Polymer Chemistry最新文献

{"title":"Spiropyran-based supramolecular elastomers with tuneable mechanical properties and switchable dielectric permittivity","authors":"Malte Beccard, Thulasinath Raman Venkatesan, Frank Alain Nüesch, Dorina Opris","doi":"10.1039/d4py00964a","DOIUrl":"https://doi.org/10.1039/d4py00964a","url":null,"abstract":"Silicone elastomers are widely used in various applications, each demanding different properties and functionalities. To be used in such a broad spectrum, silicones with easily tunable or switchable properties are needed. We showed this is achievable with novel metallo-supramolecular polysiloxanes. Poly(dimethylsiloxane-co-3-aminopropylmethylsiloxane) was reacted with an epoxy-modified spiropyran (SP) using ZnCl2 as a catalyst. We have found that the ZnCl2 functions as a catalyst and allows the formation of metallo-supramolecular polymers. The influence of the amount of ZnCl2 used on the thermal and mechanical properties of the synthesized materials was investigated by DSC, tensile test, and DMA. The ability of SP to act not only as a physical cross-linker, but also as a molecular switch was investigated by UV-Vis spectroscopy and dielectric permittivity measurements. It was found that depending on the amount of ZnCl2 used, the dielectric permittivity can either increase or decrease after exposure to UV light. Additionally, the developed materials can be reprocessed similarly to thermoplastic elastomers. Furthermore, their solubility can be manipulated from insoluble in practically any solvent to highly soluble by simply adding ZnCl2.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718443","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":"Photoinitiated thermoset polymerization through controlled release of metathesis catalysts encapsulated in poly(phthalaldehyde)†","authors":"Oleg Davydovich, Josephine Lewis, Mikayla Romero, Julia Deitz, Francesca C'deBaca, Jared M. Schwartz, Anthony C. Engler, Paul A. Kohl, Samuel C. Leguizamon and Brad H. Jones","doi":"10.1039/D4PY00882K","DOIUrl":"10.1039/D4PY00882K","url":null,"abstract":"<p >Photoinitiated polymerization enables spatiotemporal control of reaction conditions and can thereby generate materials with high complexity while consuming minimal energy. Where ring opening metathesis polymerization (ROMP) is concerned, photo-activated processes are typically enabled by chemical inhibition of ruthenium carbenes <em>via</em> the careful design of complexed ligands such that photoactivation can proceed through an isomerization or ligand dissociation event. In this contribution, we have explored a new approach to photoinitiation of ROMP based on physical inhibition through microencapsulation and controlled release of metathesis catalysts. Micron-sized particles of poly(phthalaldehyde) (PPA), catalyst, and photoacid generator were fabricated by spray drying. The particles were dispersed in dicyclopentadiene monomer, after which polymerization was initiated through temperature or UV exposure, both inducing depolymerization of the PPA particles and <em>in situ</em> catalyst release. The monomer/particle dispersions were found to be stable and reproducibly polymerizable with 3 weeks of storage at room temperature. Furthermore, the dispersions can be used for both photo- and thermal-initiated frontal ROMP, yielding a polymerized thermoset of equivalent properties to conventional bulk- and frontally-polymerized analogues. This work will ultimately enable new manufacturing techniques for ROMP-based materials, due to the modular, easily tunable nature of the underlying initiating system and its unparalleled stability.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 90-101"},"PeriodicalIF":4.1,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718895","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":"Effects of crosslink density and plasticizer on thermorheological properties of dissociative guanidine-based covalent adaptable networks†","authors":"Adelle L. Koenig, Kelsey M. Allis, John S. Lehr and Michael B. Larsen","doi":"10.1039/D4PY01124D","DOIUrl":"10.1039/D4PY01124D","url":null,"abstract":"<p >We report the effects of varying crosslink density and plasticizer loading on the thermorheological properties of guanidine-based covalent adaptable networks (CANs). CANs engage in dynamic bond-exchange reactions above <em>T</em><small>_g</small>, resulting in shifts between thermoset-like materials and states capable of flow that can be greatly impacted by network characteristics beyond the exchange reaction itself. The synthesis of guanidine-based CANs by combination of carbodiimide-containing oligomers and various ratios of amine-containing crosslinker molecules and phthalate plasticizer was used to create a library of CANs with varying crosslink density and equal concentrations of guanidine functionalities. Additionally, <em>T</em><small>_g</small> was tuned by modifying plasticizer loading. CANs at three degrees of crosslink density and three degrees of plasticizer loading were characterized by rheometry and dynamic mechanical analysis. The resulting data indicated that absolute relaxation times varied directly with crosslink density but were largely unaffected by plasticizer content or temperature relative to <em>T</em><small>_g</small>; thus, plasticizer served to decouple <em>T</em><small>_g</small> from relaxation dynamics. Moreover, little difference in activation energies was observed between each system, contrasting studies of associative CANs.