Xiaoyu Xu, Yingkai Guan, Bo Sun, Wei Xie, Yanhong Xu, Ji Qi
Covalent organic frameworks (COFs), with their abundant nitrogen and oxygen heteroatoms, have been developed for the inhibition of lithium polysulfide (LiPSs) shuttling in lithium–sulfur batteries (Li–S batteries). In this paper, we introduce the synthesis of Salen-TAPT-COF, which is rich in N and O atoms, under solvothermal conditions. Its ordered pore structure and large specific surface area are natural chemical channels and physical barriers to accelerate Li+ diffusion, while effectively inhibiting LiPSs shuttling. Therefore, we prepared a modified separator (Salen-TAPT-COF/PP) using Salen-TAPT-COF and applied it to Li–S batteries. The experimental results show that the performance of the battery modified with Salen-TAPT-COF is significantly improved. At a rate of 0.1 C, the initial discharge capacity of the Salen-TAPT-COF-modified battery can reach 1169.9 mA h g−1, and when the rate is increased to 2 C, the capacity of the battery can still be stabilized at 641.4 mA h g−1. XPS results also show the interaction of Salen-TAPT-COF with LiPSs.
{"title":"Two-dimensional salen-based covalent organic frameworks with highly electronegative groups as separators for high stability lithium–sulfur batteries","authors":"Xiaoyu Xu, Yingkai Guan, Bo Sun, Wei Xie, Yanhong Xu, Ji Qi","doi":"10.1039/d4py01357c","DOIUrl":"https://doi.org/10.1039/d4py01357c","url":null,"abstract":"Covalent organic frameworks (COFs), with their abundant nitrogen and oxygen heteroatoms, have been developed for the inhibition of lithium polysulfide (LiPSs) shuttling in lithium–sulfur batteries (Li–S batteries). In this paper, we introduce the synthesis of Salen-TAPT-COF, which is rich in N and O atoms, under solvothermal conditions. Its ordered pore structure and large specific surface area are natural chemical channels and physical barriers to accelerate Li<small><sup>+</sup></small> diffusion, while effectively inhibiting LiPSs shuttling. Therefore, we prepared a modified separator (Salen-TAPT-COF/PP) using Salen-TAPT-COF and applied it to Li–S batteries. The experimental results show that the performance of the battery modified with Salen-TAPT-COF is significantly improved. At a rate of 0.1 C, the initial discharge capacity of the Salen-TAPT-COF-modified battery can reach 1169.9 mA h g<small><sup>−1</sup></small>, and when the rate is increased to 2 C, the capacity of the battery can still be stabilized at 641.4 mA h g<small><sup>−1</sup></small>. XPS results also show the interaction of Salen-TAPT-COF with LiPSs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758446","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}
Here, we provide an insight into the molecular structure of products formed in the early stage of ring-opening polymerization (ROP) for phenol-aniline/cyclohexylamine-based mono-benzoxazines. By use of a combination of the experimental data obtained from Fourier transform infrared spectroscopy, nuclear magnetic resonance, and electrospray ionization mass spectrometry with density functional theory calculations, the ROP pathways of the mono-benzoxazines are proposed and validated by experiment. The initial polymerization products of the two mono-benzoxazines consist of a range of fragment species and a series of cyclic and linear oligomers, and these products are formed via zwitterionic intermediates. It could be predicted that polybenzoxazines with higher molecular weight would be generated through electrophilic aromatic substitution of hydrogen on the active benzene rings of the oligomers in the later stage of the ROP.
