ACS polymers Au最新文献

{"title":"Continuous Polymer Synthesis and Manufacturing of Polyurethane Elastomers Enabled by Automation","authors":"Johann L. Rapp,&nbsp;Meredith A. Borden,&nbsp;Vittal Bhat,&nbsp;Alexis Sarabia and Frank A. Leibfarth*,&nbsp;","doi":"10.1021/acspolymersau.3c00033","DOIUrl":"10.1021/acspolymersau.3c00033","url":null,"abstract":"<p >Connecting polymer synthesis and processing is an important challenge for streamlining the manufacturing of polymeric materials. In this work, the automated synthesis of acrylate-capped polyurethane oligomers is integrated with vat photopolymerization 3D printing. This strategy enabled the rapid manufacturing of a library of polyurethane-based elastomeric materials with differentiated thermal and mechanical properties. The automated semicontinuous batch synthesis approach proved enabling for resins with otherwise short shelf lives because of the intimate connection between synthesis, formulation, and processing. Structure–property studies demonstrated the ability to tune properties through systematic alteration of cross-link density and chemical composition.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"120–127"},"PeriodicalIF":0.0,"publicationDate":"2024-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139585414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"All-Polymer Nanocomposite as Salt-Free Solid Electrolyte for Lithium Metal Batteries","authors":"Jorge L. Olmedo-Martínez,&nbsp;Rafael Del Olmo,&nbsp;Antonela Gallastegui,&nbsp;Irune Villaluenga,&nbsp;Maria Forsyth,&nbsp;Alejandro J. Müller* and David Mecerreyes*,&nbsp;","doi":"10.1021/acspolymersau.3c00035","DOIUrl":"10.1021/acspolymersau.3c00035","url":null,"abstract":"<p >Solid polymer electrolytes that combine both a high lithium-ion transference number and mechanical properties at high temperatures are searched for improving the performance of batteries. Here, we show a salt-free all-polymer nanocomposite solid electrolyte for lithium metal batteries that improves the mechanical properties and shows a high lithium-ion transference number. For this purpose, lithium sulfonamide-functionalized poly(methyl methacrylate) nanoparticles (LiNPs) of very small size (20–30 nm) were mixed with poly(ethylene oxide) (PEO). The morphology of all-polymer nanocomposites was first investigated by transmission electron microscopy (TEM), showing a good distribution of nanoparticles (NPs) even at high contents (50 LiNP wt %). The crystallinity of PEO was investigated in detail and decreased with the increasing concentration of LiNPs. The highest ionic conductivity value for the PEO 50 wt % LiNP nanocomposite at 80 °C is 1.1 × 10^–5 S cm^–1, showing a lithium-ion transference number of 0.68. Using dynamic mechanic thermal analysis (DMTA), it was shown that LiNPs strengthen PEO, and a modulus of ≈10⁸ Pa was obtained at 80 °C for the polymer nanocomposite. The nanocomposite solid electrolyte was stable with respect to lithium in a Li||Li symmetrical cell for 1000 h. In addition, in a full solid-state battery using LiFePO₄ as the cathode and lithium metal as the anode, a specific capacity of 150 mAhg^–1 with a current density of 0.05 mA cm^–2 was achieved.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"77–85"},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00035","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139481957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Strength Organic–Inorganic Composites with Superior Thermal Insulation and Acoustic Attenuation","authors":"Divya Iyer,&nbsp;Mohammad Galadari,&nbsp;Fernaldy Wirawan,&nbsp;Vanessa Huaco,&nbsp;Ricardo Martinez,&nbsp;Michael T. Gallagher,&nbsp;Laurent Pilon,&nbsp;Kanji Ono,&nbsp;Dante A. Simonetti,&nbsp;Gaurav N. Sant and Samanvaya Srivastava*,&nbsp;","doi":"10.1021/acspolymersau.3c00037","DOIUrl":"10.1021/acspolymersau.3c00037","url":null,"abstract":"<p >We demonstrate facile fabrication of highly filled, lightweight organic–inorganic composites comprising polyurethanes covalently linked with naturally occurring clinoptilolite microparticles. These polyurethane/clinoptilolite (PUC) composites are shown to mitigate particle aggregation usually observed in composites with high particle loadings and possess enhanced thermal insulation and acoustic attenuation compared with conventionally employed materials (e.g., drywall and gypsum). In addition to these functional properties, the PUC composites also possess flexural strengths and strain capacities comparable to and higher than ordinary Portland cement (OPC), respectively, while being ∼1.5× lighter than OPC. The porosity, density, and mechanical and functional properties of these composites are tuned by systematically varying their composition (diisocyanate, polyurethane, and inorganic contents) and the nature of the organic (reactivity and source of polyol) components. The fabrication process involves mild curing conditions and uses commonly available reagents (naturally occurring aluminosilicate particles, polyols, and diisocyanate), thereby making the process scalable. Finally, the composite properties are shown to be independent of the polyol source (virgin or recycled), underlining the generality of this approach for the scalable utilization of recycled polyols.