Pub Date : 2026-01-28DOI: 10.1021/acs.macromol.5c03175
Xuelin Song, Shunjie Liu, Shuo Yan, Chunwei Zhuo, Xianhong Wang
A long-standing challenge in the synthesis of optical resins using styrene oxide (SO) is the inevitable SO isomerization side reactions that deteriorate the polymerization, giving low-molecular-weight products. Here, we report a CO2-mediated monomer-protection strategy that converts SO into its stable cyclic carbonate, styrene carbonate (SC), effectively preventing side reactions. Upon thermal activation, SC undergoes selective ring-opening followed by in situ decarboxylation to generate an active species, which is immediately captured by phthalic anhydride (PA) to realize efficient and controlled polymerization. The average molecular weight of the resulting polyesters was significantly increased to 178.4 kDa with a low dispersity (Đ = 1.39) under optimized conditions. Owing to the markedly enhanced molecular weight, the polyesters exhibit superior thermal stability, electrical insulation, optical transparency, and a balanced refractive index (nd = 1.588) and Abbe number (Vd = 42). This work demonstrates a rational, design-driven approach for reprogramming labile epoxides and provides a versatile platform for the synthesis of high-molecular-weight optical resins with potential applications in advanced optical, electronic, and insulating materials.
{"title":"CO2-Mediated Cyclic Carbonate Route to High-Molecular-Weight Optical Resin","authors":"Xuelin Song, Shunjie Liu, Shuo Yan, Chunwei Zhuo, Xianhong Wang","doi":"10.1021/acs.macromol.5c03175","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03175","url":null,"abstract":"A long-standing challenge in the synthesis of optical resins using styrene oxide (SO) is the inevitable SO isomerization side reactions that deteriorate the polymerization, giving low-molecular-weight products. Here, we report a CO<sub>2</sub>-mediated monomer-protection strategy that converts SO into its stable cyclic carbonate, styrene carbonate (SC), effectively preventing side reactions. Upon thermal activation, SC undergoes selective ring-opening followed by <i>in situ</i> decarboxylation to generate an active species, which is immediately captured by phthalic anhydride (PA) to realize efficient and controlled polymerization. The average molecular weight of the resulting polyesters was significantly increased to 178.4 kDa with a low dispersity (<i>Đ</i> = 1.39) under optimized conditions. Owing to the markedly enhanced molecular weight, the polyesters exhibit superior thermal stability, electrical insulation, optical transparency, and a balanced refractive index (<i>n</i><sub>d</sub> = 1.588) and Abbe number (<i>V</i><sub>d</sub> = 42). This work demonstrates a rational, design-driven approach for reprogramming labile epoxides and provides a versatile platform for the synthesis of high-molecular-weight optical resins with potential applications in advanced optical, electronic, and insulating materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"295 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.macromol.5c02921
Chenzhi Yao, Qike Sun, Hui Deng, Gongyang Chen, Heng Xia, Zhengjiang Liu, Timur Borjigin, Jiansong Yin, Jacques Lalevée, Yangyang Xu
Photoinduced radical chemistry is pivotal for synthesizing polymeric materials under light irradiation. In this study, carbazole moieties were incorporated at distinct positions within the aza-boron-dipyrromethene (aza-BODIPY) scaffold, yielding three novel push–pull dyes that function as high-performance photoinitiators for the free radical polymerization of acrylates upon exposure to visible-light LED irradiation. When combined with iodonium salts or amines as co-initiators, these aza-BODIPY derivatives form efficient two-component photoinitiating systems that exhibit outstanding initiation performance. Notably, distinct polymerization kinetics were observed for two benchmark acrylate monomers. Through a combination of experimental investigations and theoretical calculations, a comprehensive photochemical mechanism has been elucidated. Furthermore, these newly developed carbazole-substituted aza-BODIPY-based photoinitiating systems enable the fabrication of high-resolution three-dimensional macroscale architectures via 3D printing. This work advances the fundamental understanding and practical application of visible-light-induced free radical polymerization.
