Polymer Chemistry最新文献

{"title":"1,2-Dithiolane/yne photopolymerizations to generate high refractive index polymers","authors":"Marianela Trujillo-Lemon, Benjamin D. Fairbanks, Andrew N. Sias, Robert R. McLeod, Christopher N. Bowman","doi":"10.1039/d4py01337a","DOIUrl":"https://doi.org/10.1039/d4py01337a","url":null,"abstract":"Copolymerization and conjugate addition of disulfides generally and dithiolanes particularly have been reported for various applications. Here, a new framework for preparing high refractive index polymeric materials through the photoinitiated addition of methyl ester of lipoic acid (LipOMe) or methyl 4-methyl-1,2-dithiolane-4-carboxylate (Me-AspOMe) with various alkynes is explored, and an infrared spectroscopy methodology was developed for understanding the dithiolane homopolymerization kinetics. The effects of the 1,2-dithiolane and alkyne chemical structures on reaction rates, polymer structures, and optical properties of the synthesized polymers were examined. Characterization of the photopolymerization products showed significant dependence on the specific structure of the 1,2-dithiolane and alkyne reactants. The ability of the 1,2-dithiolane/alkyne reaction to introduce a large amount of sulfide linkages resulted in differences in the polymer refractive index relative to that of the unreacted materials, reaching values up to 0.07. Furthermore, the application of these 1,2-dithiolane-alkyne systems into two-stage photopolymeric holography materials in a two-dimensional, high-refractive index structure was demonstrated.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077212","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":"Tailoring Polyester Based-Diblock Copolymers for Boron-Enhanced Drug Delivery: Synthesis, Kinetics, and Nanoparticle Characterization","authors":"Robert Mundil, Pavlína Marková, Martin Orsagh, Ewa Pavlova, Zuzana Walterova, Petr Toman, Olga Kockova, Mariusz Uchman","doi":"10.1039/d4py01363h","DOIUrl":"https://doi.org/10.1039/d4py01363h","url":null,"abstract":"Here, we present the synthesis of diblock copolymers of poly(ethylene glycol) methyl ether-b-poly(ε-caprolactone) (mPEG-b-PCL) with prop-2-ynyl (propargyl) substituents on ε-caprolactone (ε-CL) units. The copolymerization of ε-CL with its propargylated derivative initiated by mPEG, followed by a thiol-yne click reaction with 1-thioglycerol, results in copolymers featuring vicinal diols capable of reversibly binding boronic acid derivatives. Detailed kinetic experiments were conducted to monitor the homo- and copolymerization of ε-CL with 7-(prop-2-ynyl)oxepan-2-one. By analyzing the kinetic data, we calculated copolymerization parameters and mapped the composition profile of the resulting copolymers. The resulting gradient copolymers exhibited a lightly tapered composition profile, with an increase in ε-CL consumption at higher conversions where the more reactive 7-(prop-2-ynyl)oxepan-2-one is almost depleted. These findings were further validated through quantum chemical calculations, providing insights into the precise structure and composition of the copolymers. Characterization of the self-assembled nanoparticles was performed using static and dynamic light scattering, and their morphology was visualized via conventional and cryogenic transmission electron microscopy, confirming the formation of small, homogeneous spherical micelles. To demonstrate their potential in drug delivery, we encapsulated a model drug composed of phenylboronic acid and metallacarborane cluster into the micelles and investigated the impact of drug loading on their properties. Our comprehensive study underscores the importance of precise synthesis and structural prediction in the development of biodegradable diblock copolymers, offering valuable insights into their synthesis, kinetic behavior, and nanoscale assembly for advanced drug delivery applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143072733","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":"Binuclear Ni catalyzed ethylene copolymerization with short chain alkenol monomers","authors":"Yuan Lu, Gang Ji, Shuyang Yu, Xiaoshan Ning, Xiu-Li Sun, Yanshan Gao, Xiaoyan Wang, Yong Tang","doi":"10.1039/d4py01480d","DOIUrl":"https://doi.org/10.1039/d4py01480d","url":null,"abstract":"Ethylene coordination copolymerization with vinyl polar monomers, particularly short chain alkenols, offers an attractive method for controlled synthesis of important hydroxy-functionalized polyethylenes under mild conditions. However, reports on short-chain alkenol copolymerization are limited due to issues like chelating coordination and β-O elimination. Here, we report the synthesis and characterization of binuclear Ni complexes for ethylene copolymerization with various alkenol monomers such as allyl-OH, 3-buten-1-ol, 4-penten-1-ol and 9-decen-1-ol. These complexes, upon activation with Et<small>₂</small>AlCl, achieved notable activity (as high as 592 kg (mol cat h atm)<small>⁻¹</small>) in ethylene/3-buten-1-ol copolymerization, producing copolymers with 1.7 mol% comonomer incorporation and a high