Practical application of high energy density lithium–metal batteries (LMBs) has remained elusive over the last several decades due to their unstable and dendritic electrodeposition behavior. Solid polymer electrolytes (SPEs) with sufficient elastic modulus have been shown to attenuate dendrite growth and extend cycle life. Among different polymer architectures, network SPEs have demonstrated promising overall performance in cells using lithium metal anodes. However, fine-tuning network structures to attain adequate lithium electrode interfacial contact and stable electrodeposition behavior at extended cycling remains a challenge. In this work, we designed a series of comb-chain cross-linker-based network SPEs with tunable compliance by introducing free dangling chains into the SPE network. These dangling chains were used to tune the SPE ionic conductivity, ductility, and compliance. Our results demonstrate that increasing network compliance and ductility improves anode-electrolyte interfacial adhesion and reduces voltage hysteresis. SPEs with 56.3 wt % free dangling chain content showed a high Coulombic efficiency of 93.4% and a symmetric cell cycle life 1.9× that of SPEs without free chains. Additionally, the improved anode compliance of these SPEs led to reduced anode-electrolyte interfacial resistance growth and greater capacity retention at 92.8% when cycled at 1C in Li|SPE|LiFePO4 half cells for 275 cycles.
{"title":"Compliant Solid Polymer Electrolytes (SPEs) for Enhanced Anode-Electrolyte Interfacial Stability in All-Solid-State Lithium–Metal Batteries (LMBs)","authors":"William R. Fullerton, Christopher Y. Li","doi":"10.1021/acsapm.4c00806","DOIUrl":"https://doi.org/10.1021/acsapm.4c00806","url":null,"abstract":"Practical application of high energy density lithium–metal batteries (LMBs) has remained elusive over the last several decades due to their unstable and dendritic electrodeposition behavior. Solid polymer electrolytes (SPEs) with sufficient elastic modulus have been shown to attenuate dendrite growth and extend cycle life. Among different polymer architectures, network SPEs have demonstrated promising overall performance in cells using lithium metal anodes. However, fine-tuning network structures to attain adequate lithium electrode interfacial contact and stable electrodeposition behavior at extended cycling remains a challenge. In this work, we designed a series of comb-chain cross-linker-based network SPEs with tunable compliance by introducing free dangling chains into the SPE network. These dangling chains were used to tune the SPE ionic conductivity, ductility, and compliance. Our results demonstrate that increasing network compliance and ductility improves anode-electrolyte interfacial adhesion and reduces voltage hysteresis. SPEs with 56.3 wt % free dangling chain content showed a high Coulombic efficiency of 93.4% and a symmetric cell cycle life 1.9× that of SPEs without free chains. Additionally, the improved anode compliance of these SPEs led to reduced anode-electrolyte interfacial resistance growth and greater capacity retention at 92.8% when cycled at 1C in Li|SPE|LiFePO<sub>4</sub> half cells for 275 cycles.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kyung Rok Han, Anam Saddique, Jihong Lyu, Jin Chul Kim, In Woo Cheong
Achieving an equilibrium between the self-healing performance and thermo-mechanical properties of polymers is crucial, but exploration of the properties of self-healing polymers based on dynamic covalent bonding (DCB) in microphase-separated polymer structures remains underinvestigated. This study examines the effects of microphase separation on the self-healing and thermo-mechanical properties of a poly(dimethylsiloxane), bis(3-aminopropyl) terminated, herein denoted as PDMS, cross-linked acrylic copolymer with hindered urea bonds (HUB). This combination leverages the benefits of both acrylic copolymers and PDMS. The phase separation of the self-healing copolymer was manipulated by using solvent blending and thermal annealing methods. Two PDMSs with different molecular lengths were used to study the effects on domain size and cross-linking density. It was confirmed that solvent blending curtails microphase separation, leading to crushed nanodomains of PDMS, while thermal annealing promotes clear microphase separation with distinct nanodomains. The observations from microphase morphology, stress–strain curves, moduli, and hardness indicate a significant correlation between self-healing performance, mechanical properties, and microphase-separated structure. The self-healing capabilities of this material were validated at nano (nanoscratch test via AFM), micro (single-scratch test using optical microscopy), and macro (crosscut-healing test using UTM) scales. These findings highlight the material’s versatile nanostructures and mechanical properties, achieved through different processes, and its potential applicability in a wide range of fields.
