Yuka Azuma, Riku Takahashi, Natsuko Sashi, Kan Hatakeyama-Sato, Yuta Nabae, Ririka Sawada, Shinji Ando, Teruaki Hayakawa
{"title":"Hydrosilylation-Derived Silicon-Containing Hydrocarbon-Based Polymers Exhibiting Ultralow Dielectric Losses and High Thermal Stabilities","authors":"Yuka Azuma, Riku Takahashi, Natsuko Sashi, Kan Hatakeyama-Sato, Yuta Nabae, Ririka Sawada, Shinji Ando, Teruaki Hayakawa","doi":"10.1039/d5py00431d","DOIUrl":"https://doi.org/10.1039/d5py00431d","url":null,"abstract":"With the continual evolution of high-frequency communication technologies, the demand for advanced insulating materials with minimal dielectric losses has become increasingly critical. In this work, Si-containing hydrocarbon-based polymers are prepared via a hydrosilylation polymerization reaction between dihydrosilanes and diynes or dienes, which are strategically engineered to achieve both a low dielectric constant (Dk) and an exceptionally low dielectric loss tangent (Df). This polymerization method proceeded efficiently under mild conditions, yielding high-purity polymers without by-product formation. The resulting materials exhibited outstanding dielectric properties, with Dk values of ~2.6 and Df values <0.002 at 20 GHz, the latter of which reached as low as 0.0011 in optimized systems. Notably, these favorable characteristics were maintained even at frequencies exceeding 75 GHz. Thermogravimetric analysis confirmed excellent thermal stabilities, with decomposition temperatures (Td-10) surpassing 400°C. Moreover, the polymers displayed good solubilities in a wide range of organic solvents (excluding alcohols), indicating their practical processability. Collectively, these results demonstrate the potential of the synthesized materials for use as next-generation interlayer dielectrics for high-speed communication applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701780","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}
Qifeng Jiang, Marissa Coschigano, Braden A. Mediavilla, Alexandra Gittens, Sophia J. Melvin, Rebekka S. Klausen
{"title":"Stereogenic-at-Silicon Hybrid Conjugated Polymers","authors":"Qifeng Jiang, Marissa Coschigano, Braden A. Mediavilla, Alexandra Gittens, Sophia J. Melvin, Rebekka S. Klausen","doi":"10.1039/d5py00405e","DOIUrl":"https://doi.org/10.1039/d5py00405e","url":null,"abstract":"Stereoregularity in carbon-based polymers impacts critical physical properties such as crystallinity, but achieving comparable precision in polysilanes remains challenging. Herein, we report the synthesis of hybrid σ,π-conjugated polysilanes with defined stereoregularity, derived from cis- and trans-cyclosilane building blocks. Using Kumada polycondensation, we accessed a series of atactic, trans-enriched, and cis-enriched polysilanes, enabling a systematic investigation of how tacticity influences thermal and optical properties. Differential scanning calorimetry revealed distinct glass transition behaviors for stereoregular polymers compared to their atactic counterpart, and UV-vis spectroscopy demonstrated enhanced spectral resolution upon annealing of stereoregular films. A linear silane-based analog further underscored the structural impact of cyclic stereogenic units. These findings highlight how stereochemical precision in silicon-containing backbones can modulate macromolecular properties, opening avenues for the rational design of stereoregular polysilanes.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"122 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701731","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}
Mahesh Prasad Timilsina, Melissa K. Stanfield, Jason Smith, Stuart C. Thickett
{"title":"Expanding the chemical functionality of levoglucosenone-based monomers for degradable thiol-ene thermosets with high bio-derived content","authors":"Mahesh Prasad Timilsina, Melissa K. Stanfield, Jason Smith, Stuart C. Thickett","doi":"10.1039/d5py00339c","DOIUrl":"https://doi.org/10.1039/d5py00339c","url":null,"abstract":"Levoglucosenol, the reduced form of levoglucosenone (LGO), was utilized in this work to synthesize seven novel monomers bearing both pendant alkene functional groups and the inherent internal double bond of the bicyclic LGO structure. Monomers possessing ester, carbonate and carbamate linkers were prepared with a specific focus on developing compounds with a high fraction of bio-derived carbon, which was achieved using fatty acids (oleic and linoleic acid) and plant-based acids (citronellic and 10-undecenoic acid). The monomers were cured via ultraviolet (UV)-initiated radical thiol-ene “click” chemistry with commercially available multifunctional thiols generating optically transparent cross-linked thermosets in typically less than 60 seconds, and which possessed tuneable thermal and mechanical properties. Thermogravimetric analysis revealed that most polymers were stable up to 300 °C, with glass transition temperatures ranging from 0.3 to 37.4 °C and tensile strength values varying from 0.5 to 54.0 MPa, depending on the nature of the structure of the LGO-based monomer. The hydrolytic degradation of these thermosets via ester hydrolysis was demonstrated in an alkaline medium, the rate of which could be controlled by the length of the monomer side chain and nature of the linker unit.