Macromolecules最新文献_第2页

Order–Disorder Tricriticality in Symmetric A n B n Star Polymer Melts 对称A、B、n星形聚合物熔体的有序-无序三临界性

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c02224

Minhoon Kim,Wonjun Kang,Junhan Cho,Daeseong Yong,Jaeup U. Kim

{"title":"Order–Disorder Tricriticality in Symmetric A\u0000 n\u0000 B\u0000 n\u0000 Star Polymer Melts","authors":"Minhoon Kim,Wonjun Kang,Junhan Cho,Daeseong Yong,Jaeup U. Kim","doi":"10.1021/acs.macromol.6c02224","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02224","url":null,"abstract":"Abstract Tricriticality usually requires tuning an additional thermodynamic parameter. Here, we show that, in symmetric AnBn star polymer melts, the arm number n itself plays this role and drives the order–disorder transition (ODT) from second order to first order. By developing a sixth-order free-energy expansion within the random phase approximation and comparing it with self-consistent field theory (SCFT) calculations, we analytically identify a tricritical arm number, ntc ≈ 5.4475. For n &lt; ntc, the lamellar ordering transition remains continuous and occurs at the spinodal point, (χN)s ≈ 10.495. For n &gt; ntc, the transition becomes first order, and (χN)ODT shifts below (χN)s with a quadratic dependence near the tricritical point. SCFT calculations confirm the predicted transition character and phase-boundary shift. The origin of this behavior is traced to inter-arm correlations generated by the common junction. We further show that the noninteger tricritical arm number can be effectively realized in binary mixtures of star polymers. This provides a rare analytically tractable example of architecture-induced tricriticality in a microphase-separating polymer system.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"4 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210161","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}

引用次数: 0

Post-Functionalized Vinyl-Addition Polynorbornenes as Modular Platforms for Anion Exchange Membranes: Structure–Property Relationships 后功能化乙烯加成聚降冰片烯作为阴离子交换膜的模块化平台：结构-性能关系

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c01487

Seungbae Jeon,Eun Woo Lee,Kyulee Jung,Seungjae Lee,Yeongsik Kim,Woohwa Lee,Taehyoung Kim,Hyun Kim,Chang-Geun Chae,Dong-Gyun Kim,Jae Hun Lee,Sungmin Park

{"title":"Post-Functionalized Vinyl-Addition Polynorbornenes as Modular Platforms for Anion Exchange Membranes: Structure–Property Relationships","authors":"Seungbae Jeon,Eun Woo Lee,Kyulee Jung,Seungjae Lee,Yeongsik Kim,Woohwa Lee,Taehyoung Kim,Hyun Kim,Chang-Geun Chae,Dong-Gyun Kim,Jae Hun Lee,Sungmin Park","doi":"10.1021/acs.macromol.6c01487","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01487","url":null,"abstract":"Abstract Fully hydrocarbon-based anion exchange membranes (AEMs) were developed through a facile post-polymerization strategy using vinyl-addition polynorbornene (VA-PNB) backbones. A high-molecular-weight poly(5-vinyl-2-norbornene) (PVNB) precursor was synthesized via chemoselective vinyl-addition polymerization, followed by hydrobromination to introduce tunable brominated functionalities. Subsequent thermal treatment enabled crosslinking through residual vinyl groups without additional crosslinkers. By systematically varying the brominated norbornene content (30–90 mol %), the relationships among ionic composition, crosslinking structure, hydration behavior, mechanical properties, and electrochemical performance were investigated. SAXS and TEM analyses revealed phase-separated ionic aggregates with characteristic d-spacings of approximately 1 nm. Increasing ionic-site density enhanced hydroxide transport but also induced excessive swelling and deterioration of mechanical properties under hydrated conditions. Among the membranes investigated, P(VNB-r-NBQA)50 exhibited a balanced combination of dimensional stability, mechanical properties, and electrochemical performance, showing a low area-specific resistance (0.060 Ω·cm2 at 50 °C) and superior alkaline water electrolysis single-cell performance compared with a commercial FAA membrane. The membrane achieved a current density of 3.06 A/cm2 at 2.0 V and 60 °C, which is approximately 15% higher than that of the commercial FAA membrane (2.66 A/cm2) under identical conditions. Although excessive hydration limited long-term operational stability, this study demonstrates that post-functionalized VA-PNBs provide a versatile platform for designing hydrocarbon-based AEMs and offers important insights into balancing ionic conductivity, swelling behavior, and mechanical stability.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"16 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209816","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}

