Polymer Chemistry最新文献

{"title":"Monodisperse amphiphilic double-crystalline block oligomers composed of linear alkyl chains and poly(vinyl alcohol) segments prepared by aldol-group transfer polymerization and recycling size-exclusion chromatography separation†","authors":"Toa Nakane ,&nbsp;Hironobu Watanabe ,&nbsp;Mineto Uchiyama ,&nbsp;Fabrice Muller ,&nbsp;Nathalie Mathieu ,&nbsp;Christophe Sinturel ,&nbsp;Masami Kamigaito","doi":"10.1039/d5py00145e","DOIUrl":"10.1039/d5py00145e","url":null,"abstract":"<div><div>As a model of block copolymers of ethylene and vinyl alcohol, monodisperse amphiphilic double crystalline diblock oligomers composed of linear alkyl chains and poly(vinyl alcohol) segments were prepared using aldol-group transfer polymerization (aldol-GTP) and recycling size-exclusion chromatography (SEC) separation. The aldol-GTP of <em>tert</em>-butyldimethylsilyl vinyl ether (TBSVE) was conducted using octadecyl aldehyde as an initiator and ZnBr₂ as a catalyst for the synthesis of oligo(TBSVE) with controlled molecular weights and a C16 alkyl chain and an aldehyde group at the α- and ω-chain ends, respectively. The obtained oligomers were separated into monodisperse unimers, dimers, trimers, tetramers, and pentamers <em>via</em> preparative recycling SEC. Reduction of the terminal aldehyde group followed by deprotection of the silyl groups resulted in monodisperse amphiphilic oligomers composed of C16 alkyl chains and poly(vinyl alcohol) (PVA) units. The effects of the number of PVA units on the thermal properties were characterized using differential scanning calorimetry. Furthermore, the morphology of the discrete block oligomer was examined by optical microscopy, atomic force microscopy, and small- and wide-angle X-ray scattering. Owing to the high incompatibility between the hydrophobic and hydrophilic blocks, self-assembly was observed despite the very low molar weights of the polymers. Based on our results, we propose that a double-crystalline lamellar structure is formed and consists of alternating hydrophobic (alkyl chains) and hydrophilic (PVA segments) domains (with a period of 6.8 nm), showing a distinct crystallization/melting process.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2471-2479"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782882","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":"Polymerization behaviour of biscarbenes derived by thermolysis of bisdiazo compounds†","authors":"Xiaosong Liu ,&nbsp;Mark G. Moloney ,&nbsp;Koji Okuda","doi":"10.1039/d4py01474j","DOIUrl":"10.1039/d4py01474j","url":null,"abstract":"<div><div>A study of the collapse of bisdiazo compounds with different terminal groups upon heating to generate reactive biscarbene intermediates has provided evidence for homopolymerization in a process that proceeds in the absence of catalysts and is tolerant of oxygen. This polymerization behaviour was monitored spectroscopically through UV-vis kinetic analysis with various combinations of temperature and solvent, and clear evidence for dimer and trimer formation was found by field desorption mass spectrometry. Oligomerization may involve the formation of CC and CN–NC linkages, as studied and validated by molecular dynamics (MD) calculations, before reaching macromolecular size. In the presence of terminal NH₂ groups, cross-linking resulting from carbene insertion is also observed. This unusual polymerization of diazo monomers, when conducted on a polyvinyl alcohol (PVA) surface in the open-air upon heating, creates a highly cross-linked structure that changes surface properties.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2480-2493"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866149","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":"Crosslinking of polymers from monofunctional acrylates via C–H bond activation†","authors":"Junkyu Kim ,&nbsp;Seokju Lee ,&nbsp;Youngjoo Park ,&nbsp;Woojin Jeon ,&nbsp;Min Sang Kwon","doi":"10.1039/d5py00239g","DOIUrl":"10.1039/d5py00239g","url":null,"abstract":"<div><div>Cross-linked acrylic polymers are highly valued for their durability and chemical resistance, making them extensively used in various applications and industries. Typically, they are synthesized by adding crosslinkers (multifunctional monomers or oligomers) or through post-treatment processes. However, our preliminary studies indicated that even monofunctional acrylic monomers can form cross-linked structures. The formation of these cross-linked structures is thought to result from a chain transfer mechanism involving hydrogen atom transfer (HAT) between monomer substituents and radicals. Despite this, the process has not been thoroughly analyzed, and few