Polymer Chemistry最新文献

{"title":"Quantitative C solid-state NMR of poly(benzimidazobenzophenanthroline) (BBL) optimized multi-CP: DFT-GIAO spectral assignment, isomer quantification, and a protocol for conjugated ladder polymers","authors":"Beatrice Tremblay,Alyssa McNarney,J. Tyler Mefford","doi":"10.1039/d6py00869k","DOIUrl":"https://doi.org/10.1039/d6py00869k","url":null,"abstract":"Poly(benzimidazobenzophenanthroline) (BBL) is among the most widely studied conjugated ladder polymers, with applications spanning organic electronics, electrochemical devices, and electrocatalysis. Despite decades of investigation, rigorous structural characterization of BBL has remained elusive: its near-total insolubility precludes solution-state NMR of the pristine polymer, while techniques such as IR spectroscopy and XPS offer limited molecular-level resolution. 13C solid-state NMR (ssNMR) offers a path forward, but BBL's long 13C T1 relaxation times (>200 s) render direct excitation impractical, and standard cross-polarization (CP) methods are non-quantitative. Here we report the first quantitative 13C ssNMR spectrum of BBL, obtained via an optimized Multi-CP pulse sequence and validated against direct excitation data. Complete peak assignment is achieved through DFT-GIAO simulations of the cis and trans configurations of the benzene and naphthalene units, which further enable the first reported quantitative determination of BBL's isomer composition. This protocol offers a practical framework for the structural characterization of BBL and related conjugated ladder polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368150","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 of Acrylamide Alternating Copolymers Carrying Tertiary Amine and Hydroxyl Groups and the Sequence-Specific Properties","authors":"Seungchul Kwak,Shimpei Maruyama,Makoto Ouchi","doi":"10.1039/d6py00831c","DOIUrl":"https://doi.org/10.1039/d6py00831c","url":null,"abstract":"In this work, we newly designed a series of alternating acrylamide copolymers bearing tertiary amine and hydroxyl groups in their side chains. These alternating copolymers were synthesized via selective cyclopolymerization of a pendanttransformable divinyl monomer, followed by quantitative aminolysis modification. Temperature and pH-responsive behaviors of the alternating copolymers in aqueous media were systematically investigated by UV-Vis is transmittance measurements and dynamic light scattering (DLS), using a series of tertiary amine substituents with different alkyl groups, (dimethyl, diethyl, and dibutyl). To clarify the effect of monomer sequence on the stimulus-response behavior, the corresponding 1:1 random copolymers were also synthesized and compared.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"100 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360263","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":"Sustainability for Fluoropolymers: Fluoropolyesters and Fluorine Recovery","authors":"Christoph Fornacon-Wood,Alex Johannes Plajer","doi":"10.1039/d6py00909c","DOIUrl":"https://doi.org/10.1039/d6py00909c","url":null,"abstract":"Fluoropolymers have played a vital role in many industries since their introduction and subsequent mass production. However, these materials also have added to a multitude of environmental concerns. Fluorinated polyesters uniquely expand the catalogue of accessible materials, yet their synthesis and application remain underdeveloped. Incorporating fluorine into a polyester backbone introduces well-established benefits: enhanced thermal stability, hydrophobicity, and chemical resistance, while the ester linkage simultaneously enables degradability and chemical recycling, properties absent in classical fluoropolymers. This review aims to first provide an overview of the synthetic strategies currently available to access fluorinated polyester structures. This is followed by an overview of the current work on fluoride recovery from fluoropolymers. Only a small percentage of fluoropolymers are currently recycled, with most ending up in landfill. Therefore, it is crucial that a sustainable end-of-life path is found, considering the finite nature of CaF2 and PFAS environmental contamination. Our contribution hopes to inspire further research into making these indispensable polymers more sustainable.