{"title":"Visible-Light-Driven Free Radical Polymerization and 3D Printing with Highly Efficient Carbazole-Substituted Aza-BODIPY Photoinitiators","authors":"Chenzhi Yao, Qike Sun, Hui Deng, Gongyang Chen, Heng Xia, Zhengjiang Liu, Timur Borjigin, Jiansong Yin, Jacques Lalevée, Yangyang Xu","doi":"10.1021/acs.macromol.5c02921","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02921","url":null,"abstract":"Photoinduced radical chemistry is pivotal for synthesizing polymeric materials under light irradiation. In this study, carbazole moieties were incorporated at distinct positions within the aza-boron-dipyrromethene (aza-BODIPY) scaffold, yielding three novel push–pull dyes that function as high-performance photoinitiators for the free radical polymerization of acrylates upon exposure to visible-light LED irradiation. When combined with iodonium salts or amines as co-initiators, these aza-BODIPY derivatives form efficient two-component photoinitiating systems that exhibit outstanding initiation performance. Notably, distinct polymerization kinetics were observed for two benchmark acrylate monomers. Through a combination of experimental investigations and theoretical calculations, a comprehensive photochemical mechanism has been elucidated. Furthermore, these newly developed carbazole-substituted aza-BODIPY-based photoinitiating systems enable the fabrication of high-resolution three-dimensional macroscale architectures via 3D printing. This work advances the fundamental understanding and practical application of visible-light-induced free radical polymerization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"19 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acs.macromol.5c03465
Yixuan Shan, Quanquan Xu, Yu Bao, Shuxun Cui
As the thermodynamically stable phase of selenium, trigonal selenium (t-Se) has long been studied as an inorganic solid, with previous studies focusing on its lattice and phase behavior while overlooking its chain-like nature. Herein, t-Se was investigated, for the first time, as a polymer material. Single-molecule force spectroscopy (SMFS) and complementary techniques reveal that t-Se consists of finite linear poly-Se chains with an average contour length of 148 nm (∼63 kDa) rather than the infinite structures traditionally assumed. The single-chain inherent elasticity of poly-Se was experimentally quantified and theoretically calculated, providing the quantitative evidence for its covalently linked Se–Se backbone and flexible mechanical behavior comparable to that of organic polymers with carbon–carbon backbones (e.g., polyethylene). These findings demonstrate t-Se as an inorganic crystal with distinct macromolecular characteristics. Unlike conventional inorganic solids, which are either fully crystalline or amorphous, t-Se shows a degree of crystallinity exceeding 98%, surpassing almost all synthetic polymers including high-density polyethylene (HDPE). This reflects the highly ordered packing of its finite-length poly-Se chains, placing t-Se among the polymers with the highest degree of crystallinity known to date. This bridges the gap between inorganic chemistry and polymer science, opening new avenues for exploring t-Se as a macromolecular material.
{"title":"Trigonal Selenium is an Inorganic Macromolecular Crystal Formed by Linear Long but Finite Polymer Chains of Se","authors":"Yixuan Shan, Quanquan Xu, Yu Bao, Shuxun Cui","doi":"10.1021/acs.macromol.5c03465","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03465","url":null,"abstract":"As the thermodynamically stable phase of selenium, trigonal selenium (t-Se) has long been studied as an inorganic solid, with previous studies focusing on its lattice and phase behavior while overlooking its chain-like nature. Herein, t-Se was investigated, for the first time, as a polymer material. Single-molecule force spectroscopy (SMFS) and complementary techniques reveal that t-Se consists of finite linear poly-Se chains with an average contour length of 148 nm (∼63 kDa) rather than the infinite structures traditionally assumed. The single-chain inherent elasticity of poly-Se was experimentally quantified and theoretically calculated, providing the quantitative evidence for its covalently linked Se–Se backbone and flexible mechanical behavior comparable to that of organic polymers with carbon–carbon backbones (e.g., polyethylene). These findings demonstrate t-Se as an inorganic crystal with distinct macromolecular characteristics. Unlike conventional inorganic solids, which are either fully crystalline or amorphous, t-Se shows a degree of crystallinity exceeding 98%, surpassing almost all synthetic polymers including high-density polyethylene (HDPE). This reflects the highly ordered packing of its finite-length poly-Se chains, placing t-Se among the polymers with the highest degree of crystallinity known to date. This bridges the gap between inorganic chemistry and polymer science, opening new avenues for exploring t-Se as a macromolecular material.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"73 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1021/acs.macromol.5c02579
Alex Palma-Cando, Felix Niebisch, Ibeth Rendón-Enríquez, Gunther Brunklaus, Kai Brinkmann, Thomas Riedl, Ullrich Scherf
The rational design of donor–acceptor (D–A) monomers enables control over porosity, electroactivity, and stability in conjugated microporous polymers (CMPs). Herein, we report the synthesis of five thiophene–benzothiadiazole-based monomers, four of them novel, and their polymerization via chemical (FeCl3 oxidative) and electrochemical routes. Structural diversity was introduced through terthiophene regiochemistry (2,3- vs 2,4-substitution) and rigid, multibranched cores including benzene, spirobifluorene, and tetraphenylmethane. Chemically synthesized bulk CMPs exhibit specific surface areas of 81–591 m2 g–1, while electropolymerized films from planar monomers suffer pore collapse. In contrast, rigid three-dimensional monomers yield smooth, highly porous films with surface areas up to 318 m2 g–1. The rigid structure of SpTBTTh enables the formation of thin polymer films with smooth morphology while preserving high porosity. Combined with favorable energy level alignment, these characteristics highlight the potential of rigid D–A CMP films as active layers in organic photovoltaic architectures.
