Polymer Chemistry最新文献

{"title":"Insights into the bulk kinetics of a 2K radical polymerization system based on the copper catalyzed cleavage of diboranes and its perspectives","authors":"F. Pieringer, Y. Catel, R. Liska, P. Knaack","doi":"10.1039/d4py01102c","DOIUrl":"https://doi.org/10.1039/d4py01102c","url":null,"abstract":"Many applications of polymer materials, such as adhesives, require a polymerization process at room temperature and ambient atmosphere. In those cases, two-component (2K) systems based on redox initiation truly stand out due to their reliable performance. Herein, we present a deep insight into the polymerization kinetics of a newly developed initiation system based on the copper catalyzed cleavage of diborane compounds, followed by rheology coupled with NIR. The analysis of different diboranes led us to further investigate the diborane concentration dependency and the effects on gel time that can be observed. Furthermore, it is shown that the diborane/Cu system yields polymers with high molecular weight at high double bond conversions. In addition, the perspectives of diborane/Cu initiation for radical polymerization are presented, as various different monomer classes showed excellent reactivity towards polymerization, enabling the great potential of this initiation system for various applications in polymer chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"142 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815627","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":"Association of Zn- and Mg-based Chain Transfer Agents in Coordinative Chain Transfer Polymerizations of Olefins for Enhanced Control and Activity","authors":"Ariane Desgranges, Ludmilla Verrieux, Victor Lancenet, Nicolas Baulu, François Jean-Baptiste-dit-Dominique, Robert Ngo, Franck D'Agosto, Marie-Eve L. Perrin, Christophe Boisson","doi":"10.1039/d4py01220h","DOIUrl":"https://doi.org/10.1039/d4py01220h","url":null,"abstract":"Based on DFT-level computational studies, ZnEt₂ was implemented as a chain transfer agent (CTA) to promote the coordinative chain transfer (co)polymerization of ethylene for the first time with a metallocene complex of Nd. The use of ZnEt₂ in combination with Mg(nBu)1.5(nOct)0.5 compared to the use of Mg(nBu)1.5(nOct)0.5 alone, improves several key aspects of the polymerization process. When ethylene is polymerized, an increase of catalytic activities is observed and narrower molar mass distributions are obtained due to reduced β-H transfer and faster reversible chain transfer reactions. In copolymerization of ethylene with butadiene, the presence of ZnEt₂ has no impact on the polymerization process in terms of polymerization kinetics and microstructure of the final copolymer. Nevertheless, it acts as an excellent CTA. Using ZnEt₂ in combination with MesMgBr rather than Mg(nBu)1.5(nOct)0.5 enables selective chain transfer between neodymium and zinc and promotes a nearly quantitative chain-end functionalization with acyl chloride.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809508","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":"Modulating packing and photovoltaic performance of (bisthiophene)benzene-linked polymer acceptors through simple methylation engineering","authors":"Ruiqi An, Mengqi Cao, Hongxiang Li, Zhongxiang Peng, Xiaofu Wu, Hui Tong, Lixiang Wang","doi":"10.1039/d4py01235f","DOIUrl":"https://doi.org/10.1039/d4py01235f","url":null,"abstract":"Three polymerized small molecular acceptors (PSMAs), namely PY-TP, PY-TPMe2, and PY-TPMe4, were designed and synthesized by employing (bisthiophene)benzene linkers containing various methyl-substituted phenylene groups. All the PSMAs exhibit similar absorption maxima in films as well as LUMO energy levels. However, the increased number of methyl groups on the linkers induces steric hindrance and decreases the coplanarity of the polymer backbones, which, in turn, increases intermolecular π-π stacking distances. When three acceptors are blended with a classical polymer donor PM6, PY-TPMe4 with the highly twisted backbone has a large π-π stacking distance and excessive phase separation, whereas PY-TP and PY-TPMe2 with moderately twisted backbones demonstrate more compact π-π stacking and suitable phase separation morphology. As a result, PY-TP and PY-TPMe2 exhibit better exciton dissociation and charge transport, leading to much higher photovoltaic performance compared to PY-TPMe4. Particularly, PY-TPMe2 effectively regulates the crystallinity