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359858","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":"Heavy-atom-assisted dinaphthoselenazine photocatalysts for visible-light-induced metal-free ATRP","authors":"Xinran Zhang,Han Hu,Ke Wang,Jiaqi Zhan,Xing Yang,Xiaodong Yang","doi":"10.1039/d6py00896h","DOIUrl":"https://doi.org/10.1039/d6py00896h","url":null,"abstract":"Metal-free organocatalysed atom-transfer radical polymerization (O-ATRP) can afford well-defined polymers without residual metal impurities, yet high-performance visible-light organic photocatalysts are highly desirable. Herein, we report three dinaphthoselenazine-based photocatalysts with methoxy- and cyano-substituted N-aryl groups. Spectroscopic, electrochemical measurements and DFT calculations show that methoxy-substituted dinaphthoselenazine (MeO-NSe) exhibits enhanced radical-cation stability with a long recovery time of 36 s, outperforming CN-NSe (31 s) and the parent phenoselenazine PSe (25 s) For visible-light-driven O-ATRP of methyl methacrylate, MeO-NSe achieves 96% monomer conversion with a narrow dispersity (Đ = 1.13), outperforming cyano-substituted CN-NSe (95%, Đ = 1.20) and the parent phenoselenazine PSe (90%, Đ = 1.28). This work provides an effective strategy to construct chalcogen-containing organic photocatalysts via π-extension and substituent tuning for controlled photopolymerization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"380 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359266","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":"Polysulfide-Cross-Linked Polyethylene-Like Vitrimers from Olefin Metathesis and Sulfur Mediated Aziridine Ring-Opening","authors":"Yaojun Deng,Jun Yao,Jiyun Xie,Zhichao Yan,Zhen Zhang,Jinxiang Dong","doi":"10.1039/d6py00759g","DOIUrl":"https://doi.org/10.1039/d6py00759g","url":null,"abstract":"Cross-linked polyethylene is widely used because of its excellent mechanical properties and chemical resistance; however, its permanent covalent network prevents melt reprocessing and recycling. In this work, polysulfide-cross-linked polyethylene-like vitrimers were prepared through sulfur-mediated ring-opening of aziridine-functionalized polyethylene. An aziridine-functionalized polyethylene-like precursor was synthesized by ruthenium-catalyzed copolymerization of cyclooctene with an aziridine-functionalized cyclooctene monomer, followed by hydrogenation to afford a saturated polyethylene-like polymer bearing pendant aziridine groups. Subsequent treatment with elemental sulfur in the presence of an organobase generated a cross-linked network containing dynamic polysulfide linkages. The resulting polyethylene-like vitrimers exhibited typical vitrimer behavior, including temperature-dependent creep, crack healing, and efficient reprocessing through polysulfide exchange. The cross-link density was readily tuned by varying the aziridine content, providing convenient control over the melting temperature and crystallinity of the nestworks. Notably, the reprocessed materials retained most of their mechanical performance after multiple reprocessing cycles. This work provides an efficient strategy for constructing dynamic polysulfide-cross-linked polyethylene-like networks and offers a practical route to recyclable polyethylene-like vitrimers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304789","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":"Poly(vinyl alcohol)-g-poly(ethylene oxide) Linker-Free Bottlebrushes via Azeotrope-Enabled Anionic Ring-Opening Polymerization","authors":"Jinzhou Liu,Lucas R Parent,Lai Sze Fung,Douglas Adamson","doi":"10.1039/d6py00686h","DOIUrl":"https://doi.org/10.1039/d6py00686h","url":null,"abstract":"We grow PEO side chains directly from a poly(vinyl alcohol) (PVA) backbone by a grafting-from anionic ring-opening polymerization in which the initiating potassium alkoxides are generated by azeotropic removal of water, driving a mixture of KOH and hydroxyl functional groups to the alkoxide side of the equilibrium. This avoids the need for pyrophoric alkylpotassium reagents. Because PVA carries a hydroxyl group on every repeat unit, the route achieves grafting densities up to 96%, approaching one graft per repeat unit, with PEO side-chain lengths tunable from DP = 2 to 47, with no linker between the graft and the backbone. A 5 mol% KOH loading gave the best balance between backbone solubility and grafting efficiency, with higher loadings reducing grafting density and eventually precipitating the alkoxide. Grafting density was quantified with 1 H NMR by resolving the backbone and chain-end hydroxyl protons. 