorporated cation–anion pairs to form poly(ionic liquid) copolymers (PILCs) can perturb inter‐ or intra‐chain vdW interactions reflected in mechanical and electrical responses. To test this hypothesis, we synthesized a series of PILCs comprising of pentafluorostyrene (PFS) and imidazolium‐based IL monomers with variable‐length aliphatic tails (methyl and butyl). Using a combination of 2D 1 H‐ 1 H and 19 F ‐ 19 F NOESY NMR and FTIR measurements supplemented by molecular dynamic (MD) simulations, these studies demonstrate that preferentially alternating/random PILCs topologies facilitate self‐healing. The introduction of cation–anion moieties modifies thefluorophilic‐σ‐lockinteractions and, along with longer aliphatic tails ─(CH 2 ) 3 CH 3 covalently attached to the imidazolium cation, enhances cation‐anion mobility, thus faster recovery from mechanical damage occurs. These findings underline how precise control over dipolar and ionic interactions through copolymer composition enables self‐healing in PILCs. These insights may open pathways for designing sustainable, mechanically resilient materials for applications in energy storage and energy harvesting.

Chemistry↗

Polymer concentration detection method based on fluorescent polymer to evaluate its retention and percolation

ABSTRACT A new fluorescent polymer was prepared by copolymerization of acrylamide and a modified rhodamine B (RhB). Fourier transformation infrared spectrometer and nuclear magnetic resonance confirmed the successful modification of RhB and the synthesis of fluorescent polymer. The rheological and fluorescence properties were studied by fluorospectrophotometer and rotational rheometer. The adsorption retention and percolation properties were evaluated by sand pack displacement experiments. The results indicated that fluorescence intensity revealed a distinct linear relationship with polymer concentration within a certain concentration range. High temperature and strong acidic conditions could diminish fluorescence intensity whereas formation water ions exerted inconsiderable influence on it. Rheological results manifested that fluorescent polymer can be used as polymer flooding agent. The sand pack displacement results proved the feasibility of using fluorescent polymer to detect polymer concentration. By this means, polymer breakthrough time and concentration variations could be confirmed. Based on the curves of injection pressure and polymer concentration, the percolation state and retention of polymer were able to be analyzed. Significantly, this work can provide support and guidance for the practical applications of fluorescent polymer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47468.

Kang, Wanli↗

Inserting Porphyrin Quantum Dots in Bottom-Up Synthesized Graphene Nanoribbons

Diels–Alder copolymerization of tetraphenylcyclopentadienone, a precursor for cove graphene nanoribbons (cGNRs), with bifunctional porphyrins yields defined nanostructures comprised of a single cGNR-porphyrin-cGNR heterojunction within each ribbon. 13 C NMR labeling and high-resolution mass spectrometry of solubilized polymer intermediates indicates that every porphyrin is covalently linked to two extended segments of cGNRs. UV/Vis absorption and fluorescence emission spectroscopy reveal a strong electronic correlation between the porphyrin and the adjacent cGNR segments that can be attenuated through reversible metalation of the porphyrin core. This versatile bottom-up synthetic strategy provides access to structurally well-defined, functional GNR-quantum dot-GNR heterostructures within a single graphene nanoribbon.

36 MATERIALS SCIENCE↗

Coupling of NMR to ACOMP for Terpolymerization Monitoring and Control

Abstract Monitoring and control of free radical copolymerization using automatic continuous online monitoring of polymerization reactions (ACOMP) with UV detection has been recently achieved. It is difficult, however, to achieve spectral separation of similar monomers with UV alone. Here, nuclear magnetic resonance (NMR) is coupled to ACOMP for the first time and terpolymerization reactions involving acrylamide (Am), sodium acrylate (Ac), and styrene sulfonate (SS) are monitored, and a first attempt at active composition control is made. The NMR resolves the concentrations of Am and Ac, while the UV resolves SS and the sum of Am and Ac. NMR analysis is performed in water, using signal suppression, to eliminate the need for deuterated solvents. From this, instantaneous fractions of each comonomer in the terpolymer are continuously known, along with weight average molecular weight and intrinsic viscosity, IV. Am and Ac have similar reactivities, whereas the reactivity ratio of SS is much larger. Hence, there is high composition drift in batch polymerization and SS is rapidly consumed, leaving a final copolymer of Am and SS to form. Maintaining constant terpolymer composition is taken as a first step toward active control.