and achieves a more suitable phase separation morphology in the blend films. The optimal PY-TPMe2-based photovoltaic device exhibits the best exciton dissociation and charge transport performance, achieving the highest power conversion efficiency (PCE) of 8.4% among the devices based on the three PSMAs, with a high open-circuit voltage (VOC) of 0.97 V, a short-circuit current density (JSC) of 14.74 mA cm⁻² and a fill factor (FF) of 59.65%. These findings provide new insights into the regulation of the molecular packing and photovoltaic performance of polymer acceptors through simple methylated modification on linkers for designing novel PSMAs materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"77 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804769","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":"Tunable circularly polarized luminescence of D-A type chiral conjugated oligomers via achiral donors","authors":"Yuxiang Wang, Yabin Feng, Qian Wang, Qi Meng","doi":"10.1039/d4py01192a","DOIUrl":"https://doi.org/10.1039/d4py01192a","url":null,"abstract":"Chiral conjugated oligomers with circularly polarized luminescence (CPL) have received great interest and been extensively researched. However, chiral conjugated oligomers with donor-acceptor (D-A) structures are poorly developed. In this paper, a series of D-A type chiral conjugated oligomers were synthesized by the copolymerization of axially chiral acceptors and achiral donors through Pd-catalyzed Buchwald-Hartwig C-N coupling reactions. The resulting chiral conjugated oligomers exhibit donor dependent fluorescence in solution with emission wavelength ranging from 500 to 574 nm and photoluminescence quantum yields (ФPL) up to 49%, which can be attributed to ICT transition derived from the D-A oligomer backbone. Obvious CPL response signals can be detected for the chiral conjugated oligomers with luminescence dissymmetry factors (glum) up to 1.3 × 10-3, which can be tuned via the variation of achiral donors. This work can provide a novel strategy for the design of chiral conjugated polymers or oligomers with D-A structure and tunable CPL signals.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804770","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 Potential Biobased Thermoplastic Elastomer based on β-Myrcene via RAFT-mediated Miniemulsion Polymerization","authors":"Uddhab Kalita, Sarthik Samanta, Bhoje Gowd, Narayan Chandra Das, Nikhil K. Singha","doi":"10.1039/d4py01182a","DOIUrl":"https://doi.org/10.1039/d4py01182a","url":null,"abstract":"In recent times, there has been an increasing focus on utilizing bioresources in polymer synthesis owing to their numerous advantages over petroleum-based polymers. Among the various types of polymers, thermoplastic elastomers (TPEs) have garnered considerable interest due to their ease of processing and ability to be recycled and reused. β-Myrcene (MY), a terpene compound, is a crucial substituted-diene monomer with a backbone comprising a conjugated diene, resembling the isoprene unit found in natural rubber. MY can be sourced from various bioresources. In this study, the reversible addition-fragmentation chain-transfer (RAFT) polymerization was used to prepare a new ABA-type triblock copolymer named poly(isobornyl methacrylate)-b-poly(β-myrcene)-b-poly(isobornyl methacrylate) (IMI). In this fully bio-derived triblock copolymer, poly(isobornyl methacrylate) (PIBMA) and poly(β-myrcene) (PMY) act as the hard block and the soft block, respectively. Initially, IBMA was polymerized using S,S-dibenzyl trithiocarbonate, a bifunctional RAFT agent. Subsequently, the obtained PIBMA served as a macro-RAFT agent for the miniemulsion polymerization of MY, resulting in the formation of the IMI triblock copolymers. The successful synthesis of the block copolymers (BCPs), their composition, and molecular weight were confirmed through FTIR, NMR, and GPC analyses. Additional investigation employing AFM in combination with DSC unveiled the phase-separated morphology of the rigid and flexible domains attributed to PIBMA and PMY, respectively. The IMI BCPs exhibited favorable tensile properties, with their scraps demonstrating effective reprocessiblity and reuse, underscoring their potential as sustainable TPE materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804999","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":"Symmetric star poly(substituted glycolide) homopolymers and their surface properties","authors":"Yonca