{"title":"Structural evolution and reaction pathways in ring-opening polymerization for mono-benzoxazines based on phenol-aniline/cyclohexylamine","authors":"Yuwei Wang, Zongran Zhang, Chang Wang, Menglei Zhen, Chunfang Zhang, Hongzan Song, Yanfang Liu","doi":"10.1039/d5py00206k","DOIUrl":"https://doi.org/10.1039/d5py00206k","url":null,"abstract":"Here, we provide an insight into the molecular structure of products formed in the early stage of ring-opening polymerization (ROP) for phenol-aniline/cyclohexylamine-based mono-benzoxazines. By use of a combination of the experimental data obtained from Fourier transform infrared spectroscopy, nuclear magnetic resonance, and electrospray ionization mass spectrometry with density functional theory calculations, the ROP pathways of the mono-benzoxazines are proposed and validated by experiment. The initial polymerization products of the two mono-benzoxazines consist of a range of fragment species and a series of cyclic and linear oligomers, and these products are formed via zwitterionic intermediates. It could be predicted that polybenzoxazines with higher molecular weight would be generated through electrophilic aromatic substitution of hydrogen on the active benzene rings of the oligomers in the later stage of the ROP.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745329","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}
Water solubility of polymers is affected by hydrophobic or hydrophilic moieties introduced into polymer chains. In this study, the introduction of hydrophobic units into polymeric ionic liquids (ILs) unexpectedly resulted in the increase in water solubility of polymers. A vinyl ether (VE) homopolymer bearing imidazolium-type IL moieties with nonanoate counteranions and poly(isobutyl VE) [poly(IBVE)] are both insoluble in water, while statistical copolymers of these VEs dissolved in water. Moreover, statistical copolymers with appropriate IBVE contents exhibited lower critical solution temperature (LCST)-type thermoresponsive behavior. Water solubility of an upper critical solution temperature (UCST)-type thermoresponsive polymeric IL with 2-naphthoate counteranions was also increased by the introduction of hydrophobic units.
{"title":"Unexpected increase in water solubility by the introduction of hydrophobic units into imidazolium-based polymeric ionic liquids with carboxylate counteranions","authors":"Nene Maruyama, Sadahito Aoshima, Arihiro Kanazawa","doi":"10.1039/d5py00139k","DOIUrl":"https://doi.org/10.1039/d5py00139k","url":null,"abstract":"Water solubility of polymers is affected by hydrophobic or hydrophilic moieties introduced into polymer chains. In this study, the introduction of hydrophobic units into polymeric ionic liquids (ILs) unexpectedly resulted in the increase in water solubility of polymers. A vinyl ether (VE) homopolymer bearing imidazolium-type IL moieties with nonanoate counteranions and poly(isobutyl VE) [poly(IBVE)] are both insoluble in water, while statistical copolymers of these VEs dissolved in water. Moreover, statistical copolymers with appropriate IBVE contents exhibited lower critical solution temperature (LCST)-type thermoresponsive behavior. Water solubility of an upper critical solution temperature (UCST)-type thermoresponsive polymeric IL with 2-naphthoate counteranions was also increased by the introduction of hydrophobic units.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736985","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}
Poly(hexamethylene 2,5-furandicarboxylate) (PHF) is a promising biobased polyester with excellent thermal, mechanical, and barrier properties. In this research, a series of high molecular weight biobased poly(hexamethylene-co-diethylene glycol furandicarboxylate) (PHDEGF) copolyesters were successfully synthesized using a two-step melt polycondensation method to improve the mechanical and hydrolytic degradation properties and extend the practical application. The thermal property, crystal structure, mechanical property, and hydrolytic degradation of PHDEGF copolyesters were investigated in detail and compared with those of PHF. PHDEGF copolyesters were random through the 13C NMR spectra study. With increasing diethylene glycol furandicarboxylate (DEGF) unit content, the glass transition temperature of PHDEGF gradually increased while the melting point decreased or even disappeared at high DEGF unit content. The elongation at break of PHDEGF copolyesters with about 20 to 65 mol% of DEGF units were significantly higher than that of PHF. PHDEGF30 containing about 20 mol% of DEGF unit displayed comparable or even superior mechanical properties to those of commercial poly(butylene adipate-co-terephthalate) and poly(butylene succinate). In addition, the hydrolytic degradation behavior of PHF and PHDEGF was studied in a NaOH solution (pH = 14, 37 oC). The incorporation of DEGF unit significantly accelerated the hydrolytic degradation of PHDEGF copolyesters.
