ACS Applied Polymer Materials最新文献

{"title":"Sugar-Based Methacrylate Resins for Use in High-Performance, Transparent, and Sustainable Thermoset Coatings","authors":"Nataliya Kiriy*,&nbsp;Pascal Gausmann,&nbsp;Pauline Shamraienko,&nbsp;Stanislav Chekhovskyi,&nbsp;Ronny Frank,&nbsp;Anton Kiriy and Brigitte Voit*,&nbsp;","doi":"10.1021/acsapm.4c0392410.1021/acsapm.4c03924","DOIUrl":"https://doi.org/10.1021/acsapm.4c03924https://doi.org/10.1021/acsapm.4c03924","url":null,"abstract":"<p >This paper reports methacrylate resins incorporating biobased building blocks, synthesized using commercially available galactarate (GalX) and xylofuranose (IPrXF), modified with methacrylate groups through efficient transesterification. The study revealed that these biobased resins, GalX Me DMA and IPrXF DMA, cure at significantly lower temperatures (100–110 °C) compared to the commercial UMA 121 derived from urethane methacrylate containing methylene bisphenyl isocyanate building blocks. Thermal analysis showed that these cured resins exhibit exceptional thermostability, with an initial decomposition temperature exceeding 230 °C and a 50% weight loss temperature above 380 °C, outperforming UMA 121 thermosets. Mechanical testing using quantitative nanomechanical mapping with atomic force microscopy revealed elastic modulus values ranging from 2.9 to 3.8 GPa, which significantly outperforms previously published biobased thermosets and was closely comparable to UMA 121, which demonstrated an elastic modulus of 4.7 GPa. Pressure testing further corroborated these findings, confirming the robust mechanical performance of the biobased resins. The biobased resins exhibited remarkable enzymatic stability against degradation by polyester hydrolase PHL7 and demonstrated excellent resistance to chemical exposure. Notably, the sugar-based resins developed in this work contain a relatively high weight percentage of biobased components, reaching up to 70%. The biobased thermosets are transparent, colorless, and exhibit excellent film-forming properties. Overall, these resins offer promising performance for sustainable, durable coatings, combining high thermal stability, mechanical strength, and favorable environmental properties.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3233–3244 3233–3244"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608813","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}

{"title":"Machine Learning Model for Predicting Dielectric Constant of Epoxy Resin with Additional Data Selection and Design of Monomer Structures for Low Dielectric Constant","authors":"Yuya Shiraki,&nbsp;Yuko Kawanami,&nbsp;Kenichi Shinmei and Hiromasa Kaneko*,&nbsp;","doi":"10.1021/acsapm.4c0327910.1021/acsapm.4c03279","DOIUrl":"https://doi.org/10.1021/acsapm.4c03279https://doi.org/10.1021/acsapm.4c03279","url":null,"abstract":"<p >The demand for materials with high insulation and low dielectric loss in the electronic material market has led to a growing need for low dielectric constant (DC) materials. Researchers have repeatedly designed, synthesized, and measured materials to develop low DC materials by utilizing their knowledge, necessitating long development periods and high costs in terms of personnel, reagents, and equipment. This study aims to propose monomer structures for epoxy resins with low DC because they are reactive small molecules that offer good processability and moldability. To this end, a DC prediction model was constructed using machine learning, and then a large number of virtual chemical structures of epoxy resins, which were 612 739 and 430 044 structures, were generated using a method based on the connection of the main and side chains and virtual chemical reactions, respectively. Subsequently, the properties of generated structures were predicted with constructed models to search for the structures of epoxy resins with low DC. Further, the predictive ability of the DC model was improved from 0.270 to 0.371 of <i>r</i>² in double cross-validation by appropriately selecting samples from the official database and adding them to the training data.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2809–2818 2809–2818"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609115","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}