引用次数: 0

Accelerated Synthesis of Internally Functionalized Dendrimers 内部功能化树状大分子的加速合成

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c02343

Juliana N. O’Brien,Carson J. Lindsay,Arianne San Buenaventura,Aditi Yadav,Stefano Menegatti,Christopher Gorman

{"title":"Accelerated Synthesis of Internally Functionalized Dendrimers","authors":"Juliana N. O’Brien,Carson J. Lindsay,Arianne San Buenaventura,Aditi Yadav,Stefano Menegatti,Christopher Gorman","doi":"10.1021/acs.macromol.6c02343","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02343","url":null,"abstract":"Abstract Poly(amidoamine) (PAMAM) dendrimers have been extensively investigated as drug delivery vectors and building blocks for biosensors, catalysts, and nanoelectronics. High-generation PAMAMs can mimic the phase behavior of biomacromolecules, while the chemical modification of their core and the addition of terminal functionalities can impart desired physicochemical and biomedical attributes. However, the high cost and molecular polydispersity of PAMAMs, as well as the complexity of post-synthesis modifications, limit their widespread application. Addressing these challenges, we previously developed a divergent approach for constructing poly(amidoamine) dendrimers hybridized with amino acid residues (DendriPeps). Unlike low-generation PAMAMs, DendriPeps in dilute solutions self-assemble into discrete nanoparticles whose size and phase behavior depend on the identity and generational placement of the “guest” amino acids and on the composition of the medium. The original synthesis method for DendriPeps, however, is laborious and provides limited product yield and purity. In this study, we developed a rapid and robust solution-phase synthesis that integrates microwave reactions and optimized synthesis conditions to afford step yields of ∼80% and increase productivity while safeguarding molecular purity, as demonstrated by LC-MS. Four guest amino acids—lysine, phenylalanine, tyrosine, and tryptophan—were integrated into Generation 2 DendriPeps with comparable yields and purities. Notably, tryptophan-hybridized DendriPeps self-assembled into intrinsically luminescent nanoparticles. This method broadens the chemical diversity and accessibility of DendriPeps, supporting further exploration of their physicochemical and functional properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"37 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210159","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}

引用次数: 0

Tuning Stiffness and Backbone Rigidity of Diels–Alder-Based Thermosets with Macrocyclic Telechelic Cyclopentadiene Monomers 含大环远旋环戊二烯单体的双醛-桤木基热固性材料的调谐刚度和骨架刚度

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c01638

Komal Komal,Yunze Wu,Conor D. Pugsley,Munshi Sahid Hossain,Angela A. Pitenis,Javier Read de Alaniz

{"title":"Tuning Stiffness and Backbone Rigidity of Diels–Alder-Based Thermosets with Macrocyclic Telechelic Cyclopentadiene Monomers","authors":"Komal Komal,Yunze Wu,Conor D. Pugsley,Munshi Sahid Hossain,Angela A. Pitenis,Javier Read de Alaniz","doi":"10.1021/acs.macromol.6c01638","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01638","url":null,"abstract":"Dynamic covalent polymer networks based on Diels–Alder (DA) chemistry provide a versatile platform for reprocessable and recyclable thermosets. While mechanical properties in these systems are typically tuned through cross-link density or chemical composition, the role of segmental mobility within network junctions has received far less attention. Here, we present a cyclopentadiene–maleimide (Cp–Mal) thermoset platform that enables direct control over segmental mobility through molecular topology. Telechelic cyclopentadiene monomers featuring either macrocyclic or acyclic backbones with nearly identical chemical reactivity were synthesized and combined to form dynamic thermoset networks with constant stoichiometry. A systematic increase in cyclic monomers is consistent with progressive restriction of segmental motion, producing a continuous transition from moderately soft to extremely stiff, glassy thermosets. These results demonstrate that backbone topology and segmental mobility serve as powerful, orthogonal design parameters for controlling thermomechanical performance of dynamic polymer networks without altering network chemistry.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"45 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218897","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}