{"title":"Novel biobased poly(hexamethylene-co-diethylene glycol furandicarboxylate) copolyesters with improved mechanical property and hydrolytic degradation rate","authors":"Shiwei Feng, Haidong Yang, Zhaobin Qiu","doi":"10.1039/d4py01458h","DOIUrl":"https://doi.org/10.1039/d4py01458h","url":null,"abstract":"Poly(hexamethylene 2,5-furandicarboxylate) (PHF) is a promising biobased polyester with excellent thermal, mechanical, and barrier properties. In this research, a series of high molecular weight biobased poly(hexamethylene-co-diethylene glycol furandicarboxylate) (PHDEGF) copolyesters were successfully synthesized using a two-step melt polycondensation method to improve the mechanical and hydrolytic degradation properties and extend the practical application. The thermal property, crystal structure, mechanical property, and hydrolytic degradation of PHDEGF copolyesters were investigated in detail and compared with those of PHF. PHDEGF copolyesters were random through the 13C NMR spectra study. With increasing diethylene glycol furandicarboxylate (DEGF) unit content, the glass transition temperature of PHDEGF gradually increased while the melting point decreased or even disappeared at high DEGF unit content. The elongation at break of PHDEGF copolyesters with about 20 to 65 mol% of DEGF units were significantly higher than that of PHF. PHDEGF30 containing about 20 mol% of DEGF unit displayed comparable or even superior mechanical properties to those of commercial poly(butylene adipate-co-terephthalate) and poly(butylene succinate). In addition, the hydrolytic degradation behavior of PHF and PHDEGF was studied in a NaOH solution (pH = 14, 37 oC). The incorporation of DEGF unit significantly accelerated the hydrolytic degradation of PHDEGF copolyesters.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736984","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}
Sarajit Naskar, Aidan Izuagbe, Vincent Lemaur, Quentin Duez, Andrea Minoia, Julien De Winter, Stephen Blanksby, Jerome Cornil, Christopher Barner-Kowollik, Pascal Gerbaux
Artificial enzymes based on polystyrene copolymers featuring a metal complex within their structure, so-called Single Chain Nanoparticles (SCNPs), are currently discussed as hybrid heterogeneous/homogeneous catalysts. Using styrene (derivative) building blocks, SCNP pre-cursor copolymers decorated with pendent triphenylphosphine ligands complexed with catalytically active gold motifs have recently been reported. It is highly challenging to determine the location and orientation of the functional groups – including the catalytic center – the coil geometry, and even the macromolecular architecture within these complex precursors via conventional analytical techniques. The use of ion mobility mass spectrometry (IMS-MS) combined with molecular dynamics (MD) simulations is emerging as a way to establish the structure of gaseous ions, including the description of the secondary interactions responsible of the folding. IMS-MS is used to separate intricate polymer mixtures, while providing structural information through collisional cross section (CCS) determination. MD simulations are used to assign a detailed internal structure to the conformations sampled by IMS-MS by comparing the experimental CCS to the theoretical values computed for the MD structures. In the present contribution, we provide an in-depth investigation of the conformation of gaseous Au-functionalized copolymer ions composed of three different monomer units, i.e., styrene, styrene-CH2-OH and styrene-PPh2-AuCl, and bearing a TEMPO unit as the initiator end group. For the styrene/styrene-CH2-OH copolymer ions, an H-bond associating protonated TEMPO and a styrene-CH2-OH unit is responsible for the ultimate folding of the polymer ions with the charge settled at the center of the globular ions. When incorporating the triphenylphosphine-AuCl unit, a strong H-bond associating the chlorine atom with protonated TEMPO is detected. However, the steric hindrance around the triphenylphosphine ligand prevents the charge from being incorporated in the core of the globular ions.
{"title":"Ion Mobility Mass Spectrometry Coupled with Molecular Dynamics Simulations: In-depth Structural Analysis of Polystyrene-based Au-Containing Copolymers","authors":"Sarajit Naskar, Aidan Izuagbe, Vincent Lemaur, Quentin Duez, Andrea Minoia, Julien De Winter, Stephen Blanksby, Jerome Cornil, Christopher Barner-Kowollik, Pascal Gerbaux","doi":"10.1039/d5py00194c","DOIUrl":"https://doi.org/10.1039/d5py00194c","url":null,"abstract":"Artificial enzymes based on polystyrene copolymers featuring a metal complex within their structure, so-called Single Chain Nanoparticles (SCNPs), are currently discussed as hybrid heterogeneous/homogeneous catalysts. Using styrene (derivative) building blocks, SCNP pre-cursor copolymers decorated with pendent triphenylphosphine ligands complexed with catalytically active gold motifs have recently been reported. It is highly challenging to determine the location and orientation of the functional groups – including the catalytic center – the coil geometry, and even the macromolecular architecture within these complex precursors via conventional analytical techniques. The use of ion mobility mass spectrometry (IMS-MS) combined with molecular dynamics (MD) simulations is emerging as a way to establish the structure of gaseous ions, including the description of the secondary interactions responsible of the folding. IMS-MS is used to separate intricate polymer mixtures, while providing structural information through collisional cross section (CCS) determination. MD