Polymer Chemistry最新文献

Stereoselective Polycondensation of Levoglucosenone leading to Water-Degradable Biopolymers

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-24 DOI: 10.1039/d4py01094a

Atsushi Tahara, Shogo Yashiro, Toshio Hokajo, Shinji Kudo, Yuta Yoshizaki, Tomohiro Konno, Takayuki Doi

{"title":"Stereoselective Polycondensation of Levoglucosenone leading to Water-Degradable Biopolymers","authors":"Atsushi Tahara, Shogo Yashiro, Toshio Hokajo, Shinji Kudo, Yuta Yoshizaki, Tomohiro Konno, Takayuki Doi","doi":"10.1039/d4py01094a","DOIUrl":"https://doi.org/10.1039/d4py01094a","url":null,"abstract":"Highly stereochemically controlled polymers were successfully synthesized from levoglucosenone (LGO), derived from cellulose. Since its discovery in the 1970s, the reactivity of LGO has been widely studied in organic chemistry, owing to its diverse functional groups that serve as linkages for polymer formation. However, most of the previous methods for synthesizing polymers from LGO lacked precise control over regio- and stereochemistry, making stereoselective polymerization from LGO a persistent challenge. Although the ketone moiety in LGO is typically reduced before polymerization, a new LGO polymer was designed, containing a C=N bond obtained by condensation with dicarboxylic dihydrazide. NMR measurements revealed that condensation occurred with high stereoselectivity to produce the E-isomer. This selectivity extended from the model compound to polymer synthesis, achieving high E / Z selectivity. The resulting polymer exhibited optical rotation (up to +89), indicating its potential as a chiral polymer. In spite of these polymers showed high tolerance toward many solvents, they were degradable in water with a simple chemical treatment. The proposed approach facilitates the development of sustainable, high-performance materials that can address both environmental and industrial needs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879780","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}

引用次数: 0

Aziridine-Based Organocatalytic Polymerization for Tunable Sulfur Incorporation in Polyureas

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-23 DOI: 10.1039/d4py01171f

Leying Xu, Changzheng Ju, Jiazi Zheng, Qingyong Chen, Zhen Zhang

{"title":"Aziridine-Based Organocatalytic Polymerization for Tunable Sulfur Incorporation in Polyureas","authors":"Leying Xu, Changzheng Ju, Jiazi Zheng, Qingyong Chen, Zhen Zhang","doi":"10.1039/d4py01171f","DOIUrl":"https://doi.org/10.1039/d4py01171f","url":null,"abstract":"Developing new methods for converting inorganic sulfur into sulfur-containing polymers is crucial for advancing both sustainable development and innovative polymeric materials. In this study, we present an aziridine-based polymerization strategy to synthesize polyureas with tunable sulfur incorporation. The process begins with the reaction of aziridine with isocyanate, followed by a ring-opening reaction with an inorganic sulfur reagent. When elemental sulfur is used, oligosulfide anions form in the presence of an organobase, which then nucleophilically attack the aziridine ring, producing oligosulfide-functionalized polyureas. Alternatively, using sodium sulfide generates poly(thioether urea)s through a similar ring-opening mechanism. Model reactions confirm successful sulfur incorporation during these processes. Additionally, a cross-linked polyurea synthesized with tri-isocyanate exhibits excellent mechanical properties, with tensile stress exceeding 30 MPa, and demonstrates good reprocessability due to the dynamic nature of the oligosulfide bonds. Overall, this polymerization approach broadens the range of sulfur-containing materials and supports further advances in aziridine-based polymer chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874100","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}

引用次数: 0

Polymerization-induced Self-assembly mediated by Vinyl-functionalized Macromolecular Chain Transfer Agents: A Straightforward Approach for Cross-linked Block Copolymer Nanoparticles with tunable Morphologies