{"title":"Microphase Separation Effects on Surface Scratch-Healing and Thermo-Mechanical Properties of Self-Healing Copolymers with Dynamic Covalent Bonds","authors":"Kyung Rok Han, Anam Saddique, Jihong Lyu, Jin Chul Kim, In Woo Cheong","doi":"10.1021/acsapm.4c00925","DOIUrl":"https://doi.org/10.1021/acsapm.4c00925","url":null,"abstract":"Achieving an equilibrium between the self-healing performance and thermo-mechanical properties of polymers is crucial, but exploration of the properties of self-healing polymers based on dynamic covalent bonding (DCB) in microphase-separated polymer structures remains underinvestigated. This study examines the effects of microphase separation on the self-healing and thermo-mechanical properties of a poly(dimethylsiloxane), bis(3-aminopropyl) terminated, herein denoted as PDMS, cross-linked acrylic copolymer with hindered urea bonds (HUB). This combination leverages the benefits of both acrylic copolymers and PDMS. The phase separation of the self-healing copolymer was manipulated by using solvent blending and thermal annealing methods. Two PDMSs with different molecular lengths were used to study the effects on domain size and cross-linking density. It was confirmed that solvent blending curtails microphase separation, leading to crushed nanodomains of PDMS, while thermal annealing promotes clear microphase separation with distinct nanodomains. The observations from microphase morphology, stress–strain curves, moduli, and hardness indicate a significant correlation between self-healing performance, mechanical properties, and microphase-separated structure. The self-healing capabilities of this material were validated at nano (nanoscratch test via AFM), micro (single-scratch test using optical microscopy), and macro (crosscut-healing test using UTM) scales. These findings highlight the material’s versatile nanostructures and mechanical properties, achieved through different processes, and its potential applicability in a wide range of fields.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ivan Hevus, Sandip Tiwari, Sagar Thorat, Luke R. Gibbon, John J. La Scala, Chad A. Ulven, Mukund P. Sibi, Dean C. Webster
We demonstrated the applicability of two vanillin-derived veratrole monomers, 4-vinyl veratrole (VV) and 3-allyl-5-vinyl veratrole (AVV), as reactive diluents for stereolithography (SLA). As structural analogues of styrene, these nonvolatile biobased monomers enable expanding the applications of styrenics to photocurable systems. Both monomers reduced the viscosity of a commercial oligomeric urethane acrylate resin to the levels acceptable for high-resolution SLA three-dimensional (3D) printing. Compared to two petrochemical controls, 2-phenoxyethyl acrylate and N-vinylpyrrolidone, the veratrole monomers required higher laser exposure to polymerize but allowed achieving high conversion of styrenic double bonds in the SLA process. Participation of the allyl group of AVV in polymerization increased the cross-link density of the 3D printed material, resulting in improved thermal stability and strength characteristics, whereas the VV-containing formulation yielded samples with superior ductility and toughness. Both vanillin-derived monomers demonstrated a significant advantage over 2-phenoxyethyl acrylate, a commercial aromatic diluent, in the thermomechanical properties of the printed materials. Furthermore, VV-based materials had higher elongation at break than the high-performing N-vinylpyrrolidone-containing formulation, whereas AVV showed superior Young’s modulus. We expect that the performance demonstrated by the veratrole monomers will accelerate the introduction of biobased styrenics into SLA resin formulations.
