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Isosorbide-based copolymers poly(isosorbide carbonate-co-alkylene naphthalate): Synthesis, properties and fluorescence Regulation 基于异山梨酯的共聚物聚(碳酸异山梨酯-萘二甲酸亚烷基酯):合成、性能和荧光调控
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-29 DOI: 10.1016/j.eurpolymj.2025.114477
Ming-Xuan Du, Chang-Hao Han, Hong-Jian Lv, Kai-Xuan Li, Yao-Nan Xiao, Shao-Hua Wu, Jia-Jian Liu, Chun-Cheng Li
Driven by growing environmental concerns, bio-based polymers have been extensively investigated in recent years. In this work, a series of poly(carbonate-ester)s were synthesized via a two-step polycondensation of bio-based monomer isosorbide (Is) with aliphatic diols (1,4-butanediol (BDO), 1,6-hexanediol (HDO), or 1,8-octanediol (ODO)), dimethyl carbonate (DMC), and dimethyl 2,6-naphthalenedicarboxylate (DMN). The synthesized poly(isosorbide carbonate-co- alkylene naphthalate) (PICANs) are intrinsically fluorescent in the bulk state and possess a tunable emission wavelength spanning from 387 nm to 455 nm. Besides, the PICANs copolymers also demonstrate robust thermal stability and substantial stretchability, positioning them as attractive materials for bio-based fluorescent flexible plastics.
在日益增长的环境问题的推动下,生物基聚合物近年来得到了广泛的研究。在这项工作中,通过生物基单体异山梨酯(Is)与脂肪二醇(1,4-丁二醇(BDO)、1,6-己二醇(HDO)或1,8-辛二醇(ODO))、碳酸二甲酯(DMC)和2,6-萘二羧酸二甲酯(DMN)两步缩聚合成了一系列聚碳酸酯(Is)。合成的聚碳酸异山梨酯-邻萘二甲酸亚烷基酯(PICANs)在体态下具有本质荧光,并且具有387nm至455nm的可调谐发射波长。此外,PICANs共聚物还表现出强大的热稳定性和可观的拉伸性,使其成为生物基荧光柔性塑料的有吸引力的材料。
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引用次数: 0
Modern theoretical and practical approaches to development, research and processing of thermoplastic elastomers and their filled composites. review 热塑性弹性体及其填充复合材料开发、研究和加工的现代理论和实践方法。审查
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-24 DOI: 10.1016/j.eurpolymj.2025.114463
Kh.V. Allahverdiyeva , N.T. Kakhramanov , F.A. Mustafayeva , A.A. Hasanova , L.M. Afandiyeva , R.V. Gurbanova , H.B. Bafadarova , E.I. Suleymanova , A.G. Habibova , T.M. Babayeva , O.M. Guliyeva
The article considers current trends in the development of relatively new types of thermoplastic elastomers (TPE) with a unique combination of structure and properties. The fundamental principles of selecting compatibilizers that improve the compatibility of thermoplastics with an elastomer component are shown. Using polyolefins and polar synthetic elastomers as an example, the possibilities of obtaining TPE with an improved set of physical, mechanical-physical and chemical properties are considered. The use of such modern physical methods for analyzing TPE and its modifications as SEM and X-ray phase analysis, derivatography, step dilatometry made it possible to obtain information on the structure–property relationship in the polymer–polymer and polymer-filler systems. Much attention is paid to studying the influence of various types of dispersed and fibrous fillers, as well as nanoparticles, on the main physical, mechanical and thermal characteristics of filled TPE. The use of the integral thermo-deformation method of analysis (Kanavets), as well as the stress–strain dependence made it possible to determine the content of the elastomer component, at which phase inversion occurs and a region of highly elastic deformation characteristic of rubbers is formed. For the first time, the influence of a cross-linking agent (sulfur and dicumyl peroxide (DCP)) on the pattern of changes in the physical and mechanical properties of filled and cross-linked TPE composites is considered. Attention is paid to problems associated with the technology of obtaining dynamically vulcanized TPE, studying the influence of the temperature regime and pressure of reaction extrusion and injection molding on the quality of the composite.