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-23 DOI: 10.1039/d4py01048e

Honggao Huang, Liwei Luo, Li Zhang, Jianbo Tan

{"title":"Polymerization-induced Self-assembly mediated by Vinyl-functionalized Macromolecular Chain Transfer Agents: A Straightforward Approach for Cross-linked Block Copolymer Nanoparticles with tunable Morphologies","authors":"Honggao Huang, Liwei Luo, Li Zhang, Jianbo Tan","doi":"10.1039/d4py01048e","DOIUrl":"https://doi.org/10.1039/d4py01048e","url":null,"abstract":"Herein, block-type and random-type vinyl-functionalized macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents were synthesized by RAFT solution polymerization and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of hydroxylpropyl methacrylate (HPMA). When using the block-type macro-RAFT agent, cross-linked block copolymer nanoparticles with various morphologies could be prepared. Control experiments demonstrate that the vinyl group in the macro-RAFT agent has little impact on the polymerization process and the morphology of block copolymer nanoparticles. Morphologies of block copolymer nanoparticles could be controlled by changing the length of the stabilizer block, the [HPMA]/[macro-RAFT] ratio, and the HPMA concentration. When using the random-type macro-RAFT agent, cross-linked block copolymer nanoparticles were still obtained. Moreover, it was found that the random distribution of vinyl group in the macro-RAFT agent facilitated the formation of higher-order morphologies. Finally, the obtained cross-linked worms and vesicles were used as seeds for seeded RAFT polymerization of tert-butyl acrylate (tBA) or glycidyl methacrylate (GlyMA), which enables the further control over the surface morphology of block copolymer nanoparticles. We expect that this study will offer new opportunities for the rational preparation of cross-linked block copolymer nanoparticles with various morphologies.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874099","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}

引用次数: 0

Photocrosslinked Hybrid Hydrogel Based on Chitosan/Hyaluronic Acid /ZnO toward Wound Sealing

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-20 DOI: 10.1039/d4py01207k

Jiale Sun, Donghao Hu, Yiling Li, Jia Wei, Yanlei Yu

引用次数: 0

Precisely Controlled yet Dynamically Exchanged Micelles via the Self-Assembly of Amphiphilic Acrylate Random Copolymers in Water

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-20 DOI: 10.1039/d4py01272k

Hiroyuki Kono, Makoto Ouchi, Takaya Terashima

{"title":"Precisely Controlled yet Dynamically Exchanged Micelles via the Self-Assembly of Amphiphilic Acrylate Random Copolymers in Water","authors":"Hiroyuki Kono, Makoto Ouchi, Takaya Terashima","doi":"10.1039/d4py01272k","DOIUrl":"https://doi.org/10.1039/d4py01272k","url":null,"abstract":"Herein, we investigated the self-assembly of amphiphilic acrylate random copolymers bearing hydrophilic poly(ethylene glycol) chains and hydrophobic dodecyl groups into micelles in water. The random copolymers formed precise yet dynamic micelles in water, dependent on degree of polymerization (DP) and composition. The copolymers shorter than a threshold DPth exclusively formed multichain micelles and the copolymers longer than the DPth self-folded into unimer micelles. The molecular weight and size of the multichain micelles were determined by the composition, and the aggregation number was controllable by the DP. Critical micelle concentration of the random copolymers was estimated to be approximately 1 × 10-3 mg/mL, and almost independent of the DP, aggregation number, monomer sequence, and backbone structures. More uniquely, owing to the flexible backbones, the acrylate random copolymer micelles induced the exchange of polymer chains even at a low temperature such as 10 °C (activation energy: Ea = ~40 kJ/mol) although corresponding methacrylate counterparts with relatively rigid backbones required at least 25 °C for polymer chain exchange.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857977","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}

引用次数: 0

Photobase-Catalyzed Thiol-ene Click Chemistry for Light-Based Additive Manufacturing

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-20 DOI: 10.1039/d4py01120a

J. Antonio Vazquez, Xabier Lopez de Pariza, Nathan Ballinger, Naroa Sadaba, Aileen Sun, Ayokunle Oluwafemi Olanrewaju, Haritz Sardon, Alshakim Nelson

