Polymer Chemistry最新文献

{"title":"Solvent and Temperature Effects in the Photoiniferter RAFT Polymerisation of PEG Methacrylate","authors":"Roujia Chang, Bryn D. Monnery, Inge Zuhorn","doi":"10.1039/d5py00300h","DOIUrl":"https://doi.org/10.1039/d5py00300h","url":null,"abstract":"Photoiniferter (PI)-RAFT polymerization is a promising approach to synthesise a broad range of (meth)acrylic and styrenic polymers because of its highly ‘living’ nature. The lack of an imbalance between initiating and chain-transfer fragments minimises the inherent bimolecular termination of conventional RAFT. Poly(poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) is a potential biocompatible material for biomedical applications, but the highly reactive free radical of PEGMA makes control of its polymerisation challenging. In this study, we investigated the synthesis of P(PEGMA) through PI-RAFT. Current studies on the PI-RAFT mechanisms are limited and the effect of solvents on kinetics has not been reported. We varied several reaction conditions: excitation wavelengths, monomer concentrations, temperatures, and solvents. The propagation constant (k<small>_p</small>) values were affected by the RAFT main equilibrium. We calculated the Arrhenius parameters, enthalpy of activation (Δ𝐻<small>^‡</small>), and entropy of activation (ΔS<small>^‡</small>) for polymerization in various solvents. Regression analysis was conducted to fit the results with extinction coefficients of CTA in seven common solvents, solvent physical properties, and solvatochromic scales. The effective collision factor A had a good fitting with an exponential regression model of the extinction coefficients, indicating a strong relationship between the reaction rate and excitation of the CTA. Solvent polarity scales, such as Kalmet-Abraham-Taft (KAT) and Catalan parameters, failed to predict kp, Arrhenius parameters, Δ𝐻<small>^‡</small>, and ΔS<small>^‡</small>. A chain transfer constant C<small>_tr</small> &gt; 1 for all syntheses indicated relatively good control over the polymerization through degenerative chain transfer with CTA radicals. In general, C<small>_tr</small> decreased with increasing temperatures, a result of the rate of excitation by photon absorption being constant, but the kp being increased by the temperature. Anisole was the best solvent, able to keep Ð = 1.30 even at 40 °C.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"151 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154087","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":"Preparation of high-performance one-component polysulfide adhesives and modification by silane side chains","authors":"Xu Han, Le Chang, Zeqian Wang, Feng Liu","doi":"10.1039/d5py00314h","DOIUrl":"https://doi.org/10.1039/d5py00314h","url":null,"abstract":"One-component polysulfide adhesive preparation by diisocyanate-terminated prepolymers and 1,4-butanedithiol (BSO) can provide convenient moisture curing and excellent mechanical properties, but the formation of polysulfide-urea (–NHCOS–) groups causes some reduction in solvent resistance limiting their further application in aircraft fuel tank sealing. Introducing silane side chains into polysulfide adhesive systems is a viable approach to improving the solvent resistance. In this work, a series of novel silane side chain-modified one-component polysulfide adhesives were synthesized by using chain extenders in different proportions of BSO and (3-(2-aminoethyl)aminopropyl)trimethoxysilane (AEAPTMS). The results showed that a moderate amount of silane side chains and restricting the formation of Si–O–Si crosslinked networks can effectively enhance the elongation, interfacial interaction and solvent resistance. The optimal overall performance was obtained when the mass ratio of BSO and AEAPTMS was 7 : 1 (Si-OCPS3). Conversely, the oil and water absorption content after 21 days of Si-OCPS3 were 2.21 ± 0.06% and 2.81 ± 0.31%, being 20.50% and 43.57% lower than before modification (Si-OCPS0), respectively. Moreover, Si-OCPS3 exhibited higher tensile strength of 17.34 ± 0.66 MPa (oil) and 15.67 ± 0.32 MPa (water) than Si-OCPS0. We believe our paradigm can provide a feasible approach for designing high-performance one-component polysulfide adhesives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"240 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154088","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":"Tuning the linkage microenvironment in imine-based covalent organic frameworks for enhanced photocatalytic hydrogen