Polymer Chemistry最新文献

{"title":"π-Conjugated polymers consisting of heavier group 13 elements","authors":"Shunichiro Ito, Kazuo Tanaka","doi":"10.1039/d5py00116a","DOIUrl":"https://doi.org/10.1039/d5py00116a","url":null,"abstract":"Boron, aluminum, gallium, indium, and thallium are group 13 elements that can induce various electronic properties and unique functions when incorporated into main-chain conjugation through polymers. As vacant p-orbitals in these elements interact with Lewis bases, stimuli responsiveness can be induced. Additionally, the chemical and thermal stability can be enhanced by connecting with extra Lewis bases as supporting ligands. Moreover, superior optoelectronic properties, such as light absorption, emission, and carrier mobility, are often observed from group 13 element-containing π-conjugated systems. The introduction of boron into conjugated systems has been widely applied not only for improving material properties but also for providing new functionalities for conventional polymers. In contrast, there are limited examples of polymers possessing the heavier group 13 elements in their repeating units. According to recent studies, it has been shown that the chemical, physical, and material properties of π-conjugated compounds can be unexpectedly modulated by these heavier group 13 elements. In this review, we mainly explain the synthesis and fundamental photophysical properties of conjugated polymers consisting of the heavier group 13 elements in their main-chains.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841917","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":"Corona-shaped two-dimensional polyaramid derivatives for poly(ethylene oxide)-based all-solid-state lithium batteries","authors":"Feifan Zheng, Liping Jiang, Xiaoli Gong, Zhengqiao Yin, Fei Wang, Yuwen Zeng","doi":"10.1039/d5py00046g","DOIUrl":"https://doi.org/10.1039/d5py00046g","url":null,"abstract":"Solid polymer electrolytes (SPEs), especially those based on poly(ethylene oxide) (PEO), have garnered significant attention in the field of all-solid-state lithium batteries due to their high processability and low cost, advantages that are typically hard to achieve with their inorganic counterparts. However, the poor ionic conductivities have retarded their further applications in all-solid-state lithium batteries. Herein, we report a series of corona-shaped two-dimensional polyaramid (2DPA) derivatives that improve the overall performance of PEO-based SPE, including ionic conductivity, ion transference number, and electrochemical stability. We demonstrate that the unique corona topology, consisting of a rigid two-dimensional polyaramid core and flexible poly(ethylene glycol) (PEG) chains grafted at its periphery, effectively inhibits the crystallization of the PEO matrix through chain entanglement, thus enhancing the ionic conductivity. Furthermore, the 2D polyaramide core provides enriched Lewis acidic binding sites for counter anions, suppressing the anion motion and resulting in selective lithium ion transport. Therefore, a blend of 30% 2DPA-PEGs and PEO exhibits enhanced room temperature ionic conductivity up to 4.39 × 10-5 S cm-1 (an order of magnitude higher than the original SPE), an elevated lithium-ion transference number of 0.78, and a high oxidation voltage of 4.7 V (vs Li/Li+). Meanwhile, the assembled all-solid-state batteries exhibit improved cycle performance and higher stability. Such a heterostructural polymer design strategy showcases the promising potential of novel 2D polymer derivatives in ion transport optimization in SPEs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841916","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":"Cyclic thioacetal carbonates for dual-stimuli degradable poly(vinyl ether)s with cleavable thioacetal and carbonate bonds evenly distributed in the main chains by cationic degenerative chain-transfer copolymerization","authors":"Mineto Uchiyama, Kaoru Matoba, Masami Kamigaito","doi":"10.1039/d5py00054h","DOIUrl":"https://doi.org/10.1039/d5py00054h","url":null,"abstract":"We report the synthesis of dual-stimuli degradable poly(vinyl ether)s with cleavable thioacetal and carbonate bonds evenly distributed in the main chains using cationic degenerative chain-transfer (DT) copolymerization of vinyl ethers with macrocyclic thioacetal carbonates (CTAC). The 22- and 26-membered cyclic thioacetal carbonates (22-CTAC and 26-CTAC) were initially synthesized by a cationic thiol-ene reaction between divinyl ether with a carbonate bond and dithiol with or without a carbonate bond under dilution conditions. These compounds were subjected to cationic copolymerization with vinyl ethers using the HCl-adduct of isobutyl vinyl ether as an initiator and ZnCl2 