{"title":"Photobase-Catalyzed Thiol-ene Click Chemistry for Light-Based Additive Manufacturing","authors":"J. Antonio Vazquez, Xabier Lopez de Pariza, Nathan Ballinger, Naroa Sadaba, Aileen Sun, Ayokunle Oluwafemi Olanrewaju, Haritz Sardon, Alshakim Nelson","doi":"10.1039/d4py01120a","DOIUrl":"https://doi.org/10.1039/d4py01120a","url":null,"abstract":"Photo-mediated additive manufacturing from liquid resins (vat photopolymerization) is a rapidly growing field that will enable a new generation of electronic devices, sensors, and soft robotics. Radical-based polymerization remains the standard for photo-curing resins during the printing process due to its fast polymerization kinetics and the range of available photoinitiators. Comparatively, there are fewer examples of non-radical chemical reactions for vat photopolymerization, despite the potential for expanding the range of functional materials and devices. Herein, we demonstrate ionic liquid resins for vat photopolymerization that utilize photo-base generators (PBGs) to catalyze thiol-Michael additions as the network forming reaction. The ionic liquid increased the rate of curing, while also introducing ionic conductivity to the printed structures. Among the PBGs explored, 2-(2-nitrophenyl)-propyloxycarbonyl tetramethylguanidine (NPPOC-TMG) was the most effective for the vat photopolymerization process wherein 250 μm features were successfully printed. Lastly, we compared the mechanical properties of the PBG catalyzed thiol-Michael network versus the radical polymerized network. Interestingly, the thiol-Michael network had an overall improvement in ductility compared to the radical initiated resin, since step-growth methodologies afford more defined networks than chain growth. These ionic liquid resins for thiol-Michael additions expand the chemistries available for vat photopolymerization and present opportunities for fabricating devices such as sensors.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867373","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}

引用次数: 0

Tuneable and degradable thermosets possessing dynamic aliphatic disulfide bonds via stereoselective thiol-yne polymerisation

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-20 DOI: 10.1039/d4py01195c

Daniele Giannantonio, Arianna Brandolese, Andrew P. Dove

引用次数: 0

One-step preparation of anisotropic snowman-like poly(ionic liquid) microspheres via microwave-assisted dispersion polymerization

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-18 DOI: 10.1039/d4py01053a

Xufeng Hu, Jingyi Li, Xiaopeng Zhao, Jianbo Yin

{"title":"One-step preparation of anisotropic snowman-like poly(ionic liquid) microspheres via microwave-assisted dispersion polymerization","authors":"Xufeng Hu, Jingyi Li, Xiaopeng Zhao, Jianbo Yin","doi":"10.1039/d4py01053a","DOIUrl":"https://doi.org/10.1039/d4py01053a","url":null,"abstract":"Anisotropic polymer microspheres (e.g. snowman-like shape) have different properties from isotropic microspheres and they are widely used in photonic crystals, bioengineering, rheology, and so on. These anisotropic polymer microspheres are usually prepared by seed emulsion polymerization, dynamic swelling, microfluidic methods, etc. However, these methods are multi-step and time cost and they are mainly used to prepare neutral polymer microspheres. Dispersion polymerization is a simple method to prepare polymer microspheres, whereas the conventional dispersion polymerization can only produce spherical polymer microspheres due to limitations of nucleation growth mechanism and minimum surface energy theory. In this paper, we report a one-step microwave-assisted dispersion polymerization method that can prepare anisotropic poly(ionic liquid) microspheres with controlled snowman-like morphology. This method is simple and only involves one-step polymerization reaction of a solution containing ionic liquid monomer, cross-linking agent, initiator and stabilizer in anhydrous ethanol at a specific temperature under microwave irradiation for 90 min. The morphology of poly(ionic liquid) microspheres formed at different reaction stages is traced by optical microscopy and scanning electron microscopy. It shows that the rapid formation of cross-linked poly(ionic liquid) microspheres with divinylbenzene as cross-linking agent under microwave irradiation is the key to the formation of anisotropic snowman-like poly(ionic liquid) microspheres. Through varying the amount of monomer, cross-linking agent, initiator, solvent and reaction temperature, the morphology of anisotropic snowman-like poly(ionic liquid) microspheres can be modulated. In addition, using discontinuous microwave irradiation can promote the phase separation and increase the anisotropic level of snowman-like poly(ionic liquid) microspheres.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"38 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841695","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}