{"title":"iClick-Mediated Au(I) Functionalization of Polystyrene: Lighting Up Polystyrene with Phosphorescence","authors":"Amran Khan,&nbsp;Sohel Ahmed,&nbsp;Yan Zhao,&nbsp;Tanjila Islam,&nbsp;Nicholas J. Campbell,&nbsp;Abul Mansur Muhammed Fahim,&nbsp;Carlos Zor-El Cabrera,&nbsp;Adam S. Veige* and Kirk S. Schanze*,&nbsp;","doi":"10.1021/acsapm.4c0389710.1021/acsapm.4c03897","DOIUrl":"https://doi.org/10.1021/acsapm.4c03897https://doi.org/10.1021/acsapm.4c03897","url":null,"abstract":"<p >A series of polystyrene-based polymers that are randomly functionalized with Au(I) chromophores that exhibit phosphorescence and electrophosphorescence are reported. The polymers feature side-chain conjugated moieties that are based on R₃P–Au(I)–C≡C–Ar (where Ar = phenyl or 1-naphthyl and R = ethyl or phenyl) and a novel digold triazole functionality that is derived from an iClick reaction between R₃P–Au(I)–N₃ and the R₃P–Au(I)–C≡C–Ar units. The R₃P–Au(I)-C≡C–Ar substituted polymers are prepared by the reaction of R₃P–AuCl with the ethynyl-functionalized polystyrenes (10 mol % ethynyl groups). Subsequently, an iClick reaction is carried out on the R₃P–Au(I)–C≡C–Ar functionalized polymers to afford the digold triazole functionalized polymers. The iClick reactions are monitored by <i>in situ</i> ¹H and ³¹P NMR spectroscopy. Molecular dynamics (MD) simulations of the monogold R₃P–Au(I)–C≡C–Ar polymers reveal that there are significant attractive interactions between the metalated repeat units, especially in the polymers featuring triethylphosphine ligands at the Au(I) centers (e.g., Et₃P–Au(I)–C≡C–Ar). The photophysical study of the polymers reveals that the emission is dominated by phosphorescence from ³π,π* excited states localized on the metalated units. The phenyl-based polymers exhibit phosphorescence in the blue region (λ_max ∼ 435 nm), whereas the naphthyl-based polymers exhibit yellow-red phosphorescence (λ_max ∼ 600 nm). Preliminary studies demonstrate the application of side-chain functionalized polymers in electroluminescent devices.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3134–3146 3134–3146"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609050","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}

{"title":"Antielectrophoretic Response-Driven Bending–Tilting Deformation of Cationic Polyelectrolyte Brushes Drives Nonlinear Electroosmotic Transport in Brush-Grafted Nanochannels","authors":"Raashiq Ishraaq,&nbsp; and ,&nbsp;Siddhartha Das*,&nbsp;","doi":"10.1021/acsapm.4c0326610.1021/acsapm.4c03266","DOIUrl":"https://doi.org/10.1021/acsapm.4c03266https://doi.org/10.1021/acsapm.4c03266","url":null,"abstract":"<p >In this paper, we use all-atom molecular dynamics (MD) simulations to describe a nonlinearly enhanced electroosmotic (EOS) flow, where, in a nanochannel grafted with cationic PMETAC ([poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride]) brushes, a 2-fold increase in the electric field strength leads to a several-fold (more than 2-fold) increase in the EOS flow strength and volume flow rate. The electric field enforces the PMETAC brushes to undergo a bending–tilting-driven deformation, with a significant portion of the brush layer becoming parallel to the grafting surface. In response, a substantial fraction of the counterions leave the brush layer (hence become more mobile) but instead of going into the bulk, accumulate at the brush–bulk interface, i.e., stay in proximity to the brush segments aligned parallel to the grafting surface. This creates an interesting situation where the counterions are not completely within the brush layer, yet they fully screen the brush charges. Such “freer” conditions enable the counterions to achieve very high velocity, thereby ensuring that the water solvating the counterions themselves moves very fast, triggering the significantly augmented EOS transport. Probing deeper, we can identify that the bending–tilting-driven brush deformation, enforcing the brushes to align parallel to the substrate, results from the antielectrophoretic behavior of the brushes, where, despite being positively charged, the brushes move against the electric field direction. Such an antielectrophoretic behavior of the PE brushes, which has not been reported before, can be associated with the very fast velocities of the negatively charged counterions and the electrostatic and hydrodynamic coupling of the counterions with the positive functional groups of the brushes. We anticipate that the findings of this paper will shed light on strategies for nanochannel flow, the antielectrophoretic response of charged polymer chains, and the significance of capturing the detailed chemical architecture of polyelectrolytes in nanoscale science and engineering.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2797–2808 2797–2808"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609117","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}