引用次数: 0

Sequence- and Microstructure-Controlled Alternating Copolymerization of 1,1-Diphenylethylene with 1-Phenyl-1,3-butadienes via Living Anionic Polymerization 序列和微观结构控制的1,1-二苯乙烯与1-苯基-1,3-丁二烯阴离子活性聚合交替共聚

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c02293

Ryosuke Honda,Kotaro Koike,Naoya Yoshida,Motoyasu Kobayashi,Takashi Ishizone,Raita Goseki

{"title":"Sequence- and Microstructure-Controlled Alternating Copolymerization of 1,1-Diphenylethylene with 1-Phenyl-1,3-butadienes via Living Anionic Polymerization","authors":"Ryosuke Honda,Kotaro Koike,Naoya Yoshida,Motoyasu Kobayashi,Takashi Ishizone,Raita Goseki","doi":"10.1021/acs.macromol.6c02293","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02293","url":null,"abstract":"Simultaneous control over the alternating sequence and diene microstructure remains a significant challenge in the anionic copolymerization of 1,1-diphenylethylene (DPE) with conjugated dienes. Herein, we report the synthesis of well-defined alternating copolymers of DPE and 1-phenyl-1,3-butadiene derivatives (E-1PBDs). Defect structures containing consecutive E-1PBD units were efficiently suppressed by employing a large excess of DPE ([DPE]/[E-1PBDs] > 13) combined with a bulky tert-butyldimethylsilyl (TBS) substituent on the E-1PBD framework under optimized polymerization conditions (THF, –40 °C). Consequently, highly alternating copolymers containing approximately 81% 1,4-units were obtained. Subsequent hydrogenation using p-toluenesulfonyl hydrazide proceeded quantitatively without any detectable side reactions, affording sequence-controlled alternating ternary copolymers. Hydrogenation caused only a small decrease in the glass transition temperature (from 103 to 92 °C), indicating that the thermal properties of the alternating copolymer were largely preserved after post-polymerization modification.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"149 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218892","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}

引用次数: 0

Interfacial Coupling Redirects Biaxial Deformation toward Diffusion-Suppressing Phase Reconstruction in Equimass Poly(3-hydroxybutyrate- co -4-hydroxybutyrate)/Poly(lactic acid) Blends 等质量聚（3-羟基丁酸- co -4-羟基丁酸）/聚乳酸共混物的界面耦合重定向双轴变形以抑制扩散相重构

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-19 DOI: 10.1021/acs.macromol.6c02133

Xunda Hu,Haomiao Sun,Yunxuan Weng,Caili Zhang

{"title":"Interfacial Coupling Redirects Biaxial Deformation toward Diffusion-Suppressing Phase Reconstruction in Equimass Poly(3-hydroxybutyrate-\u0000 co\u0000 -4-hydroxybutyrate)/Poly(lactic acid) Blends","authors":"Xunda Hu,Haomiao Sun,Yunxuan Weng,Caili Zhang","doi":"10.1021/acs.macromol.6c02133","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c02133","url":null,"abstract":"Abstract Combining poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB) with poly(lactic acid) (PLA) offers a biodegradable route to balance deformability, stiffness, and optical clarity, but interfacial instability can compromise structural integrity during biaxial deformation. Here, a 50/50 P34HB/PLA blend was reactively compatibilized with the multifunctional bio-based epoxy compound TE3, simultaneously drawn to 3 × 3 at 65 °C, and annealed at 90 °C. The compatibilized blend exhibited refined phase morphology and uniform drawability. Stretching transformed particulate PLA-rich domains into in-plane lamella-like structures, increased the P34HB orientation factor to 0.792, and increased the effective SAXS long period from 5.92 to 7.14 nm. Annealing largely preserved the crystalline orientation, with an orientation factor of 0.789. The final film achieved a tensile strength of 87.3 MPa, an elongation at break of 71.7%, and a transmittance of 81.9% at 650 nm. Oxygen permeability decreased to 4.1 × 10–12 cm3·cm/(cm2·s·cmHg). Within the solution–diffusion framework, this decrease was associated with an 87.7% reduction in the time-lag-derived diffusion coefficient, despite an increase in apparent oxygen solubility. These results support a proposed pathway linking reactive compatibilization, deformation-induced phase reconstruction, and retention of oriented structures to diffusion-suppressed oxygen transport, providing a basis for balancing mechanical and barrier properties in equimass P34HB/PLA films.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"412 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210164","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}