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"86–97"},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00037","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139481956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Poly(vinylidene fluoride) Aerogels with α, β, and γ Crystalline Forms: Correlating Physicochemical Properties with Polymorphic Structures","authors":"Sruthi Suresh,&nbsp;Turkan Nabiyeva,&nbsp;Laure Biniek* and E. Bhoje Gowd*,&nbsp;","doi":"10.1021/acspolymersau.3c00044","DOIUrl":"10.1021/acspolymersau.3c00044","url":null,"abstract":"<p >Strategic customization of crystalline forms of poly(vinylidene fluoride) (PVDF) aerogels is of great importance for a variety of applications, from energy harvesters to thermal and acoustic insulation. Here, we report sustainable strategies to prepare crystalline pure α, β, and γ forms of PVDF aerogels from their respective gels using a solvent exchange strategy with green solvents, followed by a freeze-drying technique. The crucial aspect of this process was the meticulous choice of appropriate solvents to enable the formation of thermoreversible gels of PVDF by crystallization-induced gelation. Depending on the polymer–solvent interactions, the chain conformation of PVDF can be modulated to obtain gels and aerogels with specific crystalline structures. The crystalline pure α-form and piezoelectric β-form aerogels were readily obtained by using cyclohexanone and γ-butyrolactone as gelation solvents. On the other hand, the γ-form aerogel was obtained using a binary solvent system consisting of dimethylacetamide and water. These aerogels with distinct crystalline structures exhibit different morphologies, mechanical properties, hydrophobicities, acoustic properties, and electrical properties. Measurement of thermal conductivity for these aerogels showed exceptionally low thermal conductivity values of ∼0.040 ± 0.003 W m^–1 K^–1 irrespective of their crystal structures. Our results showcase the fabrication approaches that enable PVDF aerogels with varied physicochemical properties for multifunctional applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"128–139"},"PeriodicalIF":0.0,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139458809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Inorganic Bottlebrush and Comb Polymers as a Platform for Supersoft, Solvent-Free Elastomers","authors":"Edip Ajvazi,&nbsp;Felix Bauer,&nbsp;Paul Strasser,&nbsp;Oliver Brüggemann,&nbsp;Rene Preuer,&nbsp;Milan Kracalik,&nbsp;Sabine Hild,&nbsp;Mahdi Abbasi,&nbsp;Ingrid Graz and Ian Teasdale*,&nbsp;","doi":"10.1021/acspolymersau.3c00043","DOIUrl":"10.1021/acspolymersau.3c00043","url":null,"abstract":"<p >Due to their unique rheological and mechanical properties, bottlebrush polymers are inimitable components of biological and synthetic systems such as cartilage and ultrasoft elastomers. However, while their rheological properties can be precisely controlled through their macromolecular structures, the current chemical spectrum available is limited to a handful of synthetic polymers with aliphatic carbon backbones. Herein we design and synthesize a series of inorganic bottlebrush polymers based on a unique combination of polydimethylsiloxane (PDMS) and polyphosphazene (PPz) chemistry. This non-carbon-based platform allows for simple variation of the significant architectural dimensions of bottlebrush-polymer-based elastomers. Grafting PDMS to PPz and vice versa also allows us to further exploit the unique properties of these polymers combined in a single material. These novel hybrid bottlebrush polymers were cured to give supersoft, solvent-free elastomers. We systematically studied the effect of architectural parameters and chemical functionality on their rheological properties. Besides forming supersoft elastomers, the energy dissipation characteristics of the elastomers were observed to be considerably higher than those for PDMS-based elastomers. Hence this work introduces a robust synthetic platform for solvent-free supersoft elastomers with potential applications as biomimetic damping materials.