合理的给体-受体（D-A）单体设计可以控制共轭微孔聚合物（cmp）的孔隙度、电活性和稳定性。在此，我们报道了五个噻吩-苯并噻唑基单体的合成，其中四个是新的，并通过化学（FeCl3氧化）和电化学途径进行聚合。通过噻吩区域化学（2,3- vs 2,4-取代）和包括苯、螺芴和四苯基甲烷在内的刚性多支核心，介绍了结构多样性。化学合成的块状CMPs的比表面积为81-591 m2 g-1，而平面单体电聚合膜的孔坍塌。相比之下，刚性的三维单体产生光滑，高多孔膜，表面积高达318 m2 g-1。SpTBTTh的刚性结构使其能够形成光滑的聚合物薄膜，同时保持高孔隙率。结合有利的能级排列，这些特性突出了刚性D-A CMP薄膜在有机光伏结构中作为活性层的潜力。
{"title":"Synthesis and Characterization of Donor–Acceptor Conjugated Microporous Polymer Films","authors":"Alex Palma-Cando, Felix Niebisch, Ibeth Rendón-Enríquez, Gunther Brunklaus, Kai Brinkmann, Thomas Riedl, Ullrich Scherf","doi":"10.1021/acs.macromol.5c02579","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02579","url":null,"abstract":"The rational design of donor–acceptor (D–A) monomers enables control over porosity, electroactivity, and stability in conjugated microporous polymers (CMPs). Herein, we report the synthesis of five thiophene–benzothiadiazole-based monomers, four of them novel, and their polymerization via chemical (FeCl<sub>3</sub> oxidative) and electrochemical routes. Structural diversity was introduced through terthiophene regiochemistry (2,3- vs 2,4-substitution) and rigid, multibranched cores including benzene, spirobifluorene, and tetraphenylmethane. Chemically synthesized bulk CMPs exhibit specific surface areas of 81–591 m<sup>2</sup> g<sup>–1</sup>, while electropolymerized films from planar monomers suffer pore collapse. In contrast, rigid three-dimensional monomers yield smooth, highly porous films with surface areas up to 318 m<sup>2</sup> g<sup>–1</sup>. The rigid structure of SpTBTTh enables the formation of thin polymer films with smooth morphology while preserving high porosity. Combined with favorable energy level alignment, these characteristics highlight the potential of rigid D–A CMP films as active layers in organic photovoltaic architectures.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"102 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1021/acs.macromol.5c02581
Hannelore Geeraert, Milan Den Haese, Louis M. Pitet, Dario Cavallo, Eveline Peeters, Niko Van den Brande
Crystallization in poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)) is strongly influenced by the thermal history. Additive-free P(3HB-co-5% 4HB) was biosynthesized, and melt memory domains were identified from DSC crystallization measurements after processing for 3 min at temperatures between 152 and 212 °C. A broad self-nucleation domain (∼20 °C) was confirmed by polarized optical microscopy, whereas complete melt memory erasure led to sparse nucleation and slow crystallization. Thermal degradation, already present at low processing temperatures, substantially reduced the molecular weight, which was shown to affect spherulite growth rates and overall crystallization behavior. When melt memory was evaluated after thermal history removal (3 min at TDI) and recrystallization, the self-nucleation domain narrowed (∼10 °C). Increasing TDI further weakened memory due to degradation-induced molecular weight reduction. These results demonstrate that meaningful crystallization studies of P(3HB-co-4HB) require careful optimization of processing temperatures to balance melt memory effects with molecular weight retention within the narrow thermal processing window of this copolymer.