production","authors":"Hao Li, Bin Zheng, Ming Wang, Xiaofang Su, Hui Hu, Jianyi Wang, Huanjun Xu, Jingying Shi, Yanan Gao","doi":"10.1039/d5py00361j","DOIUrl":"https://doi.org/10.1039/d5py00361j","url":null,"abstract":"Rational design of covalent organic frameworks (COFs) at the molecular level is necessary to improve the photocatalytic hydrogen evolution (PHE) performance. Herein, a photosensitive two-dimensional (2D) COF, namely Im<small>_TF–PD</small>, is first constructed through the condensation of 1,3,6,8-tetra(4-formylphenyl)pyrene (TFPPy) and <em>p</em>-phenylenediamine (PD) under solvothermal conditions. The photocatalytic activity of Im<small>_TF–PD</small> is regulated by transforming imine linkages into quinoline through the Povarov reaction between the imine groups and phenylacetylene and 4-ethynylbenzonitrile, respectively. Such a post-synthetic modification (PSM) process enables the modulation of π-conjugation and simultaneously the introduction of the electron-deficient nitrile group improves the local electron delocalization of the skeleton of Im<small>_TF–PD</small>. As a result, the modified quinoline based COF (Qu-CN) exhibited outstanding and steady hydrogen production with a maximum hydrogen production rate of 245.17 mmol g<small>⁻¹</small> h<small>⁻¹</small> under visible-light irradiation (<em>λ</em> ≥ 420 nm). Experimental and computational results revealed that Qu-CN with better electron–hole separation and lower band gap significantly improved the catalytic activity regarding kinetics and thermodynamics. This study reveals that enhancing π-conjugation and tuning the local electronic environment of COF-based photocatalysts provide a convenient and effective approach for the development of new efficient photocatalysts.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145872","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":"Photo-curable resins based on poly(globalide) for 3D printing of resorbable scaffolds: synthesis, crosslinking and post-functionalization","authors":"Laura Oliveira Rebouças, Isabela Lima Autran Dourado, Giovanne Delechiave, Denisse Esther Mallaupoma Camarena, Sandra Van Vlierberghe, Luiz Henrique Catalani","doi":"10.1039/d5py00237k","DOIUrl":"https://doi.org/10.1039/d5py00237k","url":null,"abstract":"In recent years, significant efforts have been dedicated to developing photo-curable biomaterials for medical applications such as prosthetics, tissue engineering, and drug delivery. Although light-based 3D printing techniques enable the fabrication of resorbable medical devices with tailored properties, the shortage of suitable biodegradable materials still constrains their full potential. This study focused on producing resins based on poly(globalide) diacrylate for vat photo-polymerization 3D printing of biocompatible and biodegradable materials. By incorporating into the formulation unsaturated compounds such as poly(ethylene glycol) diacrylate, 1,10-decanediol diacrylate, N-vinylpyrrolidone, and N-isopropylacrylamide, the gelation kinetics, mechanical properties, and hydrolytic degradation rates were effectively modulated. Additionally, the successful post-functionalization of photo-crosslinked films with N-acetylcysteine through thiol-ene click-like chemistry demonstrates the material’s potential for surface modification even after processing (photo-crosslinking). As part of the biological evaluation, the in vitro cytotoxicity of each material was tested according to the ISO 10993-5 standard. Finally, the suitability of one of the resins for vat photo-polymerization 3D printing was successfully validated with an LCD-based SLA printer.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"56 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145867","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":"Preparation and properties of stretchable low temperature resistant flexible epoxy resin curing agent","authors":"Hao Li, Qiang Liu, Yiming Du, Yanyan Liu, Wei Zhang, Xingyou Tian, Hua Wang","doi":"10.1039/d5py00254k","DOIUrl":"https://doi.org/10.1039/d5py00254k","url":null,"abstract":"Two innovative molecular design strategies for epoxy curing agents to address the inherent brittleness and cryogenic limitations of conventional epoxy systems are introduced. A silane-modified curing agent (DETA-Si) and a flexible-chain-engineered curing agent (NBO<small>_<em>n</em></small>) were synthesized to achieve unprecedented mechanical–electrical–thermal synergies. The DETA-Si/EP composite demonstrates a record-breaking elongation at break