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"56–65"},"PeriodicalIF":0.0,"publicationDate":"2024-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139458830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Calculating Pairwise Similarity of Polymer Ensembles via Earth Mover’s Distance","authors":"Jiale Shi,&nbsp;Dylan Walsh,&nbsp;Weizhong Zou,&nbsp;Nathan J. Rebello,&nbsp;Michael E. Deagen,&nbsp;Katharina A. Fransen,&nbsp;Xian Gao,&nbsp;Bradley D. Olsen* and Debra J. Audus*,&nbsp;","doi":"10.1021/acspolymersau.3c00029","DOIUrl":"10.1021/acspolymersau.3c00029","url":null,"abstract":"<p >Synthetic polymers, in contrast to small molecules and deterministic biomacromolecules, are typically ensembles composed of polymer chains with varying numbers, lengths, sequences, chemistry, and topologies. While numerous approaches exist for measuring pairwise similarity among small molecules and sequence-defined biomacromolecules, accurately determining the pairwise similarity between two polymer ensembles remains challenging. This work proposes the earth mover’s distance (EMD) metric to calculate the pairwise similarity score between two polymer ensembles. EMD offers a greater resolution of chemical differences between polymer ensembles than the averaging method and provides a quantitative numeric value representing the pairwise similarity between polymer ensembles in alignment with chemical intuition. The EMD approach for assessing polymer similarity enhances the development of accurate chemical search algorithms within polymer databases and can improve machine learning techniques for polymer design, optimization, and property prediction.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"66–76"},"PeriodicalIF":0.0,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00029","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139439376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Trimethylsilanol Cleaves Stable Azaylides As Revealed by Unfolding of Robust “Staudinger” Single-Chain Nanoparticles","authors":"Agustín Blázquez-Martín,&nbsp;Sebastián Bonardd,&nbsp;Ester Verde-Sesto,&nbsp;Arantxa Arbe and José A. Pomposo*,&nbsp;","doi":"10.1021/acspolymersau.3c00046","DOIUrl":"10.1021/acspolymersau.3c00046","url":null,"abstract":"<p >Herein, we disclose a unique and selective reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction, enabling the on-demand unfolding of robust single-chain nanoparticles (SCNPs). SCNPs with promising use in catalysis, nanomedicine, and sensing are obtained through intrachain folding of discrete synthetic polymer chains. The unfolding of SCNPs involving reversible interactions triggered by a variety of external stimuli (e.g., pH, temperature, light, and redox potential) or substances (e.g., competitive reagents, solvents, and anions) is well known. Conversely, methods for the unfolding (i.e., intrachain disassembly) of SCNPs with stronger covalent interactions are scarce. We show that trimethylsilanol (Me₃SiOH) triggers the efficient unfolding of robust “Staudinger” SCNPs with stable azaylide (−N═P−) moieties as intrachain cross-linking units showing exceptional stability toward water, air, and CS₂, a standard reagent for azaylides. As a consequence, Me₃SiOH arises as a rare, exceptional, and valuable reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"140–148"},"PeriodicalIF":0.0,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139422943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D Printable Modular Soft Elastomers from Physically Cross-linked Homogeneous Associative Polymers","authors":"Myoeum Kim,&nbsp;Shifeng Nian,&nbsp;Daniel A. Rau,&nbsp;Baiqiang Huang,&nbsp;Jinchang Zhu,&nbsp;Guillaume Freychet,&nbsp;Mikhail Zhernenkov and Li-Heng Cai*,&nbsp;","doi":"10.1021/acspolymersau.3c00021","DOIUrl":"10.1021/acspolymersau.3c00021","url":null,"abstract":"<p >Three-dimensional (3D) printing of elastomers enables the fabrication of many technologically important structures and devices. However, there remains a critical need for the development of reprocessable, solvent-free, soft elastomers that can be printed without the need for post-treatment. Herein, we report modular soft elastomers suitable for direct ink writing (DIW) printing by physically cross-linking associative polymers with a high fraction of reversible bonds. We designed and synthesized linear-associative-linear (LAL) triblock copolymers; the middle block is an associative polymer carrying amide groups that form double hydrogen bonding, and the end blocks aggregate to hard glassy domains that effectively act as physical cross-links. The amide groups do not aggregate to nanoscale clusters and only slow down polymer dynamics without changing the shape of the linear viscoelastic spectra; this enables