{"title":"Consequences of Melt Memory and Thermal Degradation for Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Crystallization","authors":"Hannelore Geeraert, Milan Den Haese, Louis M. Pitet, Dario Cavallo, Eveline Peeters, Niko Van den Brande","doi":"10.1021/acs.macromol.5c02581","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02581","url":null,"abstract":"Crystallization in poly(3-hydroxybutyrate-<i>co</i>-4-hydroxybutyrate) (P(3HB-<i>co</i>-4HB)) is strongly influenced by the thermal history. Additive-free P(3HB-<i>co</i>-5% 4HB) was biosynthesized, and melt memory domains were identified from DSC crystallization measurements after processing for 3 min at temperatures between 152 and 212 °C. A broad self-nucleation domain (∼20 °C) was confirmed by polarized optical microscopy, whereas complete melt memory erasure led to sparse nucleation and slow crystallization. Thermal degradation, already present at low processing temperatures, substantially reduced the molecular weight, which was shown to affect spherulite growth rates and overall crystallization behavior. When melt memory was evaluated after thermal history removal (3 min at <i>T</i><sub>DI</sub>) and recrystallization, the self-nucleation domain narrowed (∼10 °C). Increasing <i>T</i><sub>DI</sub> further weakened memory due to degradation-induced molecular weight reduction. These results demonstrate that meaningful crystallization studies of P(3HB-<i>co</i>-4HB) require careful optimization of processing temperatures to balance melt memory effects with molecular weight retention within the narrow thermal processing window of this copolymer.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"44 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1021/acs.macromol.5c02727
Amali G. Guruge, Hesam Makki, Alessandro Troisi
Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a widely used conducting polymer, whose conductivity can be enhanced by incorporation of specific chemical components, whereas diffusion of water into the material can reduce its conductivity. These changes are typically linked to morphological changes in lamella crystallite size, π–π stacking, chain orientation, and interlamella connectivity. However, an atomistic-level understanding of how specific chemical components influence these properties remains limited, particularly in relation to experimentally observed conductivity trends. In this study, molecular dynamics (MD) simulations are employed to investigate the effects of electrolytes, dopamine, and poly(ethylene glycol) 400 (PEG-400) on PEDOT:PSS morphology and relate the findings to experimental observations. All chemical components were found to screen electrostatic interactions between PEDOT and PSS, potentially affecting the conductivity. Dopamine tends to reduce conductivity by intercalating between PEDOT and PSS, disrupting interdomain connectivity. In contrast, PEG-400 enhances conductivity by improving interlamellar connectivity without altering PEDOT chain conformation, challenging conventional explanations and suggesting an alternative mechanism. CuCl2 enhances conductivity via PEDOT conformational changes associated with partial PSS loss, whereas NaCl shows minimal morphological changes, in agreement with established explanations. Overall, MD simulations confirm the established trends, provide alternative insights, and challenge commonly accepted explanations, demonstrating their utility in validating, refining, and reinterpreting molecular mechanisms in complex polymer systems.
{"title":"Morphological Changes in PEDOT:PSS under Electrolytes, Dopamine, and PEG-400 Exposure: A Molecular Simulation Perspective","authors":"Amali G. Guruge, Hesam Makki, Alessandro Troisi","doi":"10.1021/acs.macromol.5c02727","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02727","url":null,"abstract":"Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a widely used conducting polymer, whose conductivity can be enhanced by incorporation of specific chemical components, whereas diffusion of water into the material can reduce its conductivity. These changes are typically linked to morphological changes in lamella crystallite size, π–π stacking, chain orientation, and interlamella connectivity. However, an atomistic-level understanding of how specific chemical components influence these properties remains limited, particularly in relation to experimentally observed conductivity trends. In this study, molecular dynamics (MD) simulations are employed to investigate the effects of electrolytes, dopamine, and poly(ethylene glycol) 400 (PEG-400) on PEDOT:PSS morphology and relate the findings to experimental observations. All chemical components were found to screen electrostatic interactions between PEDOT and PSS, potentially affecting the conductivity. Dopamine tends to reduce conductivity by intercalating between PEDOT and PSS, disrupting interdomain connectivity. In contrast, PEG-400 enhances conductivity