McAfee, Terry↗

Synthesis and property of EPEG ‐based polycarboxylate ether superplasticizers via RAFT polymerization

Abstract Polycarboxylate ether superplasticizers (PCEs) with comb‐shaped molecular structures have attracted considerable attention in the area of admixtures for construction engineering. However, there are some contradictions in studying the relationship between the molecular structure and property of PCE due to its random structure based on traditional free radical polymerization, which is confused for designing and developing novel PCEs. In this article, a series of reversible addition fragmentation chain transfer (RAFT) polymerization‐based polycarboxylate ether superplasticizers (RPCs) were prepared by the copolymerization of acrylic acid (AA) and ethylene‐glycol monovinyl polyethylene glycol (EPEG). The chemical structure and composition of RPCs were characterized and their adsorption behavior and dispersion properties were conducted. The results demonstrate that the molecular weights of RPCs do not vary significantly with prolonging reaction time, and the actual monomer ratio in RPCs displays a significant change to the feed one due to the monomer reactivity and conversion at higher reaction temperature, which is different from conventional free radical polymerization. The dispersion and adsorption properties of RPCs to cement were evaluated by slurry fluidity tests and total organic carbon (TOC) experiments. The effect of polymerization temperature and time on the dispersion ability has been systematically studied. The results indicate that the dispersion ability and adsorption capacity of RPCs are closely related to their molecular structures. The dispersion ability of RPCs were enhanced with increasing carboxyl group density in a certain range of monomer molar ratios (≤6:1). This study will provide a new platform for designing and developing high‐performance and rational cost‐effective superplasticizers with well‐defined structure and controlled molecular weight.

Chen, Xiaodong↗

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

ABSTRACT Among the classes of synthetic polymers, disulfide‐containing structures offer unique opportunities due to their accessibility to redox chemistry that allows for degradation or reversible disulfide formation and exchange under mild conditions. Here, we examine the role of disulfides in olefin metathesis polymerization, specifically alternating diene metathesis (ALTMET) polymerization, for synthesizing unsaturated polyolefins with embedded disulfides. Our synthetic strategy hinged on the use of α,ω‐diacrylate monomers, including those connected by a disulfide unit, via copolymerization by the ALTMET mechanism to yield copolymers containing a range of disulfide content. In addition, the potential impacts of sulfur‐ruthenium interactions on the ALTMET process were investigated spectroscopically, while the degradation of the resultant polymers was affected by mild reducing agents. Overall, this study contributes to the development of degradable synthetic polymers using olefin metathesis methods, with an increased understanding of the potential for further use of disulfide groups in such metathesis reactions.

Lee, Kyoungwon↗

Diblock copolymers of polystyrene- b -poly(1,3-cyclohexadiene) exhibiting unique three-phase microdomain morphologies

Here, the synthesis and molecular characterization of a series of conformationally asymmetric polystyrene-block-poly(1,3-cyclohexadiene) (PS- b -PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ Φ PS ≤ 0.91) was studied by transmission electron microscopy and small-angle X-ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD-1,4)–shell(PCHD-1,2) cylinders in PS matrix and three-phase (PS, PCHD-1,4, PCHD-1,2) four-layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS- b -PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1564–1572

36 MATERIALS SCIENCE↗

Novel Biocomposites Based on Sunflower Oil and Alfa Fibers as Renewable Resources