molecular control over energy dissipation by varying the fraction of the associative groups. Increasing the volume fraction of the end linear blocks increases the network stiffness by more than 100 times without significantly compromising the extensibility. We created elastomers with Young’s moduli ranging from 8 kPa to 8 MPa while maintaining the tensile breaking strain around 150%. Using a high-temperature DIW printing platform, we transformed our elastomers to complex, highly deformable 3D structures without involving any solvent or post-print processing. Our elastomers represent the softest melt reprocessable materials for DIW printing. The developed LAL polymers synergize emerging homogeneous associative polymers with a high fraction of reversible bonds and classical block copolymer self-assembly to form a dual-cross-linked network, providing a versatile platform for the modular design and development of soft melt reprocessable elastomeric materials for practical applications.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"98–108"},"PeriodicalIF":0.0,"publicationDate":"2024-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139093639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Polymer Gel Elasticity on Complex Coacervate Phase Behavior","authors":"Kathryn G. Wilcox,&nbsp;Kai R. Yamagami,&nbsp;Brittany K. Roopnarine,&nbsp;Adam Linscott and Svetlana Morozova*,&nbsp;","doi":"10.1021/acspolymersau.3c00027","DOIUrl":"10.1021/acspolymersau.3c00027","url":null,"abstract":"<p >Gels are key materials in biological systems such as tissues and may control biocondensate formation and structure. To further understand the effects of elastic environments on biomacromolecular assembly, we have investigated the phase behavior and radii of complex coacervate droplets in polyacrylamide (PAM) networks as a function of gel modulus. Poly-<span>l</span>-lysine (PLL) and sodium hyaluronate (HA) complex coacervate phases were prepared in PAM gels with moduli varying from 0.035 to 15.0 kPa. The size of the complex coacervate droplets is reported from bright-field microscopy and confocal fluorescence microscopy. Overall, the complex coacervate droplet volume decreases inversely with the modulus. Fluorescence microscopy is also used to determine the phase behavior and concentration of fluorescently tagged HA in the complex coacervate phases as a function of ionic strength (100–270 mM). We find that the critical ionic strength and complex coacervate stability are nonmonotonic as a function of the network modulus and that the local gel concentration can be used to control phase behavior and complex coacervate droplet size scale. By understanding how elastic environments influence simple electrostatic assembly, we can further understand how biomacromolecules exist in complex, crowded, and elastic cellular environments.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 2","pages":"109–119"},"PeriodicalIF":0.0,"publicationDate":"2023-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139053132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carborane-Containing Polymers: Synthesis, Properties, and Applications","authors":"Xinyi Zhang,&nbsp;Louis M. Rendina* and Markus Müllner*,&nbsp;","doi":"10.1021/acspolymersau.3c00030","DOIUrl":"10.1021/acspolymersau.3c00030","url":null,"abstract":"<p >Carboranes are an important class of electron-delocalized icosahedral carbon–boron clusters with unique physical and chemical properties, which can offer various functions to polymers including enhanced heat-resistance, tuned electronic properties and hydrophobicity, special ability of dihydrogen bond formation, and thermal neutron capture. Carborane-containing polymers have been synthesized mainly by means of step-growth polymerizations of disubstituted carborane monomers, with chain-growth polymerizations of monosubstituted carborane monomers including ATRP, RAFT, and ROMP only utilized recently. Carborane-containing polymers may find application as harsh-environment resistant materials, ceramic precursors, fluorescent materials with tuned emissive properties, novel optoelectronic devices, potential BNCT agents, and drug carriers with low cytotoxicity. This review highlights carborane-containing polymer synthesis strategies and potential applications, showcasing the versatile properties and possibilities that this unique family of boron compounds can provide to the polymeric systems.</p>","PeriodicalId":72049,"journal":{"name":"ACS polymers Au","volume":"4 1","pages":"7–33"},"PeriodicalIF":0.0,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acspolymersau.3c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138680114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}