{"title":"Dipole Glass Polymer with High Dielectric Constant Based on Side Chain Functionalized Poly(ether ether ketone)","authors":"Xuexia Li,&nbsp;Thumawadee Wongwirat,&nbsp;Linqi Li,&nbsp;Yuan Xi,&nbsp;Junji Wei* and Lei Zhu,&nbsp;","doi":"10.1021/acsapm.4c0362110.1021/acsapm.4c03621","DOIUrl":"https://doi.org/10.1021/acsapm.4c03621https://doi.org/10.1021/acsapm.4c03621","url":null,"abstract":"<p >A new dipolar glass polymer, sulfonylated poly(ether ether ketone) (PPLM–PEEK-SO₂), was designed and synthesized using the postfunctionalization of <i>o</i>-cresolphthalein units. The methyl sulfonyl group, as a side chain with a large dipole moment of 4.25 D, could well utilize the free volume (FV) provided by the rigid skeleton structure. This enhanced orientational polarization resulted in a high dielectric constant of 4.55 and a low loss of 0.0057 at 25 °C and 100 Hz for PPLM–PEEK-SO₂. In addition, PPLM–PEEK exhibited excellent discharge energy density, and the discharge efficiency (η) maintained about 97% at room temperature when the electric field increased from 50 to 500 MV/m. And even at 150 °C and 300 MV/m, it can also be as high as 95.42%, which is suitable for high-temperature energy storage. Moreover, PPLM–PEEK-SO₂ exhibited a higher energy storage density, such as 3.8 J/cm³ at 100 °C and 450 MV/m.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2965–2972 2965–2972"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609125","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}

{"title":"Ultrasensitive Electrochemical Diagnostic Platform for Dual Cancer Biomarkers Using a Disposable Sheet@Polymer Nanocomposite-Based Screen-Printed Electrode","authors":"Hema Bhardwaj*,&nbsp;Ashok Sharma and Pratima R. Solanki*,&nbsp;","doi":"10.1021/acsapm.4c0317310.1021/acsapm.4c03173","DOIUrl":"https://doi.org/10.1021/acsapm.4c03173https://doi.org/10.1021/acsapm.4c03173","url":null,"abstract":"<p >In this work, two-dimensional tungsten disulfide (WS₂) nanosheets and polyaniline (PANI) as WS₂@PANI nanocomposites were used for constructing an electrochemical immunosensor for dual ovarian cancer biomarker detection, i.e., cancer antigen-125 (CA-125) and human epididymis protein 4 (HE4). A disposable screen-printed electrode (SPE) substrate, composed of graphite conductive ink, served as a platform onto which WS₂@PANI was deposited. The WS₂@PANI-modified SPE surface was further functionalized by immobilizing EDC:NHS-activated antibodies (ab-CA-125 and ab-HE4), followed by treatment with 1% bovine serum albumin (BSA) protein to block nonspecific binding sites. Further, the electrochemical performance of the fabricated immunoelectrodes, ab-CA-125/WS₂@PANI/SPE and ab-HE4/WS₂@PANI/SPE, was evaluated by a cyclic voltammetry (CV) technique. These modified immunoelectrodes demonstrated excellent detection capabilities for dual cancer biomarkers, with CA-125 detected in the concentration range from 0.0001 to 40 μg/mL and the HE4 detection range being 0.0001–500 ng/mL, respectively. The dual electrochemical biosensing system for CA-125 biomarkers demonstrated a high sensitivity of 85.28 μA/(μg/mL)/cm² with a low limit of detection (LOD) of 10 pg/mL. Similarly, the HE4 biomarker exhibited a sensitivity of 76.71 μA/(ng/mL)/cm² with an LOD of 15 fg/mL. The fabricated biosensing platform was further validated by serum samples of ovarian cancer patients, yielding results within the acceptable ranges, including %RSD and %recovery. Therefore, these findings underscore the potential of the WS₂@PANI-based biosensing platform for highly sensitive, selective, and reliable dual cancer biomarker detection, positioning it as a promising tool for clinical cancer diagnostics.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2773–2787 2773–2787"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608799","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}