1 H and 13 C NMR showed that hydroxyls in isotactic triads are less reactive than those in syndiotactic and heterotactic triads, which we attribute to repulsion between the closely spaced, same-side alkoxides of the isotactic sequences. Re-initiating a quenched and isolated bottlebrush, we were able to lengthen the grafts and raise the grafting density, as fresh base reached backbone hydroxyls that the growing grafts had previously shielded. ATR-FTIR deconvolution showed that the gauche/trans population of the grafts depends more on side-chain length than on grafting density, and liquidcell TEM revealed extended, anisotropic bottlebrushes in water.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304790","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":"Enhancing hydroxide conductivity of quaternized poly(arylene ether sulfone) anion exchange membranes by tuning cationic side-chain structures","authors":"Valerie Giscard Seyep Nguepgang,Vengatesan Singaram","doi":"10.1039/d6py00645k","DOIUrl":"https://doi.org/10.1039/d6py00645k","url":null,"abstract":"Developing alkaline anion exchange membranes (AEMs) with high hydroxide conductivity and excellent chemical stability is essential for their use in electrochemical energy conversion systems. In this context, tuning the side-chain lengths and ion-exchange groups could significantly enhance the membrane physicochemical properties, especially the hydroxide conductivity. Herein, poly(arylene ether sulfone) (PAES) and bromomethylated poly(arylene ether sulfone) (Br-PAES) copolymers were synthesized, which served as the polymer backbone for the membrane fabrications. Furthermore, 1,4-diazabicyclo[2.2.2]octane (DABCO) and two side chains derived from DABCO with different alkyl chain lengths (4 and 6) were used for quaternization of the Br-PAES copolymer to yield DABCO-PAES, C4-DABCO-PAES, and C6-DABCO-PAES AEMs, respectively. The degradation of the side chains above 275 °C, as revealed by thermal analysis, confirmed that the developed membranes were thermally stable in the operating range of electrochemical systems. The atomic force microscopy (AFM) studies demonstrated that the C4-DABCO-PAES and C6-DABCO-PAES AEM membranes showed well-defined microphase-separated morphologies, providing effective ion-transport channels. By investigating the effect of chain lengths and ion exchange groups on membrane properties, the C6-DABCO-PAES AEM was found to show the highest hydroxide conductivity of 7.87 ± 0.400 mS/cm at 25 °C and a high mechanical strength of 24 MPa, although it had a similar ion exchange capacity (IEC) to that of C4-DABCO-PAES. On the other hand, DABCO-PAES AEM (without alkyl chain) displayed the lowest water uptake (WU), IEC and ionic conductivity, due to its lower cation density and poor microphase-separated morphology of polymer backbone and ion-exchange groups.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251242","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":"Evaluation of elastic efficiency of polymer gels formed by radical polymerization: Effect of monomer-crosslinker reactivity on network defects","authors":"Ruka Ito,Rintaro Sugie,Tsukuru Masuda,Shohei Ida,Naoyuki Sakumichi,Shokyoku Kanaoka,Takamasa Sakai","doi":"10.1039/d6py00834h","DOIUrl":"https://doi.org/10.1039/d6py00834h","url":null,"abstract":"Polymer gels prepared via radical copolymerization of monomers and crosslinkers inherently possess inhomogeneous network structures. Using our hierarchical framework to evaluate gel network homogeneity, we previously showed that increasing the polymer network concentration yields osmotically homogeneous gels, whereas the factors determining elastic efficiency remain unclear. Here, we hypothesized that the monomer–crosslinker reactivity ratios, which would govern network topology, are a key determinant of elastic efficiency. To evaluate the influence of copolymerization reactivity on the elastic efficiency, N,N-dimethylacrylamide (DMAAm) and acrylamide (AAm), which share similar chemical structures and osmotic behaviors, were copolymerized with N,N’-methylenebis(acrylamide) (BIS) as a chemical crosslinker. The reactivity ratios (r_monomer and r_BIS) were 0.22 and 1.95 for DMAAm/BIS and 0.58 and 3.90 for AAm/BIS, indicating that consecutive BIS incorporation is more favored in the AAm system. For both systems, osmotically homogeneous gels were successfully obtained by appropriately adjusting the polymer network concentration to 150 g/L. In contrast, analysis of the elasticity based on the cycle rank revealed that PAAm/BIS gels exhibited lower elastic