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 52-61"},"PeriodicalIF":4.1,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142712578","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":"Fast, catalyst-free room temperature production of isocyanate-free polyurethane foams using aromatic thiols","authors":"Maxime Bourguignon, Bruno Grignard, Christophe Detrembleur","doi":"10.1039/d4py00971a","DOIUrl":"https://doi.org/10.1039/d4py00971a","url":null,"abstract":"Non-isocyanate polyurethane (NIPU) foams of the polyhydroxyurethane (PHU)-type are promising greener alternatives to their conventional isocyanate-based polyurethane counterparts that dominate the foam market. Recently, the concomitant organocatalyzed aminolysis and S-alkylation of the cyclic carbonates of PHU formulations offered a facile way to produce CO2 self-blown PHU foams. However, this process was limited to the production of foams of rather low Tg (commonly up to room temperature) and suffered from a slow foaming (i.e. 30 min.) at 120 °C, thus still far away from the foaming timeframes (1-10 min) and room temperature (r.T.) needed for adaptation on industrial foaming equipment’s. In this work, we elaborate strategies to accelerate the thiol-assisted NIPU foaming in order to be complete in 5 to 10 minutes from r.T. reactive formulations under catalyst-free conditions. This is achieved by substituting aliphatic thiols by more acidic aromatic ones, and by adding epoxides as heat release promotors that will accelerate both the foaming and curing rates. Moreover, flexible, semi-rigid and rigid foams are easily accessible by the choice of the amine comonomer and epoxide additive. This work draws general and simple concepts for strongly speeding-up the self-blowing NIPU process, a crucial step toward decreasing the energetic and production costs, offering potential retrofitting of existing foam production plants.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142712866","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":"A triple hydrogen-bond dominated fluorescent probe for monitoring the melting transition of polyurethane","authors":"Yuanyuan Guo, Geng Li, Hongyu Jiang, Yaxing Tang, Hua Wang, Jie Li, Kunpeng Guo","doi":"10.1039/d4py00597j","DOIUrl":"https://doi.org/10.1039/d4py00597j","url":null,"abstract":"Accurately characterizing the phase transition temperatures of polyurethanes (PU) is indispensable in controlling over the material processing and usage conditions yet challenging. Herein, a DDA-AAD-type triple hydrogen-bonded luminescent complex was developed based on 7-methyl-1,8-naphthyridin-2-amine (D-Ny) and 1,3-dipyridin-2-ylurea (A-Py) to serve as a novel fluorescent probe for monitoring the melting transition of PU. The complex exhibited thermoreponsive luminescence in THF, with inflection in fluorescence intensity at the melting temperature of the solvent. Taking advantage of the specific luminescence response to the phase transition of the matrix, the triple H-bonding groups were chemically bonded into a polyurethane (PU) backbone as the dynamic chain extenders. The melting transition of the soft and hard segments were demonstrated respectively in real time in the temperature-dependent PL spectra of the fluorescent probe, offering higher sensitivity than the signal in DSC curve in determining the melting temperature of the hard segment. This study provides a prospective approach to monitor the melting transition of PU using a dynamic temperature-sensitive fluorescent probe.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696953","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":"Improved thermal properties of polydimethylsiloxane by copolymerization and thiol–ene crosslinking of 2-pyrone-4,6-dicarboxylic acid moiety†","authors":"Takahiro Shimura, Yijie Jin, Keiichi Kubyama, Takuma Araki, Naofumi Kamimura, Eiji Masai, Masaya Nakamura and Tsuyoshi Michinobu","doi":"10.1039/D4PY01051E","DOIUrl":"10.1039/D4PY01051E","url":null,"abstract":"<p >Recent environmental issues, such as global warming and climate change, have prompted a shift from petroleum-derived polymers to biomass polymers. We have developed new lignin-derived biomass polymers based on 2-pyrone-4,6-dicarboxylic acid (PDC), a metabolic intermediate of lignin. In previous studies, various polymers have been synthesized using PDC. Many of them showed strong adhesion to metal surfaces and biodegradability. On the other hand, despite the quasi-aromatic ring structure of PDC, its heat resistance remained unresolved. In this study, a diallyl PDC derivative was synthesized and copolymerized with polydimethylsiloxane (PDMS) by Pt-catalyzed hydrosilylation. The resulting polymers were further cross-linked using the PDC ring as the cross-linking point by using thiol–ene click chemistry. It was found that the heat resistance of PDMS was significantly improved by polymerization and cross-linking. By using biomass-based PDC, silicone rubber with low environmental impact, excellent heat resistance, and mechanical strength was successfully developed.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 45-51"},"PeriodicalIF":4.1,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01051e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrogels constructed by multicomponent reactions","authors":"Siyu Pan, Chongyu Zhu and Lei Tao","doi":"10.1039/D4PY00885E","DOIUrl":"10.1039/D4PY00885E","url":null,"abstract":"<p >Hydrogels have been widely used in many fields. To meet the application requirements of different fields, hydrogels with different functions have been developed through efficient organic reactions. Multicomponent reactions (MCRs) have been used as distinct tools in hydrogel preparation, owing to their high efficiency, mild reaction conditions and tolerance for various functional groups. In this mini-review, we present a comprehensive overview of the roles of MCRs as crosslinking reactions and as functional group introducers in hydrogel construction. Finally, we will discuss the future perspectives of MCRs in exploring (multi)functional hydrogels.