studies have applied this concept to the design of polymer networks. To clarify this phenomenon, we conducted a series of screening experiments using ten widely-used monomers and three different photoinitiation systems, discovering that 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (HBA), and 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate (MEEEA) exhibited superior crosslinking capabilities. Furthermore, quantum chemical calculations were employed to elucidate why these specific monomers excel in forming cross-linked networks. Assuming the propagating acryl radical acts as the hydrogen acceptor for HAT, it was found that the reactions occurring in the substituents of MEEEA and under hydrogen bonding conditions in HEA and HBA are thermodynamically stable. Consequently, the cross-linked structures formed by monofunctional acrylates were determined to be due to radicals generated at the substituents of the monomers. This enhanced understanding offers a new paradigm in the synthesis of cross-linked polymers, expanding their potential across diverse applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2521-2529"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143884960","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":"Ultrahigh-resolution, high interface contrast ionic homopolymers induced by acid–base mixed electrostatic interactions and nanopattern evolution†","authors":"Sen Weng ,&nbsp;Zhen Lu ,&nbsp;Jingyu Cai ,&nbsp;Longqiang Xiao ,&nbsp;Kairui Wang ,&nbsp;Rui Zhao ,&nbsp;Xin Fu ,&nbsp;Linxi Hou","doi":"10.1039/d5py00135h","DOIUrl":"10.1039/d5py00135h","url":null,"abstract":"<div><div>Ultrahigh-resolution polymer materials with good thermal stability and high interface contrast have a wide range of application prospects in photolithography and nanomanufacturing processes. Here, we report a series of comb-like homopolymers based on polystyrene sulfonate imidazolium salts (PSS_<em>M</em>-(<em>i</em>)imi), achieving efficient self-assembly under solvent-free conditions and obtaining sub-3 nm hexagonally packed cylinders and sub-4 nm lamellar nanopatterns with high interface contrast. The sulfonic acid groups in the main chain of the homopolymers are connected to imidazole groups containing hydrophobic alkyl side chains through acid–base mixed electrostatic interactions. The electrostatic interactions enhance the incompatibility between the two functional groups, while the alkyl side chain can precisely control the domain spacing and nanostructure of the pattern, regardless of their molecular weight. Through the effect of temperature fields, the thermal stability and spatial orientation of the homopolymer nanostructures were further studied, promoting the practical application of nanopatterned materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2506-2513"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910515","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":"Sustainable one-pot synthesis of imide-containing polyesters with programmable structures and tunable performance†","authors":"Tianhua Ren ,&nbsp;Feng Yu ,&nbsp;Jialong Li ,&nbsp;Jinlin Li ,&nbsp;Kechun Zhang","doi":"10.1039/d5py00190k","DOIUrl":"10.1039/d5py00190k","url":null,"abstract":"<div><div>Sustainably producing thermoplastics with well-defined structures across various material chemistries remains challenging. Herein, we report a new synthetic methodology for thermoplastic polyesters with side-chain imide groups <em>via</em> one-pot melt polycondensation enabled by thermodynamic imide ring and ester formation, using either a two-component system of amino diol/dicarboxylic acid or a three-component system of amino diol/diol/dicarboxylic acid. Unlike traditional trifunctional systems, the amino groups of amino diols are fully converted into imide without cross-linking. This methodology was inspired by the model reaction of amino alcohol and dicarboxylic acid to form di(ester imide) <em>via</em> melt condensation, where the esterification, imidization and molecular chain propagation mechanisms can be extended to polymerization. The resulting series of imide-containing polyesters exhibited controllable weight-average molecular weights up to 110.8 kDa, a wide range of glass transition temperatures (−24.6 to 115.4 °C), and tunable mechanical properties with ultimate tensile strengths ranging from 8.0 to 34.5 MPa and elongations at break up to 472%. The programmable one-pot synthesis technology has extensive potential for sustainable and functional materials.