{"title":"Manufacturing of Continuous Microporous Polymeric Fibers for Separation Applications","authors":"Ngoc A. Nguyen*,&nbsp;Christopher C. Bowland,&nbsp;Jong K. Keum,&nbsp;Austin X. Staub,&nbsp;Logan T. Kearney,&nbsp;Yawei Gao,&nbsp;Michael D. Toomey,&nbsp;Jedidiah L. Long,&nbsp;Michelle K. Kidder and Amit K. Naskar*,&nbsp;","doi":"10.1021/acsapm.4c0323110.1021/acsapm.4c03231","DOIUrl":"https://doi.org/10.1021/acsapm.4c03231https://doi.org/10.1021/acsapm.4c03231","url":null,"abstract":"<p >Polyolefin plastic waste, particularly polypropylene, is one of the most prevalent components in the plastic waste stream generated globally. However, only a small fraction of this waste is recycled and reintegrated into second applications. These materials have significant embedded energy that could be used for additional productivity if recycled properly. Therefore, there is a critical need to develop scalable processing techniques with high throughput to effectively recycle it. We report the continuous manufacturing of microporous fibers using waste polypropylene plastic and melt-processable lignin, a plant biomass constituent produced as a byproduct in paper mills or biorefineries, as a template to create pores. These filaments with hierarchical porosity─created by controlled microphase separation during high-speed extensional flow followed by removal of lignin─exhibit exceptional capillary action for hydrophobic liquids. The resulting porous fibers can be used for various separation applications. For example, the oil uptake of the fibers is 9.59 ± 0.82 g/g for applications in oil recovery in bodies of water. In addition, polyethylenimine infiltration within these nanoporous fibers introduces cyclic room temperature sorption and thermal desorption potential of acidic gases such as CO₂ in a bench-scale experiment. The fibers exhibit multiple cycles of CO₂ absorption, with a range of 0.15 to 0.17 mmol/g. Thus, these polyethylenimine-infiltered nanoporous polypropylene fibers can also be used in removing acidic gases from a gas mixture.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2788–2796 2788–2796"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608979","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}

{"title":"Improvement of Carbon Black Dispersion in Mussel-Inspired Composites from Epoxidized Natural Rubber Using Aromatic Interactions","authors":"Kwanchai Buaksuntear,&nbsp;Phillip Kohl,&nbsp;Youli Li and Wirasak Smitthipong*,&nbsp;","doi":"10.1021/acsapm.4c0364810.1021/acsapm.4c03648","DOIUrl":"https://doi.org/10.1021/acsapm.4c03648https://doi.org/10.1021/acsapm.4c03648","url":null,"abstract":"<p >A mussel-inspired mechanism was used to solve the problem of filler aggregation in rubber composites. This research aims to improve carbon black (CB) dispersion in epoxidized natural rubber (ENR) composites through π–π stacking and cation−π interactions by adding dopamine (D). In this study, various aromatic interactions (π–π stacking and cation−π interactions) between the D-functionalized ENR molecules and the surface of the CB were observed by Fourier transform infrared (FTIR) and Raman spectroscopy. Notably, the small and wide-angle X-ray scattering (SAXS/WAXS) analyses supported our inference from the rubber processing analysis (RPA) and transmission electron microscopy (TEM) results that the aromatic interactions enhanced the CB dispersion in ENR composites. This phenomenon improved the tensile strength (138%), Young’s modulus (93%), and energy-saving properties (50%). Finally, this research provided an alternative strategy using mussel-inspired material to solve the CB aggregation problem in rubber products, yielding ENR composites with superior performance properties.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 6","pages":"3576–3587 3576–3587"},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c03648","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Degradation Behavior of Biodegradable and Conventional Polymers for Gill Nets, Exposed to Accelerated Aging","authors":"Christian W. Karl*,&nbsp;Szymon Bernat,&nbsp;Bjørnar Arstad,&nbsp;Stephan Kubowicz,&nbsp;Anna-Maria M. R. Persson,&nbsp;Gaute Stenerud,&nbsp;Kjell Olafsen,&nbsp;James Comerford,&nbsp;Eduardo Grimaldo,&nbsp;Sigrid Hakvaag and Roger B. Larsen,&nbsp;","doi":"10.1021/acsapm.4c0333310.1021/acsapm.4c03333","DOIUrl":"https://doi.org/10.1021/acsapm.4c03333https://doi.org/10.1021/acsapm.4c03333","url":null,"abstract":"<p >Replacing nondegradable plastics in fishing gear with abrasion-resistant biodegradable polymers is expected to reduce marine pollution caused by seabed contact and to lower the environmental impact of abandoned, lost, or otherwise discarded fishing gear (ALDFG). The chemical and physical properties, as well as the tribological behavior of conventional polyamide (PA6) and