molecular weight (<em>M</em><small>_n</small> = 64.2 kg mol<small>⁻¹</small>). The activity and comonomer content were influenced by Et<small>₂</small>AlCl loading, reaction temperature, and alkenol monomer length, with longer alkenols such as 9-decen-1-ol yielding higher activity, comonomer incorporation and molecular weight. Activities up to 169 kg (mol cat h atm)<small>⁻¹</small> were also achieved in ethylene/allyl-OH copolymerization with reduced molecular weight (<em>M</em><small>_n</small> = 17.2 kg mol<small>⁻¹</small>). Microstructural analysis revealed predominant in-chain and chain-end polar monomer incorporation in all cases. Notably, ethylene/allyl-OH copolymers exhibited unique olefinic end groups and microstructures assignable to Friedel–Crafts reactions, which is likely due to an alternative chain termination pathway associated with the short chain length between the O atom and the active Ni center. For comparison, ethylene/allyl-OAc copolymers showed exclusively olefinic groups, indicating a β-OAc elimination mechanism. This process resulted in lower activity and molecular weight, suggesting catalyst poisoning from rapid chain termination.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071983","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":"High Performance Polyurethanes Derived from Aromatic Acetal-Containing Polyols Enabling Closed-Loop Recycling","authors":"Patrick Schara, Tankut Türel, Anna Maria Cristadoro, Rint P Sijbesma, Željko Tomović","doi":"10.1039/d4py01428f","DOIUrl":"https://doi.org/10.1039/d4py01428f","url":null,"abstract":"Polyurethanes (PUs) are widely employed across diverse industries due to their versatility, durability, and mechanical strength. Enhancing their thermal and mechanical performance holds great potential for expanding their applicability and unlocking new market opportunities. This study addresses two key challenges: limited availability of aromatic polyols for high-performance PUs and their recycling issues. Incorporation of aromatic content in polyether polyols has traditionally been difficult using conventional methods. Herein, we developed three novel aromatic acetal-containing polyols through a green and solvent-free protocol via the polycondensation of aldehydes and diols, using acidic heterogeneous catalysts. Resulting polyols, with tailored aromatic content, significantly improved the mechanical strength of PUs, while maintaining low viscosity and easy processability. Besides that, PUs synthesized from these polyols exhibited excellent thermal stability and remarkable water resistance under neutral conditions. Additionally, these materials demonstrated efficient closed-loop recyclability through a novel transacetalization-based depolymerization under mild acidic conditions, yielding high purity monomers in good yields. This work introduces innovative aromatic polyacetal polyols, offering a sustainable approach to high-performance PUs. The approach also leverages the wide availability of diols and aldehydes, enabling the design of PUs with superior properties and closed-loop recycling.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056357","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":"Correction: Towards the synthesis of polythiazolines: a post-polymerization approach","authors":"Aikaterini Mathianaki, Aysha Kinjo Demeler, Adrian Dömling, Federico Ferrari, Frieda Clara M. Scheelje, Hilke Bahmann, Guillaume Delaittre","doi":"10.1039/d4py90157f","DOIUrl":"https://doi.org/10.1039/d4py90157f","url":null,"abstract":"Correction for ‘Towards the synthesis of polythiazolines: a post-polymerization approach’ by Aikaterini Mathianaki <em>et al.</em>, <em>Polym. Chem.</em>, 2025, https://doi.org/10.1039/d4py00930d.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"40 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056353","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":"In memoriam Acad. Prof. Dr Bogdan Simionescu (1948–2024)","authors":"Valentin Victor Jerca","doi":"10.1039/d4py90155j","DOIUrl":"https://doi.org/10.1039/d4py90155j","url":null,"abstract":"A graphical abstract is available for this content","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"62 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056280","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":"Polymethylene with Cage Silsesquioxane: Densely Grafted Structure Prevents Side-Chain Crystallization","authors":"Yu Tomioka, Tomoki Yasui, Kensuke Naka, Hiroaki Imoto","doi":"10.1039/d4py01222d","DOIUrl":"https://doi.org/10.1039/d4py01222d","url":null,"abstract":"Cage silsesquioxane (POSS, polyhedral oligomeric silsesquioxane) is a crucial building block in the development of organic-inorganic hybrid polymers. However, polymers incorporating POSS units in their side chains often exhibit poor film-forming properties because of the high crystallinity of POSS. In this study, polymethylene densely grafted with POSS units was synthesized. This POSS-polymethylene structure produced a homogeneous, transparent cast film, in contrast to the turbid film formed by POSS-polyacrylate. The