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"56 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701734","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":"Polymeric toroidal assemblies from ionic homopolymers with shackling photo-responsive behavior","authors":"Qingqing Yang, Junjun Lv, Jinye Wang, Wei Song, Liang Ding","doi":"10.1039/d5py00586h","DOIUrl":"https://doi.org/10.1039/d5py00586h","url":null,"abstract":"The uniformity and tunable ring size of toroidal nanostructures are promising in many fields but still challenging. Herein, polyolefin-based homopolymers with pyridinium cation junctions between the main chain parts and alkyl azobenzene pendants were systematically synthesized and further self-assembled into preformed spheres based on the multiple effects of solvophobic backbone, electrostatic force and strong non-covalent aromatic–aromatic interaction. Subsequently, UV-light-triggered shackling <em>trans</em>→<em>cis</em> photoisomerization transition was demonstrated, meanwhile, the uniform toroids with stable shape and adjustable dimension were observed after continuously irradiating UV-light and eventually reaching the photostationary state. The mechanistic investigation further confirmed that the strong non-covalent interaction generated during the significantly confined photoisomerization process is essential for the formation of polymeric toroid. Importantly, the toroidal morphology is insusceptible to the used solvent system, but the ring size can be optionally adjusted from nanoscale to microscale. We expect that the importance of regulation multiple non-covalent interactions in reinforcing each other will offer a new avenue to induce self-assembly of homopolymer to produce the uniform and particular morphology.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"214 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694130","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}
Cornelis Post, Dina Maniar, Rudy Folkersma, Vincent Voet, Katja Loos
{"title":"Panoramic View of Biobased BHMTHF-based Polymers","authors":"Cornelis Post, Dina Maniar, Rudy Folkersma, Vincent Voet, Katja Loos","doi":"10.1039/d5py00544b","DOIUrl":"https://doi.org/10.1039/d5py00544b","url":null,"abstract":"The biobased platform chemical 5-hydroxymethylfurfural (HMF) is widely recognized as an important precursor for the production of the monomer 2,5-furandicarboxylic acid (FDCA) and, to a lesser extent, 2,5-bishydroxymethyl furan (BHMF), which are used for the production of renewable polymers. Like FDCA and BHMF, 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) can be synthesized from HMF and can act as a monomer due to its difunctionality. The potential of BHMTHF, also known as 2,5-tetrahydrofurandimethanol (THFDM), for use in the production of innovative biobased polymers is still underexplored. This review summarizes and highlights the different types of polyesters and polyurethanes that are derived from this tetrahydrofuran building block. BHMTHF is predicted to have a bright future as a biobased monomer for the production of sustainable polymers because of its unique heterocyclic rigidity, electronegativity of the ether group and hydrogen bonding ability. This yields various polymers with reduced or absent crystallinity, improved hydrophilicity and pronounced shear thinning behavior.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685008","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":"Outstanding Reviewers for Polymer Chemistry in 2024","authors":"","doi":"10.1039/d5py90087e","DOIUrl":"https://doi.org/10.1039/d5py90087e","url":null,"abstract":"We would like to take this opportunity to thank all of <em>Polymer Chemistry</em>'s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>Polymer Chemistry</em> in 2024.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"76 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670029","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}
Sudhir Ravula, Kevin Wise, Lyndi Strange, Zihua Zhu, Jenn Yao, Pravin S. Shinde, David J Heldebrant, Jason Edward Bara
{"title":"Tailoring Tetracationic Linkers to Improve the Physical and CO2 Gas Separation Properties of Doubly Segmented PEEK-Ionene + Ionic Liquid Composites","authors":"Sudhir Ravula, Kevin Wise, Lyndi Strange, Zihua Zhu, Jenn Yao, Pravin S. Shinde, David J Heldebrant, Jason Edward Bara","doi":"10.1039/d5py00467e","DOIUrl":"https://doi.org/10.1039/d5py00467e","url":null,"abstract":"A series of doubly segmented (DS) poly(ether ether ketone)-ionenes (PEEK-ionenes) was synthesized through polycondensation via Menshutkin reaction, followed by bistriflimide [Tf2N]– anion-exchange. These newly designed tetracationic 2-methylimidazolium (C(2)-Me) linker groups employ a sequence of aromatic (p-xylyl) and aliphatic (hexylene) linkages between cations. The synthesized DS PEEK-ionenes exhibit good solubility in common organic solvents at room temperature, high number average molecular weights ranging from 123 to 159 kDa, and thermal stability up to 410 °C, which are improved compared to counterparts with C(2)-H imidazolium cations. The flexibility of the membranes depends on both the amount of free ionic liquid (IL) added to the PEEK-ionene materials and the characteristic features of the linker groups. The structure-property relationships within the series were established by comprehensively studying the physical properties and gas separation performances. All the newly developed PEEK-ionenes + IL composites have moderate CO2 permeability up to 73 barrer, and the separation performance approaches the 1991 and 2008 upper-bound for O2/N2 and CO2/H2, respectively, and with moderate selectivities for CO2/N2 and CO2/CH4. The elongated