as a catalyst and were consumed much faster than the vinyl ethers by ring-opening reactions despite the large ring to introduce thioacetal and carbonate bonds in the main chains of the products. The in-chain thioacetal bonds subsequently served as dormant bonds for the cationic DT polymerization of vinyl ethers and enabled the synthesis of poly(vinyl ether)s with controlled total and segmental molecular weights between the thioacetal and carbonate bonds. The orthogonal degradations were successful when acid and base catalysts were used for the thioacetal and carbonate bonds, respectively; this resulted in low-molecular-weight products with controlled molecular weights. Furthermore, multiblock copolymers were synthesized by the one-time addition of the second monomer (B) to the cationic DT polymerization of the first monomer (A) and 22-CTAC and were selectively degraded into ABA and BAB triblock copolymers with acid and base catalysts, respectively.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841683","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":"Covalent Design of Ionogels: Bridging with Hydrogels and Covalent Adaptable Networks","authors":"Yukikazu Takeoka, Junjia Zhang, Yian Wang, Yinglu Liu, Jeremy Odent","doi":"10.1039/d5py00217f","DOIUrl":"https://doi.org/10.1039/d5py00217f","url":null,"abstract":"Ionogels are conductive soft matter with ionic liquids as conductive media, exhibiting significant potential as multifunctional materials. Over the past two decades, ionogels have been developed for applications in sensors, actuators, supercapacitors, lithium-ion batteries, adhesives, antifouling coatings, nanotriboelectric generators, thermoelectric devices, etc. To achieve recyclability that is advantageous for various applications, dissociative supramolecular interactions—e.g. electrostatic interactions, hydrogen bonds and - stacking—have garnered significant attention in the crosslinking design of ionogels. High-strength ionogels utilizing dissociative supramolecular interactions as a crosslinking mechanism have been synthesized. However, due to the inherently low bond energy and high dynamics of dissociative supramolecular crosslinking, issues such as low thermal stability and insufficient solvent resistance arise, limiting the broader applications of ionogels. To address these challenges, the network structure can be precisely designed, and reversible covalent bonds can be introduced as a crosslinking mechanism to mitigate the trade-off between material durability and dynamic behavior. Several studies provide insights into realizing this approach. For instance, hydrogels, which are also classified as soft materials, can enhance both mechanical strength and deformability by incorporating topological network structures based on organic covalent bonds. Similarly, covalent adaptable networks (CANs), a class of dynamic materials, achieve high thermal stability, solvent resistance, and recyclability by utilizing densely reversible covalent bonds. Hence, we chiefly focus on the critical roles of designing the organic polymer network structures and utilizing reversible covalent bonding to enhance key physical properties of ionogels, including mechanical strength, electrical conductivity, and processability. Last but not least, we discuss the current challenges associated with the design and application of ionogels, while also anticipating potential strategies that leverage the superior designs from materials such as hydrogels and CANs to develop innovative ionogels.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837331","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":"Self-assembly of core-shell magnetic bottlebrush poly(ionic liquids): morphologies vs magnetic property","authors":"Chunman Li, Mingzhe Zhao, Zenian Gou, Tengda Zhao, Huimin Han, Kongying Zhu, Xiaoyan Yuan, Li-Xia Ren","doi":"10.1039/d5py00277j","DOIUrl":"https://doi.org/10.1039/d5py00277j","url":null,"abstract":"Magnetic polymers show great potential in biomedical, electronic devices and magnetic responsive materials. The structure and property relationship are very important in design of organic magnetic polymers. In this work, core-shell magnetic bottlebrush polymers (PS-b-QPDMA[FeCl4]) with polystyrene as core block and magnetic poly(ionic liquid)s (QPDMA[FeCl4]) as shell block is prepared by ring-opening metathesis polymerization and post-modification. The self-assembly of core-shell PS-b-QPDMA[FeCl4] is studied in core and shell selecting solvent, respectively. It self-assembles into single macromolecular core-shell nanorod in shell selecting solvent while it self-assembles into core-shell nanoparticles in core selecting solvent. The magnetic property of PS-b-QPDMA[FeCl4] are studied in different