{"title":"Vanillin-Derived Veratrole Reactive Diluents in Stereolithography","authors":"Ivan Hevus, Sandip Tiwari, Sagar Thorat, Luke R. Gibbon, John J. La Scala, Chad A. Ulven, Mukund P. Sibi, Dean C. Webster","doi":"10.1021/acsapm.4c01183","DOIUrl":"https://doi.org/10.1021/acsapm.4c01183","url":null,"abstract":"We demonstrated the applicability of two vanillin-derived veratrole monomers, 4-vinyl veratrole (VV) and 3-allyl-5-vinyl veratrole (AVV), as reactive diluents for stereolithography (SLA). As structural analogues of styrene, these nonvolatile biobased monomers enable expanding the applications of styrenics to photocurable systems. Both monomers reduced the viscosity of a commercial oligomeric urethane acrylate resin to the levels acceptable for high-resolution SLA three-dimensional (3D) printing. Compared to two petrochemical controls, 2-phenoxyethyl acrylate and <i>N</i>-vinylpyrrolidone, the veratrole monomers required higher laser exposure to polymerize but allowed achieving high conversion of styrenic double bonds in the SLA process. Participation of the allyl group of AVV in polymerization increased the cross-link density of the 3D printed material, resulting in improved thermal stability and strength characteristics, whereas the VV-containing formulation yielded samples with superior ductility and toughness. Both vanillin-derived monomers demonstrated a significant advantage over 2-phenoxyethyl acrylate, a commercial aromatic diluent, in the thermomechanical properties of the printed materials. Furthermore, VV-based materials had higher elongation at break than the high-performing <i>N</i>-vinylpyrrolidone-containing formulation, whereas AVV showed superior Young’s modulus. We expect that the performance demonstrated by the veratrole monomers will accelerate the introduction of biobased styrenics into SLA resin formulations.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiongyang Qi, Zilong Liu, Zihan Zhao, Zhiyuan Tan, Fangfei Liu, Nan Liu
Ionogels have gained increasing attention in the field of flexible electronic devices. However, it is a huge challenge to prepare ionogels with high toughness and adhesive property. In this study, we present a straightforward approach to fabricating tough and reusable ionogel adhesives by randomly copolymerizing two monomers with varying solubilities in an ionic liquid solvent. Specifically, acrylamide (AM) and methacryloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide ([MATAC][TFSI]) are copolymerized in situ in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) to form phase-separated ionogels, wherein the hydrogen-bond-rich phases and solvent-rich phases contribute to enhancing toughness. The abundant noncovalent interactions provide the robust internal cohesive force, which provides ionogels a stable adhesion ability during the cyclic adhesion–peeling process. The resulting ionogel adhesive exhibits elevated fracture strength (2.75 MPa), impressive toughness (9.58 MJ/m3), non-disposable adhesiveness (0.692 MPa), and exceptional environmental stability. Moreover, the sensor prepared by ionogel adhesives demonstrates fatigue resistance and a wide detection range, thus holding potential for the development of advanced and sustainable flexible electronic devices.
{"title":"A Tough and Reusable Ionogel Adhesive for Flexible Strain Sensor","authors":"Jiongyang Qi, Zilong Liu, Zihan Zhao, Zhiyuan Tan, Fangfei Liu, Nan Liu","doi":"10.1021/acsapm.4c01121","DOIUrl":"https://doi.org/10.1021/acsapm.4c01121","url":null,"abstract":"Ionogels have gained increasing attention in the field of flexible electronic devices. However, it is a huge challenge to prepare ionogels with high toughness and adhesive property. In this study, we present a straightforward approach to fabricating tough and reusable ionogel adhesives by randomly copolymerizing two monomers with varying solubilities in an ionic liquid solvent. Specifically, acrylamide (AM) and methacryloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide ([MATAC][TFSI]) are copolymerized in situ in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) to form phase-separated ionogels, wherein the hydrogen-bond-rich phases and solvent-rich phases contribute to enhancing toughness. The abundant noncovalent interactions provide the robust internal cohesive force, which provides ionogels a stable adhesion ability during the cyclic adhesion–peeling process. The resulting ionogel adhesive exhibits elevated fracture strength (2.75 MPa), impressive toughness (9.58 MJ/m<sup>3</sup>), non-disposable adhesiveness (0.692 MPa), and exceptional environmental stability. Moreover, the sensor prepared by ionogel adhesives demonstrates fatigue resistance and a wide detection range, thus holding potential for the development of advanced and sustainable flexible electronic devices.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yan Miao, Jiang Wei, Mengda Xu, Qingkang Wang, Xuesong Jiang
A guided-mode resonance filter (GMRF) in the terahertz (THz) band gaining narrow line width is a vigorous approach for THz biosensing and imaging. Limited by accessible low-loss materials above 1 THz, fabrication techniques, and tuning methods, a dynamically tunable THz GMRF implementing broad frequency range tunability faces great challenges. Here, by nanoimprinting a THz low-loss elastomer styrene–butadiene–styrene (SBS) film, we propose a dynamically tunable waveguide grating structure with an expanded work frequency. Utilizing simple tension field control and Poisson’s ratio of elastomer, remarkable blueshift and redshift tunability could both be realized. When the SBS GMRF was elongated along the grating lines, a blueshift occurred from 2.63 to 3.29 THz under 300% strain. While applying perpendicular stretching, the redshift dramatically spanned 3.72 THz under 150% strain, presenting prominent strain sensitivity. Additionally, the microscopic phase separation of SBS makes it exhibit the characteristics of shape memory; hence, the cyclically stretched SBS GMRF maintained stable mechanical and optical performance. Hence, the elastic and shape reversible SBS-based GMRF will be a brilliant strategy for a tunable THz optical device.