charged moieties per segment and introduction of C(2)-Me are key factors for finely tuning and maximizing the separation performance of designed materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"663 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144670028","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":"Elemental sulfur utilization: Construction of a reprocessable covalent crosslinked polydisulfide with enhanced mechanical properties","authors":"Ji-Yan Chao, Tian-Jun Yue, Xiaobing Lu, Wei-Min Ren","doi":"10.1039/d5py00085h","DOIUrl":"https://doi.org/10.1039/d5py00085h","url":null,"abstract":"Herein, a polydisulfide with uniformly distributed aldehyde groups was prepared through the terpolymerization of an aldehyde-containing episulfide, 2-(phenoxymethyl)thiirane, and elemental sulfur. A thermoset polydisulfide with a crosslinking network was constructed by leveraging the Schiff base reaction between amines and aldehyde groups. Compared to the linear polymers, the crosslinked polydisulfide exhibited a 2–10 °C increase in its glass transition temperature. In addition, the covalent crosslinking network enhanced the mechanical properties of the polydisulfide compared to those of the original linear polymer, and the mechanical properties could be modulated by adjusting the crosslinking density of the polymer. Moreover, the polymer exhibited processability and shape-memory properties when heated to a specific temperature.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664613","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":"Functional Fluoropolymers with Good Low-dielectric Properties and High Thermostability","authors":"Maowei Yang, Jiaren Hou, Zhiqiang Wang, Xiao Wu, Xiao Peng Sun, Qixin Zhuang, Jing Sun, Qiang Fang","doi":"10.1039/d5py00524h","DOIUrl":"https://doi.org/10.1039/d5py00524h","url":null,"abstract":"Fluoropolymers can be utilized as dielectric substrates to ensure signal transmission speed and quality in modern communication technology. However, conventional fluoropolymer materials such as polytetrafluoroethylene (PTFE) are constrained by limited thermal stability and inferior processability. In this paper, two monomers (<strong>DBA-FBCB</strong> and <strong>DBAF-FBCB</strong>) based on benzocyclobutene and fluorobenzene groups have been successfully synthesized via effective C-H bond activation and nucleophilic aromatic substitution reactions. The monomers were thermally cross-linked to fluoropolymers (p-DBA-FBCB and p-DBAF-FBCB). Those polymers exhibited superior thermal stability with a glass transition temperature (<em>T</em><small><sub>g</sub></small>) > 370 ℃, a 5% weight loss temperature (<em>T</em><small><sub>5d</sub></small>) higher than 430 ℃, and low coefficient of thermal expansion (CTE) of 60.9 ppm /℃ from 35 ℃ to 250 ℃. p-DBAF-FBCB displayed excellent dielectric properties with a low dielectric constant (<em>D</em><small><sub>k</sub></small>) of 2.51 and dielectric loss factor (tanδ) of 2.41×10<small><sup>-3</sup></small> at a high frequency of 5 GHz, as well as an average <em>D</em><small><sub>k</sub></small> of 2.45 with an average tanδ of 1.5×10<small><sup>-3</sup></small> at the frequency from 1 to 10 MHz. The results demonstrate that those fluoropolymers are promising candidates for low-dielectric substrates or packaging materials in high-frequency communications or microelectronics industries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664617","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":"Immunostimulatory pH-responsive Nanogels Derived from Poly(oxanorbornene) Precursor Polymers","authors":"Johannes Kockelmann, Lutz Nuhn","doi":"10.1039/d5py00542f","DOIUrl":"https://doi.org/10.1039/d5py00542f","url":null,"abstract":"Ring Opening Metathesis Polymerization (ROMP) provides access to well-defined poly(oxanorbornene) block copolymers that can be converted into micellar-derived immunoactive nanogels. We report on the synthesis of such immunoactive nanogels based on oxanorbornene-derived post-polymerization modification strategy. The key precursor, an oxanorbornene pentafluorophenyl ester (ONB-PFP) monomer, was synthesized and polymerized using living ring-opening metathesis polymerization (ROMP) facilitated by a third-generation Grubbs catalyst (G3) for efficient living-type block copolymerization. This approach yielded well-defined block copolymers by incorporating an active ester monomer with a hydrophilic triethylene glycol-functionalized oxanorbornene, establishing a robust platform for subsequent post-polymerization modifications. Nanogels were formed by aqueous self-assembly of the block copolymers, with various crosslinking agents employed to generate both acid-labile (D-NG) and non-degradable (ND-NG) nanogels, while without crosslinkers fully hydrophilic single polymer chains were obtained as controls. The covalent attachment of the Toll-like receptor 7/8 agonist IMDQ, an immunomodulatory imidazoquinoline agent, to the nanogels produced immunoactive nanogels, whose immunostimulatory efficacy was evaluated in vitro using a RAW-Blue macrophage reporter cell line. Flow cytometry confirmed efficient cellular uptake of only the intact nanogels by the macrophages resulting in a receptor activation and thus providing a strategy to safely control the delivery of the highly potent TLR7/8 agonist.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"95 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652649","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}