引用次数: 0

Stabilizing Multi-Stranded Helical Supercylinders via Synergistic Effect of A- and C-Block Bidispersity in Frustrated ABC/ABC Binary Blends 在受挫的ABC/ABC二元共混体系中，通过A-和c -嵌段双分散度的协同效应稳定多链螺旋超缸

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01688

Xintong You,Qingshu Dong,Weihua Li

{"title":"Stabilizing Multi-Stranded Helical Supercylinders via Synergistic Effect of A- and C-Block Bidispersity in Frustrated ABC/ABC Binary Blends","authors":"Xintong You,Qingshu Dong,Weihua Li","doi":"10.1021/acs.macromol.6c01688","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01688","url":null,"abstract":"Abstract Helical supercylindrical structures are one type of unique morphologies formed by “frustrated” linear ABC triblock copolymers, which exhibit more intricate geometrical features than straight cylinders. Their stabilization mechanism, especially the feasibility of stabilizing multi-stranded helices (such as quadruple helices) over broad parameter spaces, remains to be further elucidated. Using self-consistent field theory (SCFT), this work investigates how A- and C-block length bidispersity regulates the stability of hierarchical supercylindrical structures in the frustrated ABC/ABC linear triblock copolymer binary blends. The calculated phase diagrams reveal the distinct roles of A- and C-block bidispersity in regulating hierarchical supercylindrical phases. Introducing A-block bidispersity enhances the overall relative stability of hierarchical supercylinders and sequentially stabilizes the hierarchical supercylindrical phases H3C, C4C, H4C, and C6C. On this basis, C-block bidispersity operates through a morphology-selective mechanism by preferentially stabilizing helical supercylindrical phases with more severe C-block stretching nonuniformity within the matrix, thereby substantially expanding the phase regions of H3C and H4C. Our work not only deepens the understanding of the mechanisms governing the stability of helical supercylindrical structures but also offers a molecular design strategy for the experimental fabrication of multi-stranded helical supercylindrical structures, especially quadruple helices.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209819","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}

引用次数: 0

Azide-Capped Poly(alkoxycarbonylmethylene)s for Click Chemistry: Their Syntheses by 2-Bromoethanol-Mediated Chain Transfer Polymerization of Diazoacetate Followed by Azidation 2-溴乙醇介导的重氮乙酸酯链转移聚合-叠氮化反应合成叠氮化包覆的聚烷氧羰基亚甲基

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01954

Hiroaki Shimomoto,Momoe Kawata,Yusuke Kuzukawa,Rika Okawaki,Kaori Miyahara,Tomomichi Itoh,Eiji Ihara

引用次数: 0

Hierarchical Ion-Conducting Materials Based on Polymer-Aligned Nanoparticles within Poly(vinyl benzyl methoxy poly(ethylene oxide) ether)- block -polystyrene Diblock Copolymer 基于聚（乙烯基苄基甲氧基聚（环氧乙烷）醚）-嵌段-聚苯乙烯二嵌段共聚物内聚合物取向纳米颗粒的分级离子导电材料

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01855

Leire Unanue,Monika Król,Gabriele Lingua,Jorge L. Olmedo-Martínez,Alejandro Herranz Berzosa,Sven Schneider,Agnieszka Tercjak,Janne Ruokolainen,Patrick Théato,Alejandro J. Müller,David Mecerreyes