biodegradable poly butylene succinate-<i>co</i>-adipate-<i>co</i>-terephthalate (PBSAT) monofilaments for a commonly used fishing gear (gill nets), treated under accelerated aging simulating outdoor conditions, have been studied. A plethora of different methods have been used to investigate the degradation mechanism, including scanning electron microscopy, optical microscopy, 3D imaging and wear measurements, nanoindentation, mechanical and tribological testing, ATR-FTIR analyses (including micro-ATR-FTIR microscopy), and ¹H NMR spectroscopy. FTIR data indicate alterations in the outermost monofilament layer, and NMR analysis corroborates that the aging effects initially take place at the surface. PA6 showed signs of chain cleavage, while PBSAT did not show any sign of degradation, indicating hydrolysis to small, dissolved molecules during aging. The findings revealed that for both PA6 and PBSAT, the process of aging exerts a small influence on the tensile modulus. After a thousand hours of aging, an increase in the tensile modulus was observed, amounting to 21% and 5%, respectively, for PA6 and PBSAT. However, a pronounced impact on the elongation at break was detected. The elongation at break diminished by approximately 67% and 91% for PA6 and PBSAT, respectively. Tribological testing of the monofilaments shows higher wear and abrasion of the PBSAT monofilament under dry conditions compared to PA6. Nevertheless, under conditions of lubrication by seawater, the wear and friction force exerted by PBSAT and PA6 were found to be comparable. This study demonstrates that biodegradable PBSAT materials can replace nondegradable PA6 in gill nets.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"2830–2840 2830–2840"},"PeriodicalIF":4.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c03333","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effective Synthesis of Cationic Cellulose with a High Degree of Substitution and Its Characteristics for Battery Applications","authors":"Yutaro Hayashi,&nbsp;Mariya Usami,&nbsp;Elisabeth R. D. Ito,&nbsp;Yuko Takeoka,&nbsp;Masahiro Rikukawa and Masahiro Yoshizawa-Fujita*,&nbsp;","doi":"10.1021/acsapm.4c0367110.1021/acsapm.4c03671","DOIUrl":"https://doi.org/10.1021/acsapm.4c03671https://doi.org/10.1021/acsapm.4c03671","url":null,"abstract":"<p >Cellulose is attracting attention for the development of environmentally friendly, carbon-neutral, sustainable materials. Cellulose derivatives with cationic groups have the potential for applications in various fields, e.g., electrolytes. However, the current situation is marked by a low degree of cationic group incorporation and a need for more efficient synthesis methods. In this study, cationic cellulose was synthesized using an epoxy derivative, 2,3-epoxypropyltrimethylammonium chloride (EPTMAC), in an aqueous pyrrolidinium hydroxide solution. Since an aqueous pyrrolidinium hydroxide solution is a strong alkaline solution, the solution not only exhibits a high cellulose solubility at room temperature but also facilitates the reaction between cellulose and the epoxy derivative. We investigated the influence of reaction time, temperature, cellulose concentration, cationic reagent concentration, and the selection of a precipitation solvent for purification on the degree of substitution (DS) value of cationic cellulose. The structure of the obtained cationic cellulose was examined using ¹H NMR, ¹H–¹³C HSQC, ¹H–¹H TOCSY measurements, and Fourier-transform infrared spectroscopy (FT-IR). As a result of increasing cellulose and EPTMAC concentrations, the DS value increased, reaching a maximum value of 1.9. Solubility tests indicated that the cationic cellulose with chloride counter-anions exhibited notable solubility even in ethanol when the DS values were over 1.2. Cationic cellulose with bis(trifluoromethylsulfonyl)amide (TFSA) anion synthesized with a view to battery applications was insoluble in water and exhibited a film-forming property. Thus, the solubility of cationic cellulose could be controlled by varying the anionic species. Cationic cellulose with TFSA anion showed a thermal decomposition temperature above 300 °C. The ionic conductivity of gel electrolytes composed of cationic cellulose and an ionic liquid was evaluated.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 5","pages":"3024–3032 3024–3032"},"PeriodicalIF":4.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608966","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}