simulations are used to assign a detailed internal structure to the conformations sampled by IMS-MS by comparing the experimental CCS to the theoretical values computed for the MD structures. In the present contribution, we provide an in-depth investigation of the conformation of gaseous Au-functionalized copolymer ions composed of three different monomer units, i.e., styrene, styrene-CH2-OH and styrene-PPh2-AuCl, and bearing a TEMPO unit as the initiator end group. For the styrene/styrene-CH2-OH copolymer ions, an H-bond associating protonated TEMPO and a styrene-CH2-OH unit is responsible for the ultimate folding of the polymer ions with the charge settled at the center of the globular ions. When incorporating the triphenylphosphine-AuCl unit, a strong H-bond associating the chlorine atom with protonated TEMPO is detected. However, the steric hindrance around the triphenylphosphine ligand prevents the charge from being incorporated in the core of the globular ions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723498","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}
Qianyong Chang, Kun Zhang, Wenbin Li, Yanqing Wang, Ke Li, Yigang Wang, Xiaoan Nie, Jie Chen
The performance of carbon fiber-reinforced composites (CFRCs) is mainly influenced by the resin matrix. In this study, eleostearic acid was utilized as the raw material, with DOPO serving as the flame-retardant functional group, and dynamic ester bonds were introduced to construct tung oil-based flame-retardant epoxy vitrimers (DGEBA-MSPDGE), which were subsequently applied in the preparation of CFRCs. This approach was aimed to address two major challenges of CFRCs: flammability and recyclability. With DGEBA-MNA cured with commercial methyl nadic anhydride (MNA) as a control, DGEBA-MSPDGE-1 exhibited excellent mechanical properties, and achieved a tensile strength of 81.4 MPa and an elongation at break of 3.83%, which were both superior to those of DGEBA-MNA (76.1 MPa and 2.86%, respectively). DGEBA-MSPDGE attained a limiting oxygen index of 36.4% and a UL-94 V-0 rating in a vertical burning test, and demonstrated blow-off effects during evaluation. The peak heat release rate and total heat release for DGEBA-MSPDGE-1 compared to those of DGEBA-MNA were reduced by 40% and 46%, respectively, which indicate excellent flame retardancy properties. It displayed excellent chemical degradability by completely degrading within five hours under mild conditions. Notably, the recovered carbon fibers (CFs) retained their original chemical structure, mechanical properties, and surface morphology, which facilitated non-destructive recycling of CFs. Therefore, this research provides a viable strategy for fabricating high-performance, fire-safe and recyclable CFRCs.
{"title":"Design of degradable, intrinsically flame-retardant and high-performance tung-oil-based epoxy vitrimers","authors":"Qianyong Chang, Kun Zhang, Wenbin Li, Yanqing Wang, Ke Li, Yigang Wang, Xiaoan Nie, Jie Chen","doi":"10.1039/d5py00141b","DOIUrl":"https://doi.org/10.1039/d5py00141b","url":null,"abstract":"The performance of carbon fiber-reinforced composites (CFRCs) is mainly influenced by the resin matrix. In this study, eleostearic acid was utilized as the raw material, with DOPO serving as the flame-retardant functional group, and dynamic ester bonds were introduced to construct tung oil-based flame-retardant epoxy vitrimers (DGEBA-MSPDGE), which were subsequently applied in the preparation of CFRCs. This approach was aimed to address two major challenges of CFRCs: flammability and recyclability. With DGEBA-MNA cured with commercial methyl nadic anhydride (MNA) as a control, DGEBA-MSPDGE-1 exhibited excellent mechanical properties, and achieved a tensile strength of 81.4 MPa and an elongation at break of 3.83%, which were both superior to those of DGEBA-MNA (76.1 MPa and 2.86%, respectively). DGEBA-MSPDGE attained a limiting oxygen index of 36.4% and a UL-94 V-0 rating in a vertical burning test, and demonstrated blow-off effects during evaluation. The peak heat release rate and total heat release for DGEBA-MSPDGE-1 compared to those of DGEBA-MNA were reduced by 40% and 46%, respectively, which indicate excellent flame retardancy properties. It displayed excellent chemical degradability by completely degrading within five hours under mild conditions. Notably, the recovered carbon fibers (CFs) retained their original chemical structure, mechanical properties, and surface morphology, which facilitated non-destructive recycling of CFs. Therefore, this research provides a viable strategy for fabricating high-performance, fire-safe and recyclable CFRCs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713388","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}
Jiao Zong, Benmin Hu, Lei Li, Shihui Li, Bo Liu, Dongmei Cui
Coordination polymerization of 2,3-dimethyl-1,3-butadiene (DMB) has been investigated by using rare-earth metal catalysts. Of which the ligand-free gadolinium dibenzyl chloride precursor exhibits the highest activity and perfect cis-1,4 selectivity for DMB homopolymerization and copolymerization with butadiene (BD) to afford plastic poly(2,3-dimethyl-1,3-butadiene) (PDMB) and plastic-rubber diblock copolymer PDMB-b-PBD, respectively. In solution PDMB-b-PBD self-assembles into “core-shell” morphology with the crystalline cis-1,4 regulated PDMB segment as the core and the amorphous cis-1,4 stereoregular PBD unit as the shell, whilst in melt, PDMB block forms physical cross-linking in PBD rubbery matrix, endowing the material with an unusual high stress accompanied by excellent elongation.