The aim of this work is to develop biocomposites based on modified sunflower oil as resin and short natural fibers from Alfa plants (Stipa tenacissima) as reinforcement. Epoxidized sunflower oil (ESFO) was chemically modified via acrylation reaction to obtain acrylated epoxidized sunflower oil resin (AESFO). The AESFO resin was then copolymerized with styrene as co-monomer in the presence of boron trifluoride (BF{sub 3}) as cationic initiator and cobalt octoate (Co) as catalyst. Experimental conditions of this modification were optimized by varying styrene, Co and BF{sub 3} wt%. The styrene was varied from 30, 40 to 50 wt% while the catalyst (Co) was varied from 0, 0.01, 0.02 to 0.03 wt%. Two different percents of BF{sub 3} were considered: 0.5 and 1 wt%. The prepared samples were evaluated according to their appearance and then characterized in terms of tensile properties (stress at break, Young’s modulus and elongation at break) to determine the best ratio of styrene/BF{sub 3}/Co. Alfa fibers, used as bio-reinforcement, were treated with a 5% NaOH solution and characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA). Biocomposites were prepared by using untreated (UAF) and treated Alfa fibers (TAF) at a ratio of 5 wt% and characterized in terms of tensile properties and morphology by SEM. The best results were obtained with TAF. Then, the ratio of TAF was varied (5, 7.5 and 10 wt%) and the tensile and thermal properties of the biocomposites were characterized. The results showed that the best results were obtained with the ratio of 7.5 wt%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Characterization of High Molecular Weight Polyesters by Matrix-Assisted Laser Desorption/Ionization High-Resolution Time-of-Flight Mass Spectrometry Combined with On-plate Alkaline Degradation and Mass Defect Analysis

Matrix-assisted laser desorption ionization high-resolution time-of-flight mass spectrometry (MALDI HR TOF MS) is a powerful tool for the molecular characterization of industrial polymers. However, accurate mass determination and resolution of isobaric ions are possible for oligomer samples only typically below m/z 3000. To cut long polymer chains into oligomers suitable for high-resolution mass spectrometry, we propose a simple “on-plate” alkaline degradation of polyesters as a sample pretreatment technique prior to the MALDI TOF MS measurement. This pretreatment can be performed on a MALDI target using a small amount of sample (μg or less) and 1 μL of alkaline reagent by simple pipetting. Informative mass spectra in the oligomeric mass range are successfully recorded but complicated by the variation of end-groups and the copolymeric composition of the degradation products. Data processing is assisted by a series of advanced Kendrick mass defect (KMD) analyses recently proposed by the authors to plot visually understandable two-dimensional maps. On-plate degradation pretreatment, high-resolution MALDI TOF MS measurements, and advanced KMD analyses are innovatively combined for the compositional characterization of bacterial poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) and industrial poly(ethylene terephthalate) samples. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Mammalian nonmuscle myosin II comes in three flavors

Highlights: • Nonmuscle myosin II executes numerous mechanical tasks in cells including cytoskeleton organization and cell migration. • Three mammalian nonmuscle myosin II paralogs have distinct kinetic and dynamic properties in vitro and in vivo. • Mammalian nonmuscle myosin II paralogs mix and match their abilities to perform both individual and joint tasks in the cell. Nonmuscle myosin II is an actin-based motor that executes numerous mechanical tasks in cells including spatiotemporal organization of the actin cytoskeleton, adhesion, migration, cytokinesis, tissue remodeling, and membrane trafficking. Nonmuscle myosin II is ubiquitously expressed in mammalian cells as a tissue-specific combination of three paralogs. Recent studies reveal novel specific aspects of their kinetics, intracellular regulation and functions. On the other hand, the three paralogs also can copolymerize and cooperate in cells. Here we review the recent advances from the prospective of how distinct features of the three myosin II paralogs adapt them to perform specialized and joint tasks in the cell.

60 APPLIED LIFE SCIENCES↗

Reinforced double-threaded slide-ring networks for accelerated hydrogel discovery and 3D printing

Traditionally, slide-ring gels are stretchable but soft as a result of an elasticity-stretchability trade-off. Herein, we introduce a new approach to breaking this trade-off and creating reinforced slide-ring networks with mobile crosslinkers. Our approach involves the construction of a polyethylene glycol double-threaded γ-cyclodextrin-based pro-slide-ring crosslinker that serves as a modular component for 3D printing and copolymerization. The resulting crystalline-domain-reinforced slide-ring hydrogels, or CrysDoS-gels, exhibit both high elasticity and high stretchability. The modular synthesis allows for high-throughput synthesis of CrysDoS-gels, generating a large amount of data for structure-property analysis. Here, by employing data science techniques, such as machine learning and linear regression, not only were we able to identify which chemical components influence the mechanical properties of CrysDoS-gels, but this analysis also aided in the discovery of better-performing CrysDoS-gels. Finally, we demonstrate the potential application of the newly discovered CrysDoS-gels as sensing devices by 3D printing them as stress sensors with high sensitivity and a broad detection range.