of 125% (22× improvement over unmodified systems) while maintaining ultralow dielectric loss (tan <em>δ</em> &lt; 0.04) and thermal stability (<em>T</em><small>_d</small> = 236 °C). The NBO<small>_<em>n</em></small> series, incorporating rigid benzene rings and tunable aliphatic chains, exhibits exceptional cryogenic resilience: 18% elongation at 298 K with &gt;50% ductility retention after 24-hour immersion in liquid nitrogen (77 K). Conductive composites cured with EP/NBO<small>₁₀</small> show stable resistance (±5%) under 30-day cryogenic exposure. Free volume engineering, validated <em>via</em> WLF modeling, underpins the enhanced low-temperature performance. These advancements establish a paradigm for epoxy resins in flexible electronics operating under extreme conditions, such as flexible sensors and polar climate devices.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"149 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144145870","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 depolymerization studies of biohybrid polycarbonates derived from terpenes","authors":"Thirusangumurugan Senthamarai, Enrico Lanaro, Jack Tinker, Antoine Buchard, Arjan W. Kleij","doi":"10.1039/d5py00285k","DOIUrl":"https://doi.org/10.1039/d5py00285k","url":null,"abstract":"We here report the catalytic ring-opening copolymerization of 2-menthene oxide (<strong>MO</strong>), a terpene-based monomer derived from <small>L</small>-menthol, and CO<small>₂</small> to provide poly(menthene carbonate), <strong>PMC</strong>, with a maximum molecular weight (<em>M</em><small>_n</small>) of 10.2 kg mol<small>⁻¹</small>. The terpene monomer <strong>MO</strong> can also be combined with both limonene oxide (<strong>LO</strong>) and CO<small>₂</small> in a formal terpolymerization process providing, depending on the monomer feed ratio, different types of biohybrid polycarbonates (<strong>PLMC</strong>) with different degrees of functionality. These terpolymerizations could be extended to the use of an acyclic terpene oxide and either <strong>MO</strong>/CO<small>₂</small> or <strong>LO</strong>/CO<small>₂</small>, and a previously reported xylose-derived bicyclic oxetane. A selection of <strong>MO</strong>/<strong>LO</strong> based biohybrid <strong>PLMCs</strong> were conveniently depolymerized under TBD catalysis to regenerate the original mixture (&gt;95%) of terpene oxides thereby providing a suitable starting point for the circular use of these biohybrid macromolecules.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122718","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":"Cyclobutane-linked Nanothreads through Thermal and Photochemically Mediated Polymerization of Cyclohexadiene","authors":"Morgan Murphy, Bohan Xu, Katie E. Rank, Sikai Wu, Steven Huss, John V. Badding, Steven A. Lopez, Vincent Crespi, Elizabeth Elacqua","doi":"10.1039/d5py00470e","DOIUrl":"https://doi.org/10.1039/d5py00470e","url":null,"abstract":"Carbon nanothreads are a rapidly growing class of 1D nanomaterials with sp<small>³</small>-hybridized diamond-like backbones. They are typically synthesized through pressure-induced polymerizations of aromatics, resulting in diverse structures and functionalities. Aside from precursor selection, there are limited means to control reaction pathway or polymerization outcome. Analogous to selection rules that govern outcomes in molecular chemistry, we investigated thermally and photochemically mediated pressure-induced polymerizations of 1,4-cyclohexadiene and explored the resultant products. Thermally mediated polymerization of 1,4-cyclohexadiene yields a crystalline product; yet identification of the backbone architecture is consistent with multiple reaction pathways being accessed. While support for cyclobutane structures is present, comparison to simulated structures suggests multiple products are obtained. In contrast, the recovered product obtained from the photochemically mediated polymerization exhibits different <em>d</em>-spacings and is consistent with simulations that support a single pathway toward cyclobutane-linked nanothreads. These results suggest that photochemistry can enable reaction selectivity in nanothread synthesis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"135 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144113641","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":"Supramolecular Polymerization and Self-assembly of Transition Metal Complexes","authors":"Merlin R. Stühler, Alex Johannes