{"title":"Plastic-Rubber Diblock Copolymer from Copolymerization of Dimethyl-1,3-butadiene and Butadiene by Rare-earth Metal Catalyst","authors":"Jiao Zong, Benmin Hu, Lei Li, Shihui Li, Bo Liu, Dongmei Cui","doi":"10.1039/d4py01446d","DOIUrl":"https://doi.org/10.1039/d4py01446d","url":null,"abstract":"Coordination polymerization of 2,3-dimethyl-1,3-butadiene (DMB) has been investigated by using rare-earth metal catalysts. Of which the ligand-free gadolinium dibenzyl chloride precursor exhibits the highest activity and perfect cis-1,4 selectivity for DMB homopolymerization and copolymerization with butadiene (BD) to afford plastic poly(2,3-dimethyl-1,3-butadiene) (PDMB) and plastic-rubber diblock copolymer PDMB-b-PBD, respectively. In solution PDMB-b-PBD self-assembles into “core-shell” morphology with the crystalline cis-1,4 regulated PDMB segment as the core and the amorphous cis-1,4 stereoregular PBD unit as the shell, whilst in melt, PDMB block forms physical cross-linking in PBD rubbery matrix, endowing the material with an unusual high stress accompanied by excellent elongation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"287 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703326","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}
Ahmed Mohamed Ahmed Mahmoud, Kenji Miyatake, Fanghua Liu, Vikrant Yadav, Fang Xian, Lin Guo, Chun Yik Wong, Toshio Iwataki, Makoto Uchida, Katsuyoshi Kakinuma
A series of quaternized poly(arylene fluorenylidene piperidinium)-based copolymers were synthesized using different hydrophobic components, including biphenyl, m- or p-terphenyl, and 9,9-dimethylfluorenyl groups. Among them, the quaternized poly(biphenylene fluorenylidene piperidinium) had the best solvent solubility and membrane formability. Transmission electron microscopy showed that poly(biphenylene fluorenylidene piperidinium) (QBPh-Pip) had a well-interconnected nanoscale phase-separated morphology. The QBPh-Pip membrane with an ion exchange capacity of 1.9 mequiv. g−1 exhibited the most balanced properties, with low water uptake (95% at 80°C), low swelling (45%), and high hydroxide ion conductivity (160 mS cm−1 at 80°C). Despite the low water absorption, rapid ion mobility led to high ion conductivity, as calculated using normalized diffusion coefficients. Furthermore, the QBPh-Pip membrane exhibited excellent alkaline stability (91.5% (141 mS cm-1) of the initial conductivity after 1,000 h in 8 M potassium hydroxide at 80°C) and excellent mechanical properties (29.0 MPa of maximum stress and 134% elongation at break). In a water electrolysis cell using a nickel iron oxide anode catalyst, the QBPh-Pip membrane achieved a low cell voltage (1.7 V at 1.0 A cm−2) with 72% efficiency. The QBPh-Pip cell was durable for 1,000 h at a constant current density of 1.0 A cm−2 with minor voltage decay of 70 μV h−1.