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4799-4809"},"PeriodicalIF":4.1,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696954","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":"Effect of molar mass of poly(2-oxazoline) based glycopolymers on lectin binding†","authors":"Caitlin L. A. Nutting, James Lefley, Zivani Varanaraja, Gokhan Yilmaz and C. Remzi Becer","doi":"10.1039/D4PY01135J","DOIUrl":"10.1039/D4PY01135J","url":null,"abstract":"<p >Glycopolymers are a versatile polymer type employed in many applications, especially the biomedical field, due to their ability to exploit multivalent lectin–carbohydrate interactions. Understanding how to improve and manipulate the interactions between glycopolymers and lectins is crucial for their success within the pharmaceutical industry. Herein, we synthesised block copolymers <em>via</em> cationic ring opening polymerisation of 2-ethyl-2-oxazoline and 2-(3-butenyl-2-oxazoline) with varying quantities of 2-ethyl-2-oxazoline. These polymers were further functionalised with pendent glucose moieties to produce glycopolymers. All polymers and glycopolymers were analysed using a variety of techniques including NMR, GPC, FT-IR and MALDI-ToF MS. Their binding capabilities were evaluated by surface plasmon resonance, utilising human lectins: DC-SIGN, MBL and Langerin, to investigate how the molar mass influences lectin binding.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 5023-5031"},"PeriodicalIF":4.1,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py01135j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of counterions on the thermal and solution properties of strong polyelectrolytes†","authors":"Théophile Pelras, Julien Es Sayed, Jin Pierik, Andrea Giuntoli, Anton H. Hofman, Katja Loos and Marleen Kamperman","doi":"10.1039/D4PY01218F","DOIUrl":"10.1039/D4PY01218F","url":null,"abstract":"<p >Strong polyelectrolytes (<em>i.e.</em>, macromolecules whose charge density is independent of the medium's pH) are invaluable assets in the soft matter toolbox, as they can readily disperse in aqueous media, complex to oppositely charged species – polymers and small molecules alike – and can be implemented in a plethora of applications, ranging from surface modification to chelating agents and lubricants. However, the direct synthesis of strong polyelectrolytes in a controlled fashion remains a challenging endeavour, and their in-depth characterisation is often limited. Additionally, producing a set of charged macromolecules with the same chain length but varying counterions would open doors towards a fine control of the polymer's chemistry and physical properties. Unfortunately, this either necessitates the direct polymerisation of several monomers with potentially varying reactivities, or a time-consuming ion exchange from a single batch. Herein we explore the facile and efficient production of strong polyanions through the deprotection of a poly(3-isobutoxysulphopropyl methacrylate) using a range of inorganic and organic iodide-containing salts. Owing to the contrasting nature of their counterions, the resulting polyanions exhibit a wide range of glass transition temperatures, which follow a non-monotonic trend with increasing counterion size. While all polymers readily dissolve in water, some can also be dissolved in non-aqueous media as well. This strategy, applied to block copolymers, permits the production of a library of amphiphilic macromolecules with consistent hydrophilic and hydrophobic blocks, yet varying nature of their polyanionic segments. All amphiphiles, regardless of their counterions, readily disperse in aqueous media and form well-defined micelles featuring a hydrophobic core and a charged hydrophilic shell, as evidenced by dynamic light scattering, <em>ζ</em>-potential and transmission electron microscopy. Additionally, a handful of block copolymers are capable of yielding polymer micelles in organic solvents, opening an avenue to the build-up of nanostructured soft matter in non-aqueous media.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 69-81"},"PeriodicalIF":4.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01218f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"From Industrial By-Products to High-Value Materials: Synthesizing Sulfur-Rich Polymers for Lithium-Sulfur Battery Cathodes from C5 Fraction and Sulfur","authors":"Xingwei Xun, Jinhong Jia, Xi-Cun Wang, Xiaofeng Wu, Zheng-Jun Quan","doi":"10.1039/d4py00980k","DOIUrl":"https://doi.org/10.1039/d4py00980k","url":null,"abstract":"The dispersion and waste of petroleum resources reduce resource utilization efficiency and exacerbate environmental pollution. Therefore, optimizing resource management and improving recycling efficiency are crucial. Developing organic polysulfides through inverse vulcanization represents a novel strategy for constructing sustainable and versatile materials and comprehensively utilizing petrochemical resources. This study employs inverse vulcanization with C5 fraction, a by-product of the ethylene industry, to successfully polymerize with sulfur, resulting in a polymer material that exhibits good thermal stability and electrochemical activity. The chemical properties of the polymer were elucidated through a comprehensive array of analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and spherical aberration-corrected transmission electron microscopy (AC-TEM). As a cathode material for lithium-sulfur batteries, this polymer exhibited strong specific discharge capacity, cycling stability, and rate performance. In conclusion, these materials, derived from inexpensive and abundant by-products, provide valuable design principles for the efficient utilization of petrochemical resources.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684847","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}