本文考虑了具有独特结构和性能组合的新型热塑性弹性体(TPE)的当前发展趋势。介绍了选择增容剂提高热塑性塑料与弹性体组分相容性的基本原则。以聚烯烃和极性合成弹性体为例,讨论了获得具有改进的物理、机械物理和化学性能的TPE的可能性。使用现代物理方法来分析TPE及其改性,如扫描电镜和x射线相分析,衍生法,步进膨胀法,使得获得聚合物-聚合物和聚合物-填料体系中结构-性能关系的信息成为可能。研究了不同类型的分散填料和纤维填料以及纳米颗粒对填充TPE的主要物理、力学和热特性的影响。使用积分热变形分析方法(Kanavets),以及应力-应变依赖关系,可以确定弹性体成分的含量,在此阶段发生相变,形成橡胶的高弹性变形特征区域。首次研究了交联剂硫和过氧化二氨基(DCP)对填充和交联TPE复合材料物理力学性能变化规律的影响。重点研究了动态硫化TPE的相关技术问题,研究了反应挤出和注射成型的温度和压力对复合材料质量的影响。
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引用次数: 0
Synergistic integration of photoacid and acid-cleavable groups in polymers: An alternative approach to photo-responsive micelles for photo-switchable drug release 聚合物中光酸和酸可切割基团的协同整合:光响应胶束的另一种方法,用于光切换药物释放
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-02 DOI: 10.1016/j.eurpolymj.2026.114496
Yangyang Hu , Ammara Aslam , Runsha Zhai , Yinan Zeng , Silu Wang , Haofei Yang , Anjie Dong , Jianhua Zhang
Due to the advantages of precisely spatiotemporal control and noninvasive manner, the photo-activated micelles derived from photo-responsive block copolymers have found extensive applications in controllable drug delivery systems. However, their practical utility is often constrained, due to the commercial unavailability and high difficulty in synthesis of polymerizable photosensitive monomers, tough challenge in integration of robust blood circulation ability, high toxicity of the metabolite of conventional photo-sensitive O-nitrobenzyl and azobenzene molecules. Herein, a methacryloyl-carrying, polymerizable photoacid generator (MAPDST) was synthesized and used as monomer to prepare amphiphilic photo-responsive block copolymers (PPMT) by RAFT copolymerization with acid-cleavable monomer (TTMA) in the presence of hydrophilic PEGlyated macro-RAFT agent. The structure and physicochemical characteristics of PPMT and corresponding photo-responsive micelles (PPMT NPs) were characterized. The results demonstrated that the PPMT NPs can not only have a high stability for storage and blood circulation as well as good biocompatibility, but also can quickly generate protons and thus strong acidity under UV irradiation, leading to a significant swelling and disassembly by hydrolysis of acid-cleavable TTMA segment and thus achieving a photo-switchable on–off drug release profile. This study indicated the synergistic integration of photoacid and acid-cleavable groups in polymers can provide a facile and promising strategy to endow acid-sensitive polymers and corresponding nanocarriers with desirable photo-responsiveness by photo-triggered cascade reactions. Apparently, considering the multifarious acid-sensitive groups, this new strategy can expand the substrate range of photo-responsive polymer materials and offer alternatives to develop photo-sensitive materials without the limitations associated with conventional photosensitive reagents.
光响应嵌段共聚物的光激活胶束由于具有精确的时空控制和非侵入性等优点,在可控给药系统中得到了广泛的应用。然而,它们的实际应用往往受到限制,因为可聚合光敏单体的商业不可获得性和合成难度高,整合强大的血液循环能力面临严峻挑战,传统光敏o-硝基苯和偶氮苯分子的代谢物具有高毒性。本文合成了一种携带甲基丙烯酰的可聚合光酸发生剂(MAPDST),并以MAPDST为单体,在亲水性PEGlyated宏观RAFT试剂存在下,与酸可切割单体(TTMA) RAFT共聚制备了两亲性光响应嵌段共聚物(PPMT)。表征了PPMT及其光响应胶束(PPMT NPs)的结构和物理化学特性。结果表明,PPMT NPs不仅具有较高的储存稳定性和血液循环稳定性以及良好的生物相容性,而且在紫外线照射下可以快速产生质子,从而产生强酸性,导致酸可切割的TTMA片段被水解而显着膨胀和分解,从而实现光开关药物释放特性。该研究表明,光酸和酸可切割基团在聚合物中的协同整合可以提供一种简单而有前途的策略,通过光触发级联反应赋予酸敏感聚合物和相应的纳米载体理想的光响应性。显然,考虑到各种酸敏基团,这种新策略可以扩大光响应聚合物材料的衬底范围,并提供替代方案来开发光敏材料,而不受传统光敏试剂的限制。
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引用次数: 0
Synthesis and vat-photopolymerization of hydrogen bonding-rich eugenol-based benzoxazine resins for 4D printing of shape memory polymers 形状记忆聚合物4D打印用富氢键丁香酚基苯并恶嗪树脂的合成及光聚合