利用不同的疏水成分，包括联苯基、间或对三联苯基和 9,9-二甲基芴基，合成了一系列季铵化聚（芳基芴基哌啶）共聚物。其中，季铵化聚（联苯亚芴基哌啶）具有最佳的溶剂溶解性和成膜性。透射电子显微镜显示，聚（联苯亚芴基哌啶）（QBPh-Pip）具有良好的互连纳米级相分离形态。离子交换容量为 1.9 mequiv. g-1 的 QBPh-Pip 膜具有最均衡的特性，吸水率低（80°C 时为 95%），膨胀率低（45%），氢氧根离子导电率高（80°C 时为 160 mS cm-1）。尽管吸水率低，但根据归一化扩散系数的计算，离子的快速迁移导致了离子的高电导率。此外，QBPh-Pip 膜还具有出色的碱性稳定性（在 8 M 氢氧化钾（80°C）中 1000 小时后的初始电导率为 91.5% (141 mS cm-1)）和出色的机械性能（最大应力为 29.0 MPa，断裂伸长率为 134%）。在使用氧化镍铁阳极催化剂的水电解池中，QBPh-Pip 膜实现了较低的电池电压（1.0 A cm-2 时为 1.7 V）和 72% 的效率。QBPh-Pip 电池在 1.0 A cm-2 的恒定电流密度下可持续使用 1,000 小时，电压衰减很小，仅为 70 μV h-1。
{"title":"Effect of biphenyl groups on the properties of poly(fluorenylidene piperidinium) based anion exchange membranes for applications to water electrolyzers","authors":"Ahmed Mohamed Ahmed Mahmoud, Kenji Miyatake, Fanghua Liu, Vikrant Yadav, Fang Xian, Lin Guo, Chun Yik Wong, Toshio Iwataki, Makoto Uchida, Katsuyoshi Kakinuma","doi":"10.1039/d5py00210a","DOIUrl":"https://doi.org/10.1039/d5py00210a","url":null,"abstract":"A series of quaternized poly(arylene fluorenylidene piperidinium)-based copolymers were synthesized using different hydrophobic components, including biphenyl, m- or p-terphenyl, and 9,9-dimethylfluorenyl groups. Among them, the quaternized poly(biphenylene fluorenylidene piperidinium) had the best solvent solubility and membrane formability. Transmission electron microscopy showed that poly(biphenylene fluorenylidene piperidinium) (QBPh-Pip) had a well-interconnected nanoscale phase-separated morphology. The QBPh-Pip membrane with an ion exchange capacity of 1.9 mequiv. g−1 exhibited the most balanced properties, with low water uptake (95% at 80°C), low swelling (45%), and high hydroxide ion conductivity (160 mS cm−1 at 80°C). Despite the low water absorption, rapid ion mobility led to high ion conductivity, as calculated using normalized diffusion coefficients. Furthermore, the QBPh-Pip membrane exhibited excellent alkaline stability (91.5% (141 mS cm-1) of the initial conductivity after 1,000 h in 8 M potassium hydroxide at 80°C) and excellent mechanical properties (29.0 MPa of maximum stress and 134% elongation at break). In a water electrolysis cell using a nickel iron oxide anode catalyst, the QBPh-Pip membrane achieved a low cell voltage (1.7 V at 1.0 A cm−2) with 72% efficiency. The QBPh-Pip cell was durable for 1,000 h at a constant current density of 1.0 A cm−2 with minor voltage decay of 70 μV h−1.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703318","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}
The influence of fluorine substitution on the aggregation-induced emission enhancement of alternating tetraphenylethene-benzothiadiazole copolymers pBTPE and pBFTPE is investigated. The presence of difluorobenzothiadiazole in pBFTPE significantly enhances the intensity of emission upon aggregation, whereas pBTPE without fluorinated substituents exhibits relatively weak aggregation-enhanced emission. Furthermore, both TEM image and 2-D GIWAXS reveal denser packing for pBFTPE. The fluorine atoms on the polymer backbone may promote more pronounced inter-polymer interactions, improving molecular packing and resulting in conformational difference. It may dictate the nature of aggregation between polymers and resulting photophysical behavior.