3D-printing↗

Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

Liao, Chen↗

Mechanically and thermally robust microporous copolymer separators for lithium ion batteries

Next generation, multifunctional separators can enhance energy storage, power, and safety performance of lithium ion batteries but must be simple to fabricate and incorporate with existing roll-to-roll manufacturing. Here, this study presents a strategy to facilely prepare these separators using UV-initiated polymerization-induced phase separation (PIPS), wherein microporous polymer separators are fabricated directly from constituent monomers and ethylene carbonate (EC) porogen. This enables a wide compositional design space as co-monomers with specific chemical functionality can be readily incorporated into the PIPS precursor mixture. Herein, 1,4-butanediol diacrylate (BDDA) was copolymerized with poly(ethylene glycol) diacrylate (PEGDA) to increase the acrylate conversion in the photopolymerization and improve mechanical properties. By tuning the ratio of PEGDA and EC, separators with high porosity (41.3%) and effective ionic conductivity (2.09 mS cm –1 ) were prepared. Inclusion of PEGDA was essential to increasing the elastic modulus to > 345 MPa, which is required for cell assembly by roll-to-roll manufacturing. All separators prepared were shown to enable reversible cycling of lithium metal/LiNi 0.5 Mn 0.3 Co 0.2 O 2 half-cells for 100 cycles. Unlike conventional polyolefin separators, which were shown to melt at 160 °C and shrink by up to 29.8% at elevated temperatures, the PIPS separators possess exceptional, safety-enhancing thermomechanical properties, undergoing no phase transitions or thermal shrinkage.

25 ENERGY STORAGE↗

Influence of side-chain length on long-term release kinetics from poly(2-oxazoline)-drug conjugate networks

Four drug-conjugated poly(2-alkyl-2-oxazoline) (PAOx) networks with different hydrophobicity were synthesized via copolymerization of either 2-methyl-, 2-ethyl-, 2-propyl- or 2-butyl-2-oxazoline with the functional monomer, 2-dec-9-enyl-2-oxazoline. The incorporation of a labile ester linkage between the polymer and the drug benazepril allowed for sustained drug release over periods of months with the release rates strongly depending on the hydrophobicity of the polymer pendant groups. Drug loading of 13 ± 2 wt% was used with 10 mol% crosslinking sites simply by tuning the thiol-ene stoichiometry. The networks exhibited negligible cell toxicity but cell repulsion was observed for hydrogels based on poly(2-methyl-2-oxazoline) and poly(2-ethyl-2-oxazoline) while those based on poly(2-n-propyl-2-oxazoline) and poly(2-n-butyl-2-oxaoline) showed cell adhesion. Furthermore, these results suggest that PAOx networks have great potential as drug delivery devices for long-lasting drug release applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Transformations of Captured CO2 into Cyclic and Polymeric Carbonates

Alkylcarbonate ionic liquids are shown to be chemically active CO2 surrogates for transcarboxylating cyclohexene oxide to produce poly-carbonates. Catalytic equivalents of alkylcarbonate ionic liquids can be added to copolymerizations of cyclohexene oxide/CO2 to in-crease the yield and selectivity of the polymer. On the other hand, in the case of propylene oxide, polymerization is suppressed, and pro-pylene oxide is converted to propylene carbonate. The suppression of polymerization is due to the high activity of the alkylcarbonate ionic liquids towards carboxylation of epoxides for cyclic carbonate formation. The reactivity of alkylcarbonate ionic liquids with propylene oxide is sufficient enough that propylene carbonate is produced in the absence of catalyst at pressures as low as 1 atm at 60 °C.

Kothandaraman, Jotheeswari↗