by improving interlamellar connectivity without altering PEDOT chain conformation, challenging conventional explanations and suggesting an alternative mechanism. CuCl<sub>2</sub> enhances conductivity via PEDOT conformational changes associated with partial PSS loss, whereas NaCl shows minimal morphological changes, in agreement with established explanations. Overall, MD simulations confirm the established trends, provide alternative insights, and challenge commonly accepted explanations, demonstrating their utility in validating, refining, and reinterpreting molecular mechanisms in complex polymer systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"33 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1021/acs.macromol.5c03344
Dietrich Gloger, János Molnár, Dietmar Salaberger, Davide Tranchida, Markus Gahleitner, Wolfgang H. Binder, René Androsch
We demonstrate that long-chain branched polypropylene (LCB PP) exhibits pronounced melt memory above the equilibrium melting point due to topological constraints and gel-like structures that slow the relaxation of non-equilibrium chain states. These states, formed during synthesis and subsequent melt processing, act as self-nuclei in differential scanning calorimetry (DSC) experiments and persist beyond the conventional 5 min equilibration used in standard DSC protocols. The decay of self-nuclei, monitored via the isothermal crystallization rate, follows a power-law dependence with the equilibration time. This behavior agrees with diffusive relaxation of non-equilibrium clusters in a topologically complex environment. Morphological analyses show that self-nucleation produces nucleation densities (Nd) up to 1011 cm–3, which suppresses spherulitic growth and induces anisotropic lamellar textures. The self-nuclei are most effectively reduced in a prior solution treatment of the polymer, which decreases Nd and crystallization rate but also increases the viscoelastic relaxation time, demonstrating the link between melt structure and crystallization.
{"title":"Long Memory in Large Molecules: Self-Nucleation in Long-Chain Branched Polypropylene Melts","authors":"Dietrich Gloger, János Molnár, Dietmar Salaberger, Davide Tranchida, Markus Gahleitner, Wolfgang H. Binder, René Androsch","doi":"10.1021/acs.macromol.5c03344","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03344","url":null,"abstract":"We demonstrate that long-chain branched polypropylene (LCB PP) exhibits pronounced melt memory above the equilibrium melting point due to topological constraints and gel-like structures that slow the relaxation of non-equilibrium chain states. These states, formed during synthesis and subsequent melt processing, act as self-nuclei in differential scanning calorimetry (DSC) experiments and persist beyond the conventional 5 min equilibration used in standard DSC protocols. The decay of self-nuclei, monitored via the isothermal crystallization rate, follows a power-law dependence with the equilibration time. This behavior agrees with diffusive relaxation of non-equilibrium clusters in a topologically complex environment. Morphological analyses show that self-nucleation produces nucleation densities (<i>N</i><sub>d</sub>) up to 10<sup>11</sup> cm<sup>–3</sup>, which suppresses spherulitic growth and induces anisotropic lamellar textures. The self-nuclei are most effectively reduced in a prior solution treatment of the polymer, which decreases <i>N</i><sub>d</sub> and crystallization rate but also increases the viscoelastic relaxation time, demonstrating the link between melt structure and crystallization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1021/acs.macromol.5c03019
Shin Inagaki,Hideki Abe
The development of fully metal-free strategies for the synthesis and functionalization of polymers is crucial for advancing sustainable materials. This study introduces a platform that integrates metal-free reversible addition–fragmentation chain-transfer (RAFT) polymerization with sulfur(VI) fluoride exchange (SuFEx) chemistry to enable the controlled polymerization and postpolymerization side-chain modification of renewable polymers. Silyl-protected poly(vinylphenol) (PSVP)s and poly(vinyl catechol) (PSVC) derived from cinnamic acid analogs were synthesized and subsequently functionalized with a range of sulfonyl fluorides bearing electron-donating or electron-withdrawing substituents. High degrees of modification were achieved for para-substituted PSVP, while meta-substituted PSVP and their corresponding block copolymers exhibited high conversions with minimal side reactions. By contrast, ortho-substituted PSVP and PSVC systems generally exhibited moderate efficiencies, consistent with steric hindrance. This fully metal-free sequence provides a sustainable and versatile strategy for the functionalization of biobased polymers, expanding the scope of SuFEx chemistry and contributing to the development of environmentally sustainable polymer materials.