{"title":"Effect of Fluorine Substitution on Tetraphenylethene-Benzothiadiazole Based AIE-active Copolymers","authors":"Chih-Hsien Chen, Yen-Ting Cao, Yi-Ting Ou, Man-Hsin Hsieh","doi":"10.1039/d5py00049a","DOIUrl":"https://doi.org/10.1039/d5py00049a","url":null,"abstract":"The influence of fluorine substitution on the aggregation-induced emission enhancement of alternating tetraphenylethene-benzothiadiazole copolymers pBTPE and pBFTPE is investigated. The presence of difluorobenzothiadiazole in pBFTPE significantly enhances the intensity of emission upon aggregation, whereas pBTPE without fluorinated substituents exhibits relatively weak aggregation-enhanced emission. Furthermore, both TEM image and 2-D GIWAXS reveal denser packing for pBFTPE. The fluorine atoms on the polymer backbone may promote more pronounced inter-polymer interactions, improving molecular packing and resulting in conformational difference. It may dictate the nature of aggregation between polymers and resulting photophysical behavior.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703317","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}
Jonas Quandt, Rustam A. Gumerov, Timon Kratzenberg, Max Hohenschutz, David Kulczycki, Walter Richtering, Igor Potemkin, Cesar Rodriguez-Emmenegger
Arborescent (dendrigraft) polymers are high-molecular-weight dendritic macromolecules with a regular, multilevel branched topology and a high density of functional end groups in their periphery. Their well-defined architecture, devoid of cross-links or loops, imparts a particle-macromolecule duality that becomes particularly pronounced at interfaces. However, the underlying mechanisms governing their interfacial behavior remain largely unexplored. Here, we elucidate how the unique topology dictates the interfacial organization of water-soluble arborescent polymers. Using an iterative grafting-from approach via single-electron transfer living radical polymerization, we synthesized narrowly dispersed polymers with controlled branching and ultra-high molecular weight of 6.2·10⁶ g·mol⁻¹. These polymers transition from spherical rigid particles in solution, to highly flexible, two-dimensional conformations upon interfacial adsorption. At solid interfaces, increasing segment density shifts surface morphologies from quasi-2D discs to fried-egg-like structures, as observed by atomic force microscopy and corroborated by dissipative particle dynamics simulations. At liquid-liquid interfaces, the absence of substrate constraints facilitates complete spreading into uniform 2D discs, driven by the energy gain due to polymer-segment adsorption. Furthermore, we uncover that macromolecular crowding and topological constraints inherent to the arborescent architecture dictate the response to compression of the adsorbed polymer layer, contrasting sharply with the behavior of conventional flexible linear or star polymers. The combination of high interfacial activity, spatially adaptable end groups, and extreme molecular flexibility will enable arborescent polymers to adapt to complex interfaces, acting as versatile platform for multivalent and superselective interactions. These properties open new avenues for designing multivalent nanocarriers and adaptive interfacial materials with cooperative binding effects.
{"title":"Synthesis of water-soluble, highly branched arborescent poly(acrylate)s: a colloid-macromolecule chimera","authors":"Jonas Quandt, Rustam A. Gumerov, Timon Kratzenberg, Max Hohenschutz, David Kulczycki, Walter Richtering, Igor Potemkin, Cesar Rodriguez-Emmenegger","doi":"10.1039/d5py00104h","DOIUrl":"https://doi.org/10.1039/d5py00104h","url":null,"abstract":"Arborescent (dendrigraft) polymers are high-molecular-weight dendritic macromolecules with a regular, multilevel branched topology and a high density of functional end groups in their periphery. Their well-defined architecture, devoid of cross-links or loops, imparts a particle-macromolecule duality that becomes particularly pronounced at interfaces. However, the underlying mechanisms governing their interfacial behavior remain largely unexplored. Here, we elucidate how the unique topology dictates the interfacial organization of water-soluble arborescent polymers. Using an iterative grafting-from approach via single-electron transfer living radical polymerization, we synthesized narrowly dispersed polymers with controlled branching and ultra-high molecular weight of 6.2·10⁶ g·mol⁻¹. These polymers transition from spherical rigid particles in solution, to highly flexible, two-dimensional conformations upon interfacial adsorption. At solid interfaces, increasing segment density shifts surface morphologies from quasi-2D discs to fried-egg-like structures, as observed by atomic force microscopy and corroborated by dissipative particle dynamics simulations. At liquid-liquid interfaces, the absence of substrate constraints facilitates complete spreading into uniform 2D discs, driven by the energy gain due to polymer-segment adsorption. Furthermore, we uncover that macromolecular crowding and topological constraints inherent to the arborescent architecture dictate the response to compression of the adsorbed polymer layer, contrasting sharply with the behavior of conventional flexible linear or star polymers. The combination of high interfacial activity, spatially adaptable end groups, and extreme molecular flexibility will enable arborescent polymers to adapt to complex interfaces, acting as versatile platform for multivalent and superselective interactions. These properties open new avenues for designing multivalent nanocarriers and adaptive interfacial materials with cooperative binding effects.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695113","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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