太赫兹（THz）波段的导模共振滤波器（GMRF）线宽较窄，是太赫兹生物传感和成像的一种有效方法。受 1 太赫兹以上可获得的低损耗材料、制造技术和调谐方法的限制，实现宽频率范围可调的动态可调太赫兹 GMRF 面临着巨大挑战。在此，我们通过纳米压印太赫兹低损耗弹性体苯乙烯-丁二烯-苯乙烯（SBS）薄膜，提出了一种具有扩展工作频率的动态可调波导光栅结构。利用简单的张力场控制和弹性体的泊松比，可以实现显著的蓝移和红移可调性。当 SBS GMRF 沿着光栅线拉伸时，在 300% 的应变下，蓝移从 2.63 太赫兹增加到 3.29 太赫兹。当施加垂直拉伸时，在 150% 应变下，红移显著跨越 3.72 THz，显示出突出的应变敏感性。此外，SBS 的微观相分离使其具有形状记忆特性，因此循环拉伸 SBS GMRF 可保持稳定的机械和光学性能。因此，基于 SBS 的弹性和形状可逆 GMRF 将成为可调谐太赫兹光学器件的绝佳策略。
{"title":"Dynamic Terahertz Guided-Mode Resonance Filter for Broadband Tunability","authors":"Yan Miao, Jiang Wei, Mengda Xu, Qingkang Wang, Xuesong Jiang","doi":"10.1021/acsapm.4c01125","DOIUrl":"https://doi.org/10.1021/acsapm.4c01125","url":null,"abstract":"A guided-mode resonance filter (GMRF) in the terahertz (THz) band gaining narrow line width is a vigorous approach for THz biosensing and imaging. Limited by accessible low-loss materials above 1 THz, fabrication techniques, and tuning methods, a dynamically tunable THz GMRF implementing broad frequency range tunability faces great challenges. Here, by nanoimprinting a THz low-loss elastomer styrene–butadiene–styrene (SBS) film, we propose a dynamically tunable waveguide grating structure with an expanded work frequency. Utilizing simple tension field control and Poisson’s ratio of elastomer, remarkable blueshift and redshift tunability could both be realized. When the SBS GMRF was elongated along the grating lines, a blueshift occurred from 2.63 to 3.29 THz under 300% strain. While applying perpendicular stretching, the redshift dramatically spanned 3.72 THz under 150% strain, presenting prominent strain sensitivity. Additionally, the microscopic phase separation of SBS makes it exhibit the characteristics of shape memory; hence, the cyclically stretched SBS GMRF maintained stable mechanical and optical performance. Hence, the elastic and shape reversible SBS-based GMRF will be a brilliant strategy for a tunable THz optical device.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
4,5-Epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ether cyclic carbonate (EDDC) was synthesized by chemical addition of carbon dioxide with 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidylester (EDD) and then cross-linked with isophorondiamine (IPDA) and amino-modified poly(dimethylsiloxane) (AMPDMS) to prepare a unique fluorine-free antismudge nonisocyanate polyurethane coating (NIPU). Notably, the specific surface energy of NIPU was affected dramatically by the AMPDMS component. When its content was 1.0 wt %, the NIPU demonstrated more than 98% optical transmittance with a surface roughness of about 0.401 nm. Moreover, the NIPU coatings exhibited remarkable repellency toward different liquids, such as pump oil, corn oil, water, milk, cola, orange juice, fingerprint solution, and so on, where the CaCO3 powders could slide down with water, and no liquid droplets or CaCO3 powder remained on the coating surface. When applied to different substrate surfaces including glass, tinplate, and ceramics, the NIPU coatings still demonstrated strong antigraffiti performance. Therefore, the NIPU possessed excellent easy-to-clean, antismudge property and wear resistance, showing great application prospects.