morphologies via magnetic field and temperature dependent magnetization, respectively. Compared with the paramagnetic linear block copolymer, the bottlebrush polymer without self-assembly shows ferromagnetic interaction at low temperature with the bifurcation temperature (Tb) of the zero field cooling and field cooling curves of 3.2 K. The nanoparticle self-assemblies show the similar Tb at 3.8 K, while the single macromolecular nanorod self-assemblies show a high Tb of 9.8 K, demonstrating the much stronger ferromagnetic interaction for the nanorod self-assemblies. The increasing of Tb is probably due to the confinement of glassy PS core in the nanorod self-assemblies, which decreases the Fe(III)-Fe(III) distance to enhanced the ferromagnetic interaction of FeCl4- units.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827194","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":"Soluble polyimide-based colorless-to-orange–red switching electrochromic film by incorporating universal joint-like structure","authors":"Xiaoqing Sun, Chongwen Yu, Xingyao Liu, Taolve Wang, Xigao Jian, Yujie Song, Jian Xu","doi":"10.1039/d5py00149h","DOIUrl":"https://doi.org/10.1039/d5py00149h","url":null,"abstract":"Polyimide (PI) exhibits good thermal performance and high stability due to its highly rigid main chain and excellent mechanical properties, making it an ideal electrochromic material. However, its applicability is limited by poor solvent solubility, which results from the rigid backbone, and film yellowing, caused by charge-transfer complexes (CTC). Herein, a novel phenothiazine-based diamine (THZ-DA) was synthesized, where a universal joint-like structure was constructed during its formation. The introduction of the non-coplanar universal joint reduced intermolecular interactions and suppressed CTC formation, improving the solubility and enabling high transmittance of THZ-PIs in the neutral state. Moreover, the lone pair of electrons on the nitrogen atom of THZ allowed for the formation of a cationic radical (THZ+·) under electrochemical oxidation, which was stabilized by the resonance effect, enabling reversible color switching between colorless and orange–red state. Among the three systems, THZ-b, composed of THZ-DA and 3,3’,4,4’-biphenyl tetracarboxylic dianhydride, showed the best thermal stability, with a Td5% above 406 °C and Tg of 347 °C. It also exhibited good electrochemical cycling stability, with redox potentials of 1.09 and 0.88 V, as well as excellent electrochromic performance, achieving an electrochromic efficiency of 222 cm2 C–1. These results show the application potential of THZ-PI in smart windows and adaptive camouflage.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819379","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":"Highly Isotactic Polylactide by Binary Organocatalyzed Polymerization of 1,3-Dioxolan-4-Ones","authors":"Mengyu Wang, Sumin Lee, Hyunhee Lee, Byeong-Su Kim","doi":"10.1039/d5py00205b","DOIUrl":"https://doi.org/10.1039/d5py00205b","url":null,"abstract":"Ring-opening polymerization (ROP) of dioxolanones (DOXs) provides access to functional polyesters with properties that are challenging to achieve via traditional polymerization of lactones. However, typical catalysts often induce epimerization in DOXs, limiting the synthesis of isotactic, crystalline polymers. This study reports a binary organocatalytic system that enables controlled ROP of chiral 2,2,5-trimethyl-1,3-dioxolan-4-ones under mild conditions, effectively minimizing epimerization by activating both the monomer and initiator via hydrogen bonding. This strategy facilitates the synthesis of highly isotactic poly(lactic acid) (PLA) with a stereoregularity parameter of 0.92. Moreover, blending enantiomeric PLA chains form a crystalline stereocomplex with a high melting temperature of 195.1 °C. These findings highlight a sustainable and scalable approach for synthesizing stereoregular polyesters, paving the way for advanced material applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813747","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":"Design, synthesis and applications of thermosensitive linear poly(ether amide)s with unconventional cluster luminescence and tunable LCST","authors":"Zixian Liu, Yangdan Ou, Sisi Li, Wenyan Huang, Hongjun Yang, Xiaoqiang Xue, Qimin Jiang, Bibiao Jiang","doi":"10.1039/d4py01386g","DOIUrl":"https://doi.org/10.1039/d4py01386g","url":null,"abstract":"The design of stimuli-responsive polymers with both tunable lower critical solution temperature (LCST) and unconventional cluster luminescence represents a significant challenge in materials science. In this study, thermosensitive linear poly(ether amide)s with cluster fluorescence and LCST tunability were prepared