{"title":"SuFEx Chemistry Enables Sustainable Side-Chain Modification of Renewable Phenylpropanoid Polymers","authors":"Shin Inagaki,Hideki Abe","doi":"10.1021/acs.macromol.5c03019","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03019","url":null,"abstract":"The development of fully metal-free strategies for the synthesis and functionalization of polymers is crucial for advancing sustainable materials. This study introduces a platform that integrates metal-free reversible addition–fragmentation chain-transfer (RAFT) polymerization with sulfur(VI) fluoride exchange (SuFEx) chemistry to enable the controlled polymerization and postpolymerization side-chain modification of renewable polymers. Silyl-protected poly(vinylphenol) (PSVP)s and poly(vinyl catechol) (PSVC) derived from cinnamic acid analogs were synthesized and subsequently functionalized with a range of sulfonyl fluorides bearing electron-donating or electron-withdrawing substituents. High degrees of modification were achieved for para-substituted PSVP, while meta-substituted PSVP and their corresponding block copolymers exhibited high conversions with minimal side reactions. By contrast, ortho-substituted PSVP and PSVC systems generally exhibited moderate efficiencies, consistent with steric hindrance. This fully metal-free sequence provides a sustainable and versatile strategy for the functionalization of biobased polymers, expanding the scope of SuFEx chemistry and contributing to the development of environmentally sustainable polymer materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"40 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing high-performance polyurethane (PU) elastomers requires overcoming the inherent trade-off between strength and toughness through precise control of the microphase separation morphology. Advances in nanostructure control and nondestructive microstructural detection are therefore essential. Herein, we report a hyperbranched PU elastomer (PU-HPAEx) synthesized using hyperbranched poly(amino ester) (HPAE) as a dual-function macromonomer that acts simultaneously as a chain extender and a nonconventional fluorescent probe. The hyperbranched architecture creates a three-dimensional network enriched with high-density sacrificial hydrogen bonds (H-bonds) and a well-defined microphase-separated morphology, resulting in exceptional strength (65.80 MPa), elongation (1031.70%), and toughness (185.3 MJ m–3)─overcoming classical strength–toughness conflicts. In addition, the hyperbranched topology promotes efficient cluster-triggered emission (CTE) via through-space conjugation (TSC), endowing PU-HPAEx with exceptionally strong fluorescence (quantum yield 11.16%). Critically, HPAE serves as an intrinsic fluorescent probe, enabling in situ visualization of micrometer-scale phase separation and its dynamic evolution, thereby providing key insights into the morphology–performance relationship. Furthermore, HPAE exhibits stimuli-responsive fluorescence under both mechanical strain and humidity, highlighting its potential application in smart sensing. By leveraging topological structure regulation, this work successfully establishes a novel strategy for fluorescent PU elastomers that integrates high performance with nondestructive visualization of microphase morphology.
{"title":"In Situ Visualization of Microphase Separation in High-Performance Hyperbranched Polyurethane","authors":"Jingyuan Wei,Yufei Zhang,Huan Ma,Jia Li,Junzhuo Cheng,Haotian Ma,Shenggui Du,Kai Cheng,Hefeng Zhang,Tianqi Zhou,Yu Jiang,Daohong Zhang,Nikos Hadjichristidis","doi":"10.1021/acs.macromol.5c02875","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02875","url":null,"abstract":"Developing high-performance polyurethane (PU) elastomers requires overcoming the inherent trade-off between strength and toughness through precise control of the microphase separation morphology. Advances in nanostructure control and nondestructive microstructural detection are therefore essential. Herein, we report a hyperbranched PU elastomer (PU-HPAEx) synthesized using hyperbranched poly(amino ester) (HPAE) as a dual-function macromonomer that acts simultaneously as a chain extender and a nonconventional fluorescent probe. The hyperbranched architecture creates a three-dimensional network enriched with high-density sacrificial hydrogen bonds (H-bonds) and a well-defined microphase-separated morphology, resulting in exceptional strength (65.80 MPa), elongation (1031.70%), and toughness (185.3 MJ m–3)─overcoming classical strength–toughness conflicts. In addition, the hyperbranched topology promotes efficient cluster-triggered emission (CTE) via through-space conjugation (TSC), endowing PU-HPAEx with exceptionally strong fluorescence (quantum yield 11.16%). Critically, HPAE serves as an intrinsic fluorescent probe, enabling in situ visualization of micrometer-scale phase separation and its dynamic evolution, thereby providing key insights into the morphology–performance relationship. Furthermore, HPAE exhibits stimuli-responsive fluorescence under both mechanical strain and humidity, highlighting its potential application in smart sensing. By leveraging topological structure regulation, this work successfully establishes a novel strategy for fluorescent PU elastomers that integrates high performance with nondestructive visualization of microphase morphology.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"64 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.1021/acs.macromol.5c03069