Çolak, Sema Nur Belen, Duygu Çetin, Ugur Cengiz, Olcay Mert","doi":"10.1039/d4py01229a","DOIUrl":"https://doi.org/10.1039/d4py01229a","url":null,"abstract":"Well-defined star poly(substituted glycolide) (s-PSG) homopolymers with predetermined lengths and numbers of arms, which are alternatives to polylactides and polyglycolides, may offer great opportunity for the modulation of their physical properties, such as glass transition temperature (<em>T</em><small>_g</small>), crystallinity, hydrophobicity, and surface characteristics due to their geometric and structural differences. Herein, we report the synthesis of s-PSG homopolymers, including a four-armed symmetrical poly(<small>L</small>-diisopropyl glycolide) (4s-PLDIPG) and poly(<small>L</small>-diisobutyl glycolide) (4s-PLDIBG) from the ring opening polymerization (ROP) of their monomers in the presence of tin(<small>II</small>) 2-ethylhexanoate [Sn(Oct)<small>₂</small>] as a catalyst and pentaerythritol as an initiator <em>via</em> a core-first approach under melt conditions. 4s-PLDIPG <strong>8</strong> exhibits lower <em>T</em><small>_g</small>, melting temperature (<em>T</em><small>_m</small>) and crystallinity % than 4s-PLDIPG <strong>10</strong> (<em>T</em><small>_g</small>: 33.7 °C <em>vs</em>. 35.9 °C; <em>T</em><small>_m</small>: 143.9 °C <em>vs</em>. 183.4 °C; <em>X</em><small>_c</small>: 16.7% <em>vs</em>. 19.1%) due to its lower <em>M</em><small>_n</small> per arm. 4s-PLDIPG <strong>8</strong> also has a dramatically lower <em>T</em><small>_m</small> and crystallinity % than its linear counterpart PLDIPG <strong>17</strong> (<em>T</em><small>_m</small>: 143.9 °C <em>vs</em>. 190.6 °C; <em>X</em><small>_c</small>: 16.7% <em>vs</em>. 26.7%) due to its short arm length. As the side chain length of s-PSG homopolymers increased, there was a corresponding increase in the water contact angles and surface roughness values of the thin films, while the surface free energy decreased. This correlation between side chain length and surface properties was further validated by SEM and AFM profiles, which confirmed the impact of extended side chains on the polymer's surface characteristics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797569","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":"The carbonate exchange reaction strategy for chemical recycling of poly(bisphenol A carbonate) into epoxy-curing agent","authors":"Zengping Peng, Haoyue Chen, Maoqing Chai, Rulin Yang, Guangqiang Xu, Hongguang Sun, Qinggang Wang","doi":"10.1039/d4py01175a","DOIUrl":"https://doi.org/10.1039/d4py01175a","url":null,"abstract":"Using chemical methods to depolymerize or convert plastic materials for recycling is a useful process to achieve the sustainable and circular plastic economy. Herein, different from conventional chemical methodologies to convert waste plastics into monomers or high value-added chemicals, a “waste polymer to precursor of polymer to new polymer” protocol was proposed. For the chemical recycling of poly(bisphenol A carbonate) (BPA-PC), a novel carbonate exchange strategy was explored, in which BPA-PC was depolymerized into the “DPC-PC” via diphenyl carbonate (DPC) mediated carbonate exchange reaction. The unique structure enables DPC-PC to serve as a curing agent for preparing high-performance and recyclable epoxy thermoset, thus blazing a new trail for the chemical recycling of BPA-PC.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797570","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":"Gelation-free synthesis of high-molecular-weight hyperbranched aromatic polymers containing silicon by Suzuki-Miyaura polycondensation of tri- or tetra(bromoaryl)silane with arylenediboronate","authors":"Ryusuke Shimada, Masato Kubota, Yoshihiro Ohta, Tsutomu Yokozawa","doi":"10.1039/d4py01024h","DOIUrl":"https://doi.org/10.1039/d4py01024h","url":null,"abstract":"Suzuki-Miyaura polycondensation of tri- or tetra(bromoarylsilane) 1 with arylenediboronic acid (ester) 4 in the presence of tBu3PPd precatalyst 3 was investigated for the synthesis of silicon-containing hyperbranched aromatic polymers by means of simple A2 + Bx (x = 3, 4) polycondensation without gelation. The key reaction in this polycondensation, successive substitution of 1 with 4 through intramolecular Pd catalyst transfer on the silyl group and π-face of 1, was investigated by means of model reactions of 1 with a variety of arylboronates 2 in the presence of 3 at room temperature. The Suzuki-Miyaura