{"title":"Fluorine-Free Nonisocyanate Polyurethane Antismudge Coating Carrying 4,5-Epoxycyclohexane-1,2-dicarboxylic Acid Diglycidyl Ether Groups","authors":"Canqun Liu, Zhenyong He, Yiyang Liu, Zhijun Wu, Jinqing Qu","doi":"10.1021/acsapm.4c01475","DOIUrl":"https://doi.org/10.1021/acsapm.4c01475","url":null,"abstract":"4,5-Epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ether cyclic carbonate (EDDC) was synthesized by chemical addition of carbon dioxide with 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidylester (EDD) and then cross-linked with isophorondiamine (IPDA) and amino-modified poly(dimethylsiloxane) (AMPDMS) to prepare a unique fluorine-free antismudge nonisocyanate polyurethane coating (NIPU). Notably, the specific surface energy of NIPU was affected dramatically by the AMPDMS component. When its content was 1.0 wt %, the NIPU demonstrated more than 98% optical transmittance with a surface roughness of about 0.401 nm. Moreover, the NIPU coatings exhibited remarkable repellency toward different liquids, such as pump oil, corn oil, water, milk, cola, orange juice, fingerprint solution, and so on, where the CaCO<sub>3</sub> powders could slide down with water, and no liquid droplets or CaCO<sub>3</sub> powder remained on the coating surface. When applied to different substrate surfaces including glass, tinplate, and ceramics, the NIPU coatings still demonstrated strong antigraffiti performance. Therefore, the NIPU possessed excellent easy-to-clean, antismudge property and wear resistance, showing great application prospects.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mousumi R. Bepari, Lauren R. Sullivan, Kathryn E. O’Harra, Gabriel D. Barbosa, C. Heath Turner, Jason E. Bara
Polyethylene terephthalate (PET) is a ubiquitous commodity plastic used in applications that include textiles, food packaging, drink bottles, and thermoplastic resins. Like other synthetic polymers, the massive accumulation of PET on Earth’s surface has presented formidable environmental challenges. As a polyester, PET is susceptible to chain cleavage (i.e., depolymerization) via various “chemolysis” methods. Here, we introduce an approach to PET cleavage by imidazole (and related compounds): “imidazolysis”. Reacting PET with excess imidazole yields 1,1′-terephthaloylbisimidazole (TBI) which can be further transformed into an array of small products such as amides, benzimidazoles, and esters or potentially used as monomers for polymers. The TBI molecules obtained via imidazolysis are versatile intermediates (owed to their activated carbonyl groups), which can be stored and subsequently converted to specific final products later. This means that the target products do not have to be predetermined when the depolymerization reaction is carried out, and this methodology could provide flexibility to meet demands for various chemical products based on the terephthalic acid (or p-xylene) motif. Based on these results, imidazolysis may also be of broad utility in depolymerizing other polyesters, as well as polyurethanes (PUs).