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2552-2563"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920447","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 butadiene-derived polyolefin graft copolymers and their crystallization behaviors†","authors":"Jin Qian ,&nbsp;Zhe Qiang","doi":"10.1039/d5py00243e","DOIUrl":"10.1039/d5py00243e","url":null,"abstract":"<div><div>The ability to synthesize polyolefin-based copolymers with controlled chemical composition and chain microstructure provides great opportunities for their use in compatibilizing polyolefin blends, particularly including polyethylene (PE) and polypropylene (PP), to address their waste recycling challenges. In this study, polyolefin graft copolymers comprising semicrystalline PE side chain and amorphous polyethylethylene (PEE) backbone were synthesized by grafting amine-terminated 1,4-polybutadiene (PB) onto carboxyl-grafted 1,2-PB, followed by hydrogenation. A suite of characterization techniques were employed to assess the degree of functionalization, polymer microstructure, and molecular weight of these graft copolymers containing different side chain lengths and graft densities. Moreover, since most commodity polyolefins are semicrystalline, understanding the crystallization behavior of these polyolefin copolymers is important. Specifically, the non-isothermal crystallization behavior of these graft copolymers was investigated using differential scanning calorimetry (DSC) and the Jeziorny-modified Avrami model. Both the graft copolymers and their homopolymer grafts exhibited heterogeneous nucleation with predominantly one-dimensional crystal growth and similar overall crystallization rates. However, PEE-<em>g</em>-PE_10k and PEE-<em>g</em>-PE_5k showed opposite trends in activation energy, likely due to a competition between nucleation facilitation and crystal growth restriction introduced by the graft structure. A preliminary investigation indicates that the incorporation of these graft copolymers into mixed PE : PP (50 : 50) blends can lead to improved mechanical performance. This study reveals the impact of graft architecture on the crystallization behavior of polyolefin-based blend compatibilizers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2530-2542"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898149","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":"Understanding the competition between hydrodechlorination and Friedel–Crafts alkylation in PVC dechlorination with silylium ions†","authors":"Nicholas J. Roubineau ,&nbsp;Eunice C. Castro ,&nbsp;Kaustubh Rane ,&nbsp;Zachary A. Wood ,&nbsp;Angelyn N. Nguyen ,&nbsp;Nancy G. Bush ,&nbsp;Ayon Das ,&nbsp;Shaama Mallikarjun Sharada ,&nbsp;Megan E. Fieser","doi":"10.1039/d5py00242g","DOIUrl":"10.1039/d5py00242g","url":null,"abstract":"<div><div>The combination of hydrodechlorination and Friedel–Crafts alkylation using silylium ions is a rapid route to fully dechlorinate poly(vinyl chloride) (PVC), while producing organic and chlorine-based products that have value for a second life. This silylium reaction has been optimized for full dechlorination under ambient conditions for a range of temperatures. Additionally, tetramethyldisiloxane is introduced as a cheaper and more moisture-stable silane, which shows similar activity as triethylsilane. While high selectivity for Friedel–Crafts alkylation has been achieved for molecular silylium chemistry, analogous attempts with PVC as a substrate have revealed a maximum arene incorporation below 30%. However, reaction conditions and choice of aromatic solvent show dramatic changes in thermal properties of the polyethylene-<em>co</em>-poly(vinyl arene) polymer product. These differences in thermal properties align with a variable side reaction of secondary Friedel–Crafts alkylation, either intramolecularly to form polyindene repeating units or intermolecularly to form crosslinks.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2514-2520"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910512","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, characterization and efficient catalytic ethylene polymerization reactions of phenylphosphine half-metallocene zirconium complexes†","authors":"Di Wu ,&nbsp;Xiaohui Mao ,&nbsp;Biao Li ,&nbsp;Xianghan Zhang ,&nbsp;Zihao Jiang ,&nbsp;Li Pan ,&nbsp;Yuesheng Li","doi":"10.1039/d5py00307e","DOIUrl":"10.1039/d5py00307e","url":null,"abstract":"<div><div>A series of half-metallocene zirconium complexes with phenylphosphine ligands, CpZr(thf)Cl₂[O-2-R₁-4-R₂-6-(PPh₂)C₆H₂] (: R₁ = ^<em>t</em>Bu, R₂ = ^<em>t</em>Bu; : R₁ = C(CH₃)₂CH₂CH₃, R₂ = C(CH₃)₂CH₂CH₃; : R₁ = ^<em>t</em>Bu, R₂ = OCH₃; and : R₁ = cumenyl, R₂ = OCH₃), were synthesized. Density functional theory calculations were conducted to investigate the structure of the cationic active species, revealing the impact of the complex structure