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-20 DOI: 10.1016/j.eurpolymj.2025.114465
Nuttinan Boonnao , Minwook Jeon , Krittapas Charoensuk , Ibrahim Lawan , Cheol-Hee Ahn , Sarawut Rimdusit
This work presents a novel strategy for developing a UV-curable bio-based eugenol-derived benzoxazine resin for 4D printing of shape-memory polymers (SMPs) via vat photopolymerization (VPP). The methacrylate group of 2-isocyanatoethyl methacrylate (IEM) was grafted onto the benzoxazine monomer through an isocyanate–hydroxyl reaction, introducing urethane linkages and a methacrylate functional group that enhances hydrogen bonding, improves chain segmental mobility, and imparts UV-reactive functionality. The resulting photoreactive resin exhibits moderate viscosity (25.0 Pa·s at 25 °C and at a shear rate of 30 s−1) and high UV reactivity. After dual UV/thermal curing, the polymer shows high stiffness (storage modulus 2.2 GPa), thermal stability (Td5 = 256 °C), and excellent shape memory performance, with shape fixity and shape recovery ratios ∼ 99 % over 30 cycles. In comparison with conventional benzoxazine-based SMPs, the developed 4D printing SMPs polymer also supports larger temporary shape deformation. Structure–property analyses using solubility testing and DMA indicate a relatively low crosslink density (gel content 56.6 %), suggesting that the thermo-mechanical and shape memory performance primarily arises from the dense hydrogen bonding network within the dual-cured polymer. This study establishes a molecular-design strategy for hydrogen-bonding-rich UV-curable benzoxazine systems and demonstrates the critical role of hydrogen bonding in governing the thermo-mechanical and shape memory properties. The 4D-printed structures produced in this work exhibit large deformation capability and excellent shape memory stability, highlighting their potential for durable and flexible high-performance 4D printing applications.
本研究提出了一种新型的紫外光固化生物基丁香酚衍生苯并恶嗪树脂,用于通过还原光聚合(VPP)进行形状记忆聚合物(SMPs)的4D打印。2-异氰基甲基丙烯酸乙酯(IEM)的甲基丙烯酸基团通过异氰酸-羟基反应接枝到苯并恶嗪单体上,引入氨基甲酸乙酯键和甲基丙烯酸官能团,增强氢键,提高链段迁移率,并赋予紫外线反应官能团。所得光反应树脂具有中等粘度(25°C时为25.0 Pa·s,剪切速率为30 s−1)和高紫外反应性。在双UV/热固化后,聚合物表现出高刚度(存储模量2.2 GPa)、热稳定性(Td5 = 256°C)和优异的形状记忆性能,在30次循环中具有形状固定性和形状恢复率~ 99%。与传统的苯并恶嗪基SMPs相比,所开发的4D打印SMPs聚合物还支持更大的临时形状变形。使用溶解度测试和DMA进行的结构性能分析表明,交联密度相对较低(凝胶含量56.6%),表明热机械和形状记忆性能主要来自双固化聚合物内部致密的氢键网络。本研究建立了一种富氢键的紫外光固化苯并恶嗪体系的分子设计策略,并证明了氢键在控制热力学和形状记忆性能中的关键作用。在这项工作中生产的4D打印结构表现出大的变形能力和优异的形状记忆稳定性,突出了它们在耐用和灵活的高性能4D打印应用中的潜力。
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引用次数: 0
Naphthoxazine outperforms benzoxazine: carbazole-based polymers with enhanced blue luminescence and high thermal stability 萘甲恶嗪优于苯并恶嗪:咔唑基聚合物,具有增强的蓝色发光和高热稳定性
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-24 DOI: 10.1016/j.eurpolymj.2025.114471
Osama Younis , Faten M. Taher , Marwa M. Sayed, Mostafa Sayed, Mostafa Ahmed
This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, Mono-BenzOx and Mono-NaphthOx, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While Poly-BenzOx showed residual excimer emission, Poly-NaphthOx displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with Poly-NaphthOx exhibiting a higher decomposition temperature (Td5 = 275 °C) and a significantly greater char yield (27 %) than Poly-BenzOx (Td5 = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts Poly-NaphthOx as a premier multifunctional material for advanced optoelectronic and high-performance applications.