{"title":"Depolymerizing Polyethylene Terephthalate (PET) via “Imidazolysis” for Obtaining a Diverse Array of Intermediates from Plastic Waste","authors":"Mousumi R. Bepari, Lauren R. Sullivan, Kathryn E. O’Harra, Gabriel D. Barbosa, C. Heath Turner, Jason E. Bara","doi":"10.1021/acsapm.4c01525","DOIUrl":"https://doi.org/10.1021/acsapm.4c01525","url":null,"abstract":"Polyethylene terephthalate (PET) is a ubiquitous commodity plastic used in applications that include textiles, food packaging, drink bottles, and thermoplastic resins. Like other synthetic polymers, the massive accumulation of PET on Earth’s surface has presented formidable environmental challenges. As a polyester, PET is susceptible to chain cleavage (i.e., depolymerization) via various “chemolysis” methods. Here, we introduce an approach to PET cleavage by imidazole (and related compounds): “imidazolysis”. Reacting PET with excess imidazole yields 1,1′-terephthaloylbisimidazole (TBI) which can be further transformed into an array of small products such as amides, benzimidazoles, and esters or potentially used as monomers for polymers. The TBI molecules obtained via imidazolysis are versatile intermediates (owed to their activated carbonyl groups), which can be stored and subsequently converted to specific final products later. This means that the target products do not have to be predetermined when the depolymerization reaction is carried out, and this methodology could provide flexibility to meet demands for various chemical products based on the terephthalic acid (or <i>p</i>-xylene) motif. Based on these results, imidazolysis may also be of broad utility in depolymerizing other polyesters, as well as polyurethanes (PUs).","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Salman Syed, Baku Nagendra, Maria Rosaria Acocella, Christophe Daniel, Paola Rizzo, Oreste Tarallo, Gaetano Guerra
Co-crystalline and nanoporous-crystalline poly(2,6-dimethyl-1,4-phenylene) oxide (PPO) phases can be achieved for randomly functionalized PPO. In fact, WAXD, DSC, and FTIR studies show the presence of remarkable crystallinity in PPO films with chloroacetyl (−COCH2Cl) side groups up to 17 mol %. More surprisingly, polymer melting temperature remains constant in the range 244−246 °C up to a degree of functionalization of 12 mol %. This behavior is unprecedented in polymer science and can be rationalized by side-group inclusion in PPO intrahelical crystalline channels.
{"title":"Crystallinity and Melting of Functionalized Poly(2,6-dimethyl-1,4-phenylene) oxide (PPO)","authors":"Salman Syed, Baku Nagendra, Maria Rosaria Acocella, Christophe Daniel, Paola Rizzo, Oreste Tarallo, Gaetano Guerra","doi":"10.1021/acsapm.4c01314","DOIUrl":"https://doi.org/10.1021/acsapm.4c01314","url":null,"abstract":"Co-crystalline and nanoporous-crystalline poly(2,6-dimethyl-1,4-phenylene) oxide (PPO) phases can be achieved for randomly functionalized PPO. In fact, WAXD, DSC, and FTIR studies show the presence of remarkable crystallinity in PPO films with chloroacetyl (−COCH<sub>2</sub>Cl) side groups up to 17 mol %. More surprisingly, polymer melting temperature remains constant in the range 244−246 °C up to a degree of functionalization of 12 mol %. This behavior is unprecedented in polymer science and can be rationalized by side-group inclusion in PPO intrahelical crystalline channels.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141520875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nowadays, attractive progress has been made on flexible humidity sensors for multifunctional applications, yet most of them still suffer from intrinsic instability due to the device structure based on flexible substrates. Herein, high-performance flexible humidity sensors were constructed using alkali metal halide doped polyvinylpyrrolidone (PVP)/polyvinylidene fluoride (PVDF) freestanding films. These films are prepared via a versatile thermally induced phase separation procedure with a network-like porous structure. After doping with metal salts of MCl (M = Li, Na, K), the humidity sensing performance is highly improved, among which the LiCl@PVP/PVDF film is the optimized one. In the relative humidity range of 11–97% at room temperature, the LiCl@PVP/PVDF sensor exhibits high response (2.3 × 103), fast response (10 s), small hysteresis (0.41%), and excellent repeatability. Notably, the LiCl@PVP/PVDF film is featured as fully self-supporting without the assistance of any substrate, readily tailorable that can be cut into different shapes, as well as highly flexible that can be bent to certain angles, and meanwhile almost maintains its response without significant decrease. Furthermore, the excellent performance enables the LiCl@PVP/PVDF sensor to demonstrate great potential in real-time noncontact diaper and finger detection. This contribution provides a practical humidity sensing candidate for moisture monitoring and gives insights into the fields of humidity sensors and flexible electronics.