significant difference in the film quality was attributed to the inhibition of POSS crystallization, facilitated by the dense tethering of POSS on the polymethylene backbone","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055503","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(butylene succinate) filaments for fused deposition modelling (FDM) 3D-printing","authors":"Yong Chen, Jielin Xu, Ye Chen, Chaosheng Wang, Huaping Wang, Jing Wu","doi":"10.1039/d4py01351d","DOIUrl":"https://doi.org/10.1039/d4py01351d","url":null,"abstract":"Polybutylene succinate (PBS) is an aliphatic degradable polyester prepared by melt polycondensation of succinic acid and 1,4-butanediol; the highly symmetrical molecular structure and linear polymerization monomer result in a polymer exhibiting rapid crystallization and low melt strength, limiting its fiber development and application in melt processing. In order to investigate the feasibility of using PBS as a printing consumable, in this work, a series of long-chain branched PBS filaments were synthesized by using branching agents including glycerol, diglycerol, pentaerythritol and di-pentaerythritol. The chemical structure of different branching agents significantly affects the crystallization properties of PBS polyesters. The branched structure disturbs the symmetry and regularity of the polymer and reduces the crystallization ability of the polymer. Chain topology was obtained through rheological investigations and the synthesized polymers showed a typical behavior of linear and branched PBS. The complex viscosity, storage modulus and loss modulus of long chain branched PBS at low frequency were significantly enhanced compared to those of linear PBS. To reduce the fluidity of the polymer, the melt strength of the polymer was increased by about 2.7 times. PBS filaments have been developed for the application of 3D-printing <em>via</em> fused deposition modeling (FDM), which provides a broader research field for PBS polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"49 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055502","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":"Sonochemistry-assisted Reversible Addition-Fragmentation Transfer Polymerization for Multicolor Room-temperature Phosphorescent Polymers","authors":"Zhenhua Wang, Wenjing Liu, Ruoqing Zhao, Jinhong Han, Chen Wang, Xiaoyang Shao","doi":"10.1039/d5py00018a","DOIUrl":"https://doi.org/10.1039/d5py00018a","url":null,"abstract":"Invitation to submit to Polymer Chemistry The coupling of ultrasound with reversible-deactivation radical polymerization offers intriguing possibilities to synthesize polymers in hetergenous medium as ultrasonic wave is benificial to achieve uniform monomer dispersion and mitigate aggregation. In this study, sonochemistry-assisted reversible addition-fragmentation chain transfer polymerization (SA-RAFT) was demonstrated to exhibit first-order kinetics throughout polymerization and excellent control over the growth of the polymer nanoobjects in suspension, providing a high monomer conversion (~90%) and a gradient copolymer (GCP) with predetermined molecular weight. In addition, the GCP films could emit full-visible-spectrum room-temperature phosphorescence under UV irradiation via Förster resonance energy transfer. Remarkably, the GCP films could be stretched to approximately 400% and maintain stable RTP emission under a strain up to 150%.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050492","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":"pH-responsive polymer-supported pyrene-based fluorescent dyes for CO2 detection in aqueous environments","authors":"David Londono, David Chappell, Bilal Rashid, Blaine Tookey, Calum T. J. Ferguson, Rachel K. O'Reilly","doi":"10.1039/d4py01186d","DOIUrl":"https://doi.org/10.1039/d4py01186d","url":null,"abstract":"Detecting fluctuations in carbon dioxide by switching ‘on’ or ‘off’ fluorescence in aqueous environments has often been targeted for efficient monitoring. This switch needs to occur in a drastic and fast way that is visually observable to be effective. CO2 dissolves in water, leading to a reduction in pH, which can be used to trigger a response. Specifically, the modification of fluorescent dyes with pH-responsive units could create a dye that responds to CO2 and switches ‘off’ fluorescence. Here, we developed a water-soluble polymer functionalized with a CO2-responsive pyrene dye. This functional dye contains a tertiary amine conjugated to the aromatic pyrene, which can be protonated at pH ~6.5 or lower. After only 15 s of CO2 bubbling, a significant fluorescence ‘off’ response was observed, with a drastic reduction in fluorescence at 480 nm as a consequence of disrupting non-covalent excimer bonds. Moreover, the exposure to atmospheric air results in a recovery of the excimer state and, therefore, the fluorescence, demonstrating its reversible nature.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"53 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055504","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}