引用次数: 0

Transformation of Semicrystalline Polymer Mechanics by Cyclic Polymers

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-18 DOI: 10.1039/d4py01269k

Yishayah Bension, Andrew Wijesekera, Coby S. Collins, Juncheng Zheng, Hai Zhao, Ting Ge, Chuanbing Tang, Siteng Zhang, Shiwang Cheng, Morgan Stefik

{"title":"Transformation of Semicrystalline Polymer Mechanics by Cyclic Polymers","authors":"Yishayah Bension, Andrew Wijesekera, Coby S. Collins, Juncheng Zheng, Hai Zhao, Ting Ge, Chuanbing Tang, Siteng Zhang, Shiwang Cheng, Morgan Stefik","doi":"10.1039/d4py01269k","DOIUrl":"https://doi.org/10.1039/d4py01269k","url":null,"abstract":"Cyclic polymers, lacking chain ends and featuring unique topological constraints, offer distinctive mechanical and thermal behaviors. This study synthesizes and compares semicrystalline linear and cyclic polycyclooctene (PCOE), with linear PCOE produced via ring-opening metathesis polymerization (ROMP) and cyclic PCOE via ring-expansion metathesis polymerization (REMP). Mechanical, thermal, and crystalline properties were evaluated through tensile testing, dynamic mechanical analysis (DMA), and wide-angle X-ray scattering (WAXS). Findings reveal that crosslinked cyclic PCOE exhibits lower tensile strength but greater stretchability than its linear counterpart, indicating enhanced network softness. DMA results show cyclic PCOE has a lower glass transition temperature T_g and rubbery plateau modulus G_rubbery^', while WAXS indicates lower crystallinity in cyclic PCOE < 25%, stabilizing at approximately 15% under a tensile strain of 100%. These differences suggest that polymer topology, not crystallinity, primarily dictates the mechanical response. Molecular dynamics simulations, using a crystallizable model of polyethylene, replicate the lower stress and higher stretchability observed experimentally, highlighting more compact cyclic polymer conformations with fewer entanglements. The results align with past studies on amorphous cyclic polymers, providing deeper insights into how cyclic structures affect semicrystalline polymer mechanics. This combined experimental and simulation approach advances understanding of cyclic polymer architectures and their transformative impact on polymer properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841694","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}

引用次数: 0

Guanidinium based ionic porous organic polymer as a propitious material for inordinate uptake of permanganate ions from water

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2024-12-18 DOI: 10.1039/d4py01329h

P. S. Nandamol, Mintu Porel

{"title":"Guanidinium based ionic porous organic polymer as a propitious material for inordinate uptake of permanganate ions from water","authors":"P. S. Nandamol, Mintu Porel","doi":"10.1039/d4py01329h","DOIUrl":"https://doi.org/10.1039/d4py01329h","url":null,"abstract":"Metal based oxo anions remains as one of the major contributor towards fresh water contamination. The bioaccumulation and biomagnification through food chain poses threat to the sustainability of environment. We introduce a novel guanidinium based cationic porous organic polymer which was designed aiming to the fast and efficient removal of permanganate via electrostatic interaction between cationic polymer and the anionic pollutant permanganate. The polymer unveiled exceptionally high uptake of 9.4 g/g for permanganate ions. This is far superior than the existing literature reports. The material exhibited fast sorption kinetics and a removal efficiency of 100 %. Moreover, selectivity, pH and recyclability experiments were also evaluated to confirm the practical applicability of the material. Additionally, we have employed two distinct strategies for the synthesis of guanidinium based cationic porous organic polymer: solvothermal and mechanochemical. Both the polymers were characterized using CPMAS 13C NMR, FT-IR, Powder-XRD, N2 sorption analysis, TGA and FE-SEM. The physicochemical properties of both the polymers were compared. Further, the polymers showed 100 % removal efficiency for permanganate from aqueous solution. Since the mechanochemical method does not involve energy consumption, long time duration or involvement of any toxic organic solvents, the process is environmentally benign and economically viable. Whilst the solvothermal method consumed more energy and time. Hence, mechanochemical method was found to be more efficient, cost-effective and environmentally sustainable method in the fabrication of a highly efficient guanidinium based polymeric adsorbent material for permanganate removal from aqueous solution","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841692","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}

引用次数: 0