via phosphazene base (t-BuP2)-catalyzed oxa-Michael addition polymerization of N,N'-methylene-bis(acrylamide) (MBA) with diols containing different numbers of carbon atoms. The fluorescence properties and LCST tunable behavior of the linear poly(ether amide)s were investigated by ultraviolet-visible (UV-Vis) and fluorescence spectroscopy. The fluorescence results demonstrate that the resulting linear poly(ether amide)s exhibit aggregation-induced emission (AIE) and excitation-dependent emission properties due to cluster fluorescence, which is formed by the aggregation of nonconjugated chromophores, such as amide, ether, and hydroxyl groups. It is noteworthy that the fluorescent polymers display temperature-responsive and LCST tunable characteristics, which can be attributed to the interactions between the hydrophobic carbon chains and the hydrophilic ether, amide, and hydroxyl groups present in the linear polyether amides. Moreover, linear poly(ether amide)s display distinctive LCST-dependent fluorescence characteristics, exhibiting a pronounced shift in fluorescence intensity with temperature that closely aligns with their LCST values. The intrinsic fluorescence and temperature response of linear poly(ether amide)s were exploited to demonstrate their potential as a versatile tool for security tamper-evident labels, physiological cell imaging, and traceable and controlled release of doxorubicin. This study provides an LCST-tunable strategy for linear nonconjugated fluorescent polymers, which enriches and develops the synthesis, mechanism and application studies of stimuli-responsive nonconjugated fluorescent polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813746","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":"Dynamic by Design: Unlocking Full Relaxation in Disulfide Epoxy Networks","authors":"Paula Fanlo, Osman Konuray, Olaia Ochoteco, Marta Ximenis, Alaitz Rekondo, Hans J Grande, Xavier Fernández-Francos, Haritz Sardon, Alaitz Ruiz de Luzuriaga","doi":"10.1039/d5py00124b","DOIUrl":"https://doi.org/10.1039/d5py00124b","url":null,"abstract":"Aromatic disulfide-containing epoxy networks offer a promising approach to achieving sustainable materials due to their reparable, recyclable, and reprocessable properties. However, in all cases, an excess of hardener is required to achieve full reparability. In this study, a theoretical analysis demonstrates that when aromatic disulfide is incorporated into the amine hardener, the resulting epoxy vitrimer does not fully relax due to epoxy group homopolymerization, which leads to the formation of non-dynamic crosslinks. To overcome this limitation, an epoxy monomer containing disulfide bonds was synthesized. This monomer enables complete relaxation, as the homopolymerized epoxy system also contributes to the formation of dynamic crosslinks. Using this new monomer, epoxy vitrimers were prepared that can relax without requiring an excess of amine. However, these materials exhibit inferior properties compared to those prepared with an aromatic disulfide-based diamine. To enhance their properties, a non-dynamic epoxy was introduced into the formulation. Both experimental and computational results demonstrate that up to 32% of non-dynamic epoxy can be incorporated without compromising dynamic features such as repairability, reprocessability, and recyclability, making this system significantly more suitable for industrial implementation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813776","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":"Synthesis and self-assembly of a diblock copolymer consisting of a cyclic olefin copolymer and polycaprolactone","authors":"Yung-Chuan Chuang, Jing-Wen Su, Yu-Chuan Sung, Jing-Cherng Tsai, Jian-Wei Huang, Sheng-Wei Shao, Rong-Ming Ho","doi":"10.1039/d4py00855c","DOIUrl":"https://doi.org/10.1039/d4py00855c","url":null,"abstract":"The cyclic olefin copolymer (COC), a unique cyclic monomer-containing copolymer, is used in numerous modern technical applications. This paper reports the preparation of COC-<em>block</em>-polycaprolactone through a metallocene-catalyst mediated selective chain transfer pathway, which facilitates the generation of a functionalized COC end-capped with a hydroxyl group. Subsequently, living block copolymerization of ε-caprolactone using the hydroxyl-capped COC as a macroinitiator facilitated the synthesis of COC-<em>block</em>-polycaprolactone with excellent block length control. The resulting COC-<em>block</em>-polycaprolactone can self-organize into an ordered nanopattern, offering the potential application of the COC in the manufacture of ordered nanomaterials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806549","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}