on catalytic performance. By designing the catalyst structure and controlling the polymerization conditions, all four complexes demonstrated efficient ethylene polymerization. Notably, complex exhibited an exceptionally high activity of 58 000 kg mol_Zr⁻¹ h⁻¹ for the homopolymerization of ethylene at 100 °C. Furthermore, complex also demonstrated impressive activity of over 10⁴ kg mol_Zr⁻¹ h⁻¹ in the copolymerization of ethylene with norbornene or 1-hexene, with monomer incorporation rates reaching 56.2% for norbornene and 8.0% for 1-hexene. These findings indicated that the catalyst possessed high-temperature stability, outstanding catalytic activity, and excellent comonomer incorporation capabilities, holding significant potential in the polyolefin industry.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 21","pages":"Pages 2543-2551"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910518","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":"Initiation of radical photopolymerization via the long-lived triplet charge-separated state of donor−acceptor thermally activated delayed fluorescence compounds†","authors":"Yuying Pei, Xi Chen, Yuqi Hou, Jianzhang Zhao, Yanqin Li and Shaomin Ji","doi":"10.1039/D5PY00351B","DOIUrl":"10.1039/D5PY00351B","url":null,"abstract":"<p >Long-lived charge-separated (CS) states are observed in a series of organic electron donor–acceptor (D–A) thermally activated delayed fluorescence (TADF) emitters (<strong>PTZ-DTO</strong>, <strong>PSeZ-DTO</strong>, and <strong>DPTZ-DTO</strong>). We report, for the first time, the initiation of radical photopolymerization <em>via</em> the long-lived <small>³</small>CS state. After adding a co-initiator, diphenyliodonium hexafluorophosphate (<strong>DPI</strong>), we monitored the fluorescence intensity and lifetime quenching of the TADF initiators. The lifetime quenching study showed that the quenching of the <small>³</small>CS state is more significant than that of the <small>¹</small>CS state. Using nanosecond transient absorption (ns-TA) spectroscopy, we analyzed the quenching of the <small>³</small>CS and the triplet localized excited (<small>³</small>LE) states in detail, and the Stern–Volmer quenching constants (<em>K</em><small>_SV</small>) were found to be <em>K</em><small>_SV</small>(<small>³</small>CS) = 3.4 × 10<small>⁴</small> M<small>⁻¹</small>, <em>K</em><small>_SV</small>(<small>³</small>LE) = 2.9 × 10<small>⁴</small> M<small>⁻¹</small>, and <em>K</em><small>_SV</small>(<small>¹</small>CS) = 8.6 × 10<small>²</small> M<small>⁻¹</small>. These results demonstrated that the quenching of the <small>³</small>CS state predominates in the intermolecular electron process with <strong>DPI</strong> as the electron acceptor. This concept is different from the use of conventional photoinitiators (PIs) that use <small>³</small>LE state to initiate the intermolecular electron transfer with the co-initiator, and thus this work represents a paradigm shift of photoinitiated polymerization. Finally, the PIs <strong>PTZ-DTO</strong> was applied in lithography to obtain a series of high-resolution patterns.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 22","pages":" 2600-2610"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910514","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":"New trends in research on poly(2-oxazoline)s with antimicrobial activity","authors":"Natalia Oleszko-Torbus, Marcelina Bochenek and Agnieszka Kowalczuk","doi":"10.1039/D5PY00283D","DOIUrl":"10.1039/D5PY00283D","url":null,"abstract":"<p >Recently, the design and preparation of antimicrobial materials have received considerable interest. Over the past few years, poly(2-oxazoline)s (POx)-based systems have been intensively studied for their antibacterial, antifouling, and antifungal activity. This article highlights recent and significant developments in the field of POx with antimicrobial activity. Special attention is given to the synthesis of 2-oxazoline (co)polymers containing active compounds or specific functional groups that, in addition to enhancing or introducing antimicrobial properties, maintain high levels of biocompatibility. Interest has also been focused on the preparation of POx-based materials, such as layers on substrates, nanoparticles or hydrogels to combat microorganisms. The challenges and opportunities associated with antimicrobial POx systems are also discussed to further emphasize the potential of these materials in biomedical applications.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 22","pages":" 2574-2579"},"PeriodicalIF":4.1,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910511","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}