reaction of tri(bromophenyl)silane 1a, tri(bromofluorenyl)silane 1b, and tetra(bromophenyl)silane 1c with phenylboronic acid and carbazoleboronate yielded exclusively tri- and tetrasubstituted products, even though the bromine sites in 1 were present in excess relative to the boronic acid (ester) sites in 2. The polycondensation of 1a with phenylenediboronate 4a, fluorenylenediboronate 4b, thienylenediboronate 4c, and carbazolylenediboronate 4d afforded high-molecular-weight silicon-containing aromatic hyperbranched polymers without gelation. The use of 1c instead of 1a resulted in the formation of some polymers with low solubility, but the polycondensations of 1c with phenylenediboronic acid 4a’ having a branched side chain and with 4b yielded the corresponding high-molecular-weight polymers. In the polycondensation of 1b with 4, 4a afforded a moderate-molecular-weight polymer (Mn = 7610), whereas 4b-d yielded polymers with Mn = 64700-80700. It turned out that donor and/or extensively conjugated compounds 4 were particularly effective for the Suzuki-Miyaura polycondensation of extensively conjugated tribromide 1b. The UV-vis absorption and emission spectra in solution of the silicon-containing hyperbranched polyphenylenes, obtained by the polycondensation of 1a or 1c with 4a, were similar to those of hyperbranched polyphenylene with no silicon (HBPP), whereas the fluorescence quantum yields were considerably higher (50-53%) than that of HBPP (16%).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793725","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 macromonomer chemical structure on the rate of grafting-through ring-opening metathesis polymerization","authors":"Keelee C. McCleary-Petersen, Yating Feng, Damien Guironnet","doi":"10.1039/d4py01228c","DOIUrl":"https://doi.org/10.1039/d4py01228c","url":null,"abstract":"Ring-opening metathesis polymerization (ROMP) of norbornenyl macromonomers (MM) has become a preferred method to synthesize bottlebrush (BB) polymers with perfect grafting density. Prior investigations had established that fast ROMP rates were necessary to synthesize clean BB polymers and that the chemical structure of the anchor group linking the MM polymeric chain and norbornene unit had the most influence on the rate of ROMP. While the order of fastest anchor groups was predicted to be a general trend across all MM chemistry, we observed that the fastest anchor group for a poly(propylene oxide) (PPO) MM is not the fastest for a poly(lactic acid) (PLA) MM. From our kinetic analysis, we showed that PLA MMs are faster with a methylene linker and that PPO MMs are faster with a dicarboximide linker. Interestingly, however, the fast rate of the dicarboximide PPO MM did not lead to the synthesis of a PPO BB polymer with lower dispersity. While the root cause for this MM chemistry sensitivity is still unclear, this study shows that despite being far from the reactive group of the norbornene unit, the chemical structure of MM polymeric chain influences the rate of ROMP beyond the anchor group chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"83 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793582","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":"Multifunctionalization of polybutadiene by RAFT/MADIX technology","authors":"Congze He, Jin Dong, Chaoran Xu, Zhujun Huang, Samir Zard, Xiangcheng Pan","doi":"10.1039/d4py00935e","DOIUrl":"https://doi.org/10.1039/d4py00935e","url":null,"abstract":"Polybutadiene, a widely used synthetic rubber containing unsaturated bonds, has traditionally undergone functionalization processes such as thiol-ene radical addition, hydrogenation, and epoxidation. In this study, we present a new approach for multi-functionalizing polybutadiene through the reversible addition-fragmentation chain transfer polymerization/macromolecular design by interchange of xanthates (RAFT/MADIX) technology. The addition of xanthates onto polybutadiene was accomplished by thermal initiation, photoinitiation, or oxygen-mediated processes. Leveraging the sustained reactivity of dithiocarbonate on functionalized polymer, we further realized dexanthylation and transformation of dithiocarbonate. Finally, xanthate crosslinkers were synthesized for the simultaneous functionalization and cross-linking of polybutadiene.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"82 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793581","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}