Plajer","doi":"10.1039/d5py00315f","DOIUrl":"https://doi.org/10.1039/d5py00315f","url":null,"abstract":"Metallo-supramolecular polymers (MSPs) have emerged as a dynamic field in soft materials and nanomaterials over the past three decades. The unique interplay of ligands and metal ions plays a crucial role in defining their properties, such as binding strength and topology making these systems distinct from their all-organic counterparts. Furthermore, the incorporation of metal centers introduces redox activity, unique photophysical properties, and electronic functionality. Hereby the systems can exhibit stimuli-responsive behavior, essential for applications in optoelectronics and biology. However, challenges remain in achieving precise control over self-assembly, morphology, and spatiotemporal responsiveness as well as a clear rationale between coordination and self-assembly behavior. Our review therefore summarizes recent advances in ligand design, coordination modulation, and polymerization techniques offering new strategies to rationally develop MSPs with tailored functionalities","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104079","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":"5-Ethylidene-2-norbornene (ENB) and 5-Vinyl-2-norbornene (VNB) based Alicyclic Polyols for the Synthesis of Polyesters","authors":"Brigita Bratić, Peter Altenbuchner, Thomas Heuser, Bernhard Rieger","doi":"10.1039/d5py00247h","DOIUrl":"https://doi.org/10.1039/d5py00247h","url":null,"abstract":"Amorphous polyesters derived from rigid alicyclic monomers with high glass transition temperatures are of great interest as potential substitute for poly(carbonate)s. Therefore, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) were identified as interesting diol monomer precursors to enhance the thermal properties of polyesters. The regioselective synthesis of the corresponding diols from ENB and VNB were optimized and first scale up experiments gave promising results for a potential large scale production of these polyester monomers. Moreover, for proof of concept, an alternative procedure was established to synthesize exclusively branched diols. Polymerization experiments were conducted with dimethyl terephthalate (DMT) as model compound to compare the polyesters with commonly used poly(ethylene terephthalate)s. Therefore, a series of polyesters were produced containing branched or linear or a mixture of both regioisomers, and structure property relationships were investigated with GPC, TGA and DSC analysis. The Tg values ranged from 75 to 103 °C, depending on the branched and linear moieties in the polyester microstructure and their molecular weights. Moreover, isosorbide (IS) was introduced as biobased comonomer, resulting in amorphous copolyesters with promising Tgs ranging from 81 to 97 °C.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104077","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":"Efficient synthesis of polylactide and copolymers under industrial conditions by multinuclear β-ketoimide zinc complexes","authors":"Yu Cheng, Zihe Zhao, Xiaowei Xu, Chun-Xiao Ren, Xiaohui Wei, Yanxiang Yang, Jin Li, Daqiang Jiang, Kunyu Zhang, Bin Wang, Yi Luo","doi":"10.1039/d4py01486c","DOIUrl":"https://doi.org/10.1039/d4py01486c","url":null,"abstract":"Polylactic acid (PLA), as a representative degradable aliphatic polyester, has the advantages of biodegradability, biocompatibility, good thermal and mechanical properties. The industrial production of high molecular weight PLA is from the the ring opening polymerization (ROP) of L-lactide (L-LA) catalyzed by Sn(II)2-ethyl-hexanoate (Sn(Oct)2) under melt and bulk conditions. Although huge efforts have been paid to develop organometallics with low toxicity and many highly active catalyst under laboratory mild conditions were found, very few candidates can compete with Sn(Oct)2 under industrially relevant conditions. Here, we reported novel multinuclear β-ketoiminate zinc complexes, as efficient catalysts for the L-LA polymerization under industrially relevant conditions, with a turnover frequency as high as 5880 h-1. The catalysts exhibited good stability and activity and compete well with Sn(Oct)2 under industrial conditions, affording colorless PLLA with high crystallinity. Preliminary copolymerization experiments suggested that the zinc catalyst can also catalyze the random copolymerization of L-LA with ε-caprolactone and dioxanone under melt and bulk conditions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097067","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}