Yen-Ling Kuan,Yu-Chun Chiu,Yun-Sheng Ye,Shiao-Wei Kuo
In this study, the chain end of a reversible addition–fragmentation chain transfer (RAFT) polymerization agent of poly(cyclohexene carbonate) (PCHC) was synthesized via the ring-opening copolymerization of CO2 and cyclohexene oxide (CHO) by using s-dodecyl-s’-(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (DDMAT) as a chain transfer agent. Various block copolymers of poly(cyclohexene carbonate)-b-poly(styrene-alt-N-(hydroxyphenyl)maleimide) (PCHC-b-PSHPMI) were subsequently synthesized by the RAFT copolymerization of styrene and N-(hydroxyphenyl)maleimide (HPMI) in the presence of azobis(isobutyronitrile) (AIBN), which were characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). DSC thermal analyses indicated that the single Tg values were observed for all PCHC-b-PSHPMI copolymers, indicating miscible behavior, and the Tg value was 194 °C for the PCHC-b-PSHPMI78 copolymer. One- and two-dimensional (2D) FTIR spectroscopy revealed that these PCHC-b-PSHPMI copolymers actually provide relatively weak intermolecular O–H···O═C hydrogen bonding, which was attenuated by the self-association of hydrogen bonding within the pure PCHC and pure PSHPMI segments. In the solid-state 13C NMR spectra, a pronounced chemical shift variation of the C–OH and C═O units of the PSHPMI segment and C═O units of the PCHC segment was also observed, which is attributable to the intermolecular hydrogen interactions in these PCHC-b-PSHPMI copolymers. Rotating-frame 1H spin–lattice relaxation [T1ρ(H)] analyses also indicated the complete miscible behavior of these block copolymers within the 2–3 nm length scale, and the relaxation times exhibited positive deviations from the linear predicted rule. These results suggest that the loose chain structure was formed because of the weaker intermolecular hydrogen bonding between the PCHC and PSHPMI segments in the block copolymers.
{"title":"Highly Thermally Stable and Miscible CO2-Based Block Copolymers by the Combination of Ring-Opening and RAFT Copolymerizations through Mediated Hydrogen Bonding Interactions","authors":"Yen-Ling Kuan,Yu-Chun Chiu,Yun-Sheng Ye,Shiao-Wei Kuo","doi":"10.1021/acs.macromol.5c03069","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c03069","url":null,"abstract":"In this study, the chain end of a reversible addition–fragmentation chain transfer (RAFT) polymerization agent of poly(cyclohexene carbonate) (PCHC) was synthesized via the ring-opening copolymerization of CO2 and cyclohexene oxide (CHO) by using s-dodecyl-s’-(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (DDMAT) as a chain transfer agent. Various block copolymers of poly(cyclohexene carbonate)-b-poly(styrene-alt-N-(hydroxyphenyl)maleimide) (PCHC-b-PSHPMI) were subsequently synthesized by the RAFT copolymerization of styrene and N-(hydroxyphenyl)maleimide (HPMI) in the presence of azobis(isobutyronitrile) (AIBN), which were characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). DSC thermal analyses indicated that the single Tg values were observed for all PCHC-b-PSHPMI copolymers, indicating miscible behavior, and the Tg value was 194 °C for the PCHC-b-PSHPMI78 copolymer. One- and two-dimensional (2D) FTIR spectroscopy revealed that these PCHC-b-PSHPMI copolymers actually provide relatively weak intermolecular O–H···O═C hydrogen bonding, which was attenuated by the self-association of hydrogen bonding within the pure PCHC and pure PSHPMI segments. In the solid-state 13C NMR spectra, a pronounced chemical shift variation of the C–OH and C═O units of the PSHPMI segment and C═O units of the PCHC segment was also observed, which is attributable to the intermolecular hydrogen interactions in these PCHC-b-PSHPMI copolymers. Rotating-frame 1H spin–lattice relaxation [T1ρ(H)] analyses also indicated the complete miscible behavior of these block copolymers within the 2–3 nm length scale, and the relaxation times exhibited positive deviations from the linear predicted rule. These results suggest that the loose chain structure was formed because of the weaker intermolecular hydrogen bonding between the PCHC and PSHPMI segments in the block copolymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"7 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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