{"title":"Hierarchical Ion-Conducting Materials Based on Polymer-Aligned Nanoparticles within Poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-\u0000 block\u0000 -polystyrene Diblock Copolymer","authors":"Leire Unanue,Monika Król,Gabriele Lingua,Jorge L. Olmedo-Martínez,Alejandro Herranz Berzosa,Sven Schneider,Agnieszka Tercjak,Janne Ruokolainen,Patrick Théato,Alejandro J. Müller,David Mecerreyes","doi":"10.1021/acs.macromol.6c01855","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01855","url":null,"abstract":"Abstract Solid polymer electrolytes based on poly(ethylene oxide) (PEO) are promising alternatives to liquid electrolytes for safer lithium-ion batteries. Here, we report hierarchical solid polymer electrolytes obtained by selectively incorporating lithium sulfonamide-functionalized polymer nanoparticles (LiNPs) into a microphase-separated poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-block-polystyrene block copolymer. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) demonstrate that the phase-segregated lamellar morphology of the block copolymer is preserved upon nanoparticle incorporation. Notably, the LiNPs preferentially localize within the poly(ethylene glycol)-rich lamellae, generating hierarchical structures with ordering across multiple length scales arising from block copolymer self-assembly, selective nanoparticle organization, and poly(ethylene glycol) crystallization. Differential scanning calorimetry (DSC) reveals that the crystallinity of the poly(ethylene glycol) phase depends strongly on nanoparticle loading and plasticizer content. These hierarchical electrolytes exhibit high ionic conductivity, which is further enhanced by the addition of sulfolane as a plasticizer. These results elucidate the interplay between hierarchical morphology, phase crystallinity, and ion transport in block copolymer-based solid electrolytes, providing design guidelines for mechanically robust solid electrolytes with enhanced transport performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"1 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209822","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}

引用次数: 0

Red-Light-Activated Dual Photocatalytic ATRP of Methacrylates and Acrylates Enabled by Copper Phthalocyanines 酞菁铜催化甲基丙烯酸酯和丙烯酸酯的红光活化双光催化ATRP

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-16 DOI: 10.1021/acs.macromol.6c01816

Edina Rusen,Cristina Stavarache,Aurel Diacon,Alexandra Mocanu,Gabriela Toader,Oana Brincoveanu,Ana-Mihaela Gavrila,Livia Alexandra Dinu

{"title":"Red-Light-Activated Dual Photocatalytic ATRP of Methacrylates and Acrylates Enabled by Copper Phthalocyanines","authors":"Edina Rusen,Cristina Stavarache,Aurel Diacon,Alexandra Mocanu,Gabriela Toader,Oana Brincoveanu,Ana-Mihaela Gavrila,Livia Alexandra Dinu","doi":"10.1021/acs.macromol.6c01816","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01816","url":null,"abstract":"Abstract Copper phthalocyanines (Pc) represent a promising yet underexplored class of low-cost and photostable dyes for visible-light-mediated polymerizations. In this study, we demonstrate that copper phthalocyanine (CuPc) and its derivatives efficiently mediate dual photocatalyst/copper atom transfer radical polymerization (PC/Cu-ATRP) of acrylates and methacrylates under red-light irradiation (λ = 628 nm). Using methyl acrylate (MA) as a model monomer, CuPc and its chlorinated derivative (CuPc-Cl) enable controlled polymerization in DMSO at ambient temperature, whereas the aminated analogue (CuPc-NH2) exhibits substantially lower activity. Kinetic analysis reveals apparent first-order behavior with respect to the monomer, with higher polymerization rates observed for CuPc compared to CuPc-Cl, consistent with differences in solubility. The resulting polymers display predictable molar mass evolution, low dispersity (Đ &lt; 1.3), and good temporal control under intermittent irradiation. High chain-end fidelity is confirmed by successful chain extension, affording PMA-b-PMMA block copolymers. Molecular weight can be readily tuned by varying the monomer-to-initiator ratio. As a practical demonstration, CuPc was applied in the suspension polymerization of methyl methacrylate (MMA), yielding polymer particles (3–20 μm) incorporating the dye, as confirmed by optical microscopy and scanning electron microscopy (SEM). These findings establish copper phthalocyanines as efficient and accessible photocatalysts for red-light-driven controlled radical polymerization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"37 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209817","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}

引用次数: 0