{"title":"High-Performance Flexible Humidity Sensors Based on MCl (M = Li, Na, K) Doped PVP/PVDF Self-Supporting Films for Boosted Real-Time Noncontact Moisture Monitoring","authors":"Zhao-Lei Huo, Jia-Yu Qiao, Le-Xi Zhang, Yao-Wen Yue, Qi-Da Qiu, Zhi-Jiang Hou, Jing Yin, Li-Jian Bie","doi":"10.1021/acsapm.4c00773","DOIUrl":"https://doi.org/10.1021/acsapm.4c00773","url":null,"abstract":"Nowadays, attractive progress has been made on flexible humidity sensors for multifunctional applications, yet most of them still suffer from intrinsic instability due to the device structure based on flexible substrates. Herein, high-performance flexible humidity sensors were constructed using alkali metal halide doped polyvinylpyrrolidone (PVP)/polyvinylidene fluoride (PVDF) freestanding films. These films are prepared via a versatile thermally induced phase separation procedure with a network-like porous structure. After doping with metal salts of MCl (M = Li, Na, K), the humidity sensing performance is highly improved, among which the LiCl@PVP/PVDF film is the optimized one. In the relative humidity range of 11–97% at room temperature, the LiCl@PVP/PVDF sensor exhibits high response (2.3 × 10<sup>3</sup>), fast response (10 s), small hysteresis (0.41%), and excellent repeatability. Notably, the LiCl@PVP/PVDF film is featured as fully self-supporting without the assistance of any substrate, readily tailorable that can be cut into different shapes, as well as highly flexible that can be bent to certain angles, and meanwhile almost maintains its response without significant decrease. Furthermore, the excellent performance enables the LiCl@PVP/PVDF sensor to demonstrate great potential in real-time noncontact diaper and finger detection. This contribution provides a practical humidity sensing candidate for moisture monitoring and gives insights into the fields of humidity sensors and flexible electronics.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hikaru Sano, Aya Yoshimura, Lei Zhang, Haruki Ebisawa, Takeshi Kiyokawa, Koichi Fujita, Yohji Misaki, Masaru Yao
Lithium-ion batteries have become the dominant technology for portable electronics and electric vehicles over the past few decades; however, high costs and limited resources have prompted the need for alternative materials. Organic batteries made of abundant and inexpensive materials have the potential to address these challenges. Our previous study focused on tetrathiafulvalene (TTF) bearing triphenylamine (TPA) moieties, TTF-4TPA, wherein TTF exhibits redox activity and TPA shows both polymerization properties and redox activity. Polymerization of active material molecules contributes to long cyclability. TTF-4TPA has been reported to polymerize during the first charge and exhibit high cyclability thereafter. This study investigated the electrochemical properties of a TTF-4TPA-based organic battery. The TTF-4TPA battery was found to exhibit excellent rate performance in a Li-ion system. Moreover, the TTF-4TPA battery was found to be operable even in a Na-ion system.
{"title":"Cation-Independent Anion Battery Using Organic Cathodes Utilizing a Triphenylamine Moiety for In-Cell Electropolymerization","authors":"Hikaru Sano, Aya Yoshimura, Lei Zhang, Haruki Ebisawa, Takeshi Kiyokawa, Koichi Fujita, Yohji Misaki, Masaru Yao","doi":"10.1021/acsapm.4c00973","DOIUrl":"https://doi.org/10.1021/acsapm.4c00973","url":null,"abstract":"Lithium-ion batteries have become the dominant technology for portable electronics and electric vehicles over the past few decades; however, high costs and limited resources have prompted the need for alternative materials. Organic batteries made of abundant and inexpensive materials have the potential to address these challenges. Our previous study focused on tetrathiafulvalene (TTF) bearing triphenylamine (TPA) moieties, TTF-4TPA, wherein TTF exhibits redox activity and TPA shows both polymerization properties and redox activity. Polymerization of active material molecules contributes to long cyclability. TTF-4TPA has been reported to polymerize during the first charge and exhibit high cyclability thereafter. This study investigated the electrochemical properties of a TTF-4TPA-based organic battery. The TTF-4TPA battery was found to exhibit excellent rate performance in a Li-ion system. Moreover, the TTF-4TPA battery was found to be operable even in a Na-ion system.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141529251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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