efficiency, indicating the formation of topological defects. Together with the reactivity ratios, this result indicates that elastic efficiency is governed not by the amount of incorporated BIS but by its sequence distribution along the chain. Consistent with this, reversible addition–fragmentation chain transfer polymerization of the DMAAm/BIS system, in which nearly all chains grow slowly and simultaneously, suppressed such consecutive incorporation and improved the elastic efficiency. These findings establish a direct link between molecular-level reactivity during radical polymerization and the macroscopic properties of polymer gels, providing rational guidelines for designing polymer gels with homogeneous network structures.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149251221","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":"Ring-Opening Polymerization of Cyclic Ethylene Oxalate: Mechanistic Insights, Chain Microstructure, and Structure–Property Relationships","authors":"Ziyue Jiao,Zuxin Yao,Xiaohui Kang,Ping Chen,Zhiyong Wei","doi":"10.1039/d6py00817h","DOIUrl":"https://doi.org/10.1039/d6py00817h","url":null,"abstract":"Bulk ring-opening polymerization (ROP) of cyclic ethylene oxalate (EOx) provides a complementary route to poly(ethylene oxalate) (PEOx), yet its elementary ring-opening sequence and the relationship between polymerization pathway and chain microstructure remain incompletely understood. Here, Sn(Oct)2/BnOH-mediated bulk ROP afforded an initiator-regulated PEOx series with number-average molar masses of 13.9–117.3 kDa and dispersities of 1.67–1.81. Density functional theory calculations identified an energetically preferred sequence involving nucleophilic addition, coordination reorganization, and endocyclic acyl–O bond cleavage, in which stabilization of an oxygen-rich, Sn-coordinated tetrahedral intermediate emerged as a distinctive feature of EOx ring opening. End-group and mass-spectrometric analyses further identified dibenzyl-terminated and cyclic species, consistent with transesterification and cyclization/back-biting during ROP. Comparative 1D and 2D NMR analyses resolved diethylene glycol-related ether environments and terminal-group heterogeneity in polycondensation-derived PEOx, whereas these environments were much less evident in ROP-derived material. The resulting differences in molar mass and chain microstructure were associated with distinct crystallization behavior, apparent equilibrium melting temperatures (205.1 versus 185.1 °C), melt viscoelasticity, melt-handling behavior, and thermal residence stability. Together, these results establish molecular-level relationships among EOx ring-opening chemistry, chain microstructure, and the bulk behavior of PEOx.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149241585","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":"Controllable synthesis of α-phenyl-substituted aromatic polyhydroxyalkanoates with high glass transition temperature and tensile strength","authors":"Mengchang Feng,Shuaiming Meng,Yifan Jia,Junfeng Yu,Chenyang Hu,Zhiqiang Sun,Yanchuan Zhou,Chunsheng Xiao,Xuan Pang","doi":"10.1039/d6py00754f","DOIUrl":"https://doi.org/10.1039/d6py00754f","url":null,"abstract":"Poly(hydroxyalkanoates) (PHAs) have emerged as promising candidates to replace nondegradable plastics, driving significant research efforts toward the synthesis of PHA materials with versatile structures. Despite considerable advances in aliphatic PHAs, synthetic strategies for their aromatic counterparts remain relatively underdeveloped. Herein, we report a systematic investigation into the synthesis of α-phenyl-substituted PHAs via the ring-opening polymerization of α-phenyl-β-propiolactone with organometallic Al complexes as catalysts. Among them, a modified Al complex exhibited precise polymerization controllability alongside favorable syndioselectivity up to 0.80, which further improved the thermal properties and crystalline behaviours of the resultant polymers. Besides, the phenyl substituent imparted superior mechanical properties to poly(α-phenyl-β-propiolactone) (P(PhPL)) materials, with the tensile strength reaching 33.0 MPa. Moreover, P(PhPL) could be depolymerized to the original tropic acid under mild conditions, with atropic acid as the sole byproduct that serves as a key synthetic intermediate, demonstrating the sustainability of this aromatic PHA material.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230023","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}