本研究设计、合成和表征了两种新型咔唑基恶嗪单体,单苯氧苄和单萘氧苄及其相应的聚合物。通过缩合、还原、曼尼希环化等一系列反应合成了具有n -乙基咔唑基团的单体,其结构经FTIR和NMR确证。光致发光分析表明,由于空间位阻阻止了准分子的形成,这两种单体在溶液中表现出与浓度无关的蓝色发射。然而,在固体状态下,聚合产生了明显的差异。Poly-BenzOx表现出残余的准分子发射,而Poly-NaphthOx表现出强烈的、高纯度的蓝色光致发光(CIE: 0.16, 0.05),这是由于它在刚性交联网络中有效地分离了发色团。热重分析进一步确定了萘基体系与苯并恶嗪类似物相比的优势,聚萘酚的分解温度(Td5 = 275℃)和碳产率(27%)明显高于聚苯氧苄(Td5 = 233℃,碳产率:4%)。高效的固态蓝色发射,卓越的热稳定性和高炭产率的独特组合使Poly-NaphthOx成为先进光电和高性能应用的首选多功能材料。
{"title":"Naphthoxazine outperforms benzoxazine: carbazole-based polymers with enhanced blue luminescence and high thermal stability","authors":"Osama Younis ,&nbsp;Faten M. Taher ,&nbsp;Marwa M. Sayed,&nbsp;Mostafa Sayed,&nbsp;Mostafa Ahmed","doi":"10.1016/j.eurpolymj.2025.114471","DOIUrl":"10.1016/j.eurpolymj.2025.114471","url":null,"abstract":"<div><div>This study presents the design, synthesis, and characterization of two novel carbazole-based oxazine monomers, <strong>Mono-BenzOx</strong> and <strong>Mono-NaphthOx</strong>, and their corresponding polymers. The monomers, featuring an N-ethyl carbazole moiety, were synthesized through a sequential process of condensation, reduction, and Mannich cyclization, with structures confirmed by FTIR and NMR spectroscopy. Photoluminescence analysis revealed that both monomers exhibit concentration-independent blue emission in solution due to steric hindrance preventing excimer formation. In the solid state, however, a stark difference emerged upon polymerization. While <strong>Poly-BenzOx</strong> showed residual excimer emission, <strong>Poly-NaphthOx</strong> displayed intense, high-purity blue photoluminescence (CIE: 0.16, 0.05) due to the effective isolation of chromophores within its rigid cross-linked network. Thermogravimetric analysis further established the superiority of the naphthalene-based system compared to the benzoxazine analogue, with <strong>Poly-NaphthOx</strong> exhibiting a higher decomposition temperature (T<sub>d5</sub> = 275 °C) and a significantly greater char yield (27 %) than <strong>Poly-BenzOx</strong> (T<sub>d5</sub> = 233 °C, char yield: 4 %). The unique combination of efficient solid-state blue emission, exceptional thermal stability, and high char yield puts <strong>Poly-NaphthOx</strong> as a premier multifunctional material for advanced optoelectronic and high-performance applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114471"},"PeriodicalIF":6.3,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839548","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}
引用次数: 0
A definitive molecular design strategy towards coumarin-based polymers exhibiting reversible acid/base responsivity and high solubility −Exploring the effects of substituent groups at the C4 position of asymmetric coumarin monomer on their ring-opening and closing properties- 具有可逆酸碱反应性和高溶解度的香豆素基聚合物的确定分子设计策略-探索不对称香豆素单体C4位置取代基对其开环和闭环性能的影响-
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-02 DOI: 10.1016/j.eurpolymj.2025.114491
Yuya Kaneko, Aohan Wang
Innovative coumarin-based π-conjugated polymers have been successfully developed, possessing remarkable solubility and reversible alteration of fluorescence in response to changes in acid and base. Through meticulous molecular design, we synthesized two novel dibromo coumarin monomers: 3,7-dibromo-4-methyl-8-octyloxycoumarin and 3,6-dibromo-7,8-dioctyloxy-4-methylcoumarin. By strategically introducing the alkoxy side chains into the benzene ring, rather than the α-pyrone ring of the coumarin backbone, we achieved exceptional ring-opening and ring-closing properties within the polymer mainchain. The resulting coumarin polymers exhibit high molecular weight and reversible turn-on/off fluorescence. Moreover, the effects of the position of the alkoxy side chain on the ring-opening and ring-closing properties were investigated by using coumarin-based model compounds. Our research involved the synthesis of models featuring methyl, methoxy, and octyloxy moieties at the C4 position, along with an octyloxy chain at the C8 position. The results revealed that the positioning of the alkoxy chain plays a pivotal role that directly influences the ring-opening and ring-closing mechanism in the coumarin unit. Furthermore, the chemical structures of the ring-opened coumarin polymer in the basic state and the ring-closed coumarin polymer in the acidic state were examined. We found clear evidence in the ring-opened form that the C=O double bonds in the lactone ring converted to the COO chelate structure in FT-IR spectra, and potassium was detected in XPS spectra.
以香豆素为基础的π共轭聚合物具有良好的溶解度和可逆的荧光随酸碱变化。通过细致的分子设计,我们合成了两个新的二溴香豆素单体:3,7-二溴-4-甲基-8-辛基氧基香豆素和3,6-二溴-7,8-二辛基氧基-4-甲基香豆素。通过将烷氧侧链而不是香豆素主链的α-吡酮环引入苯环中,我们在聚合物主链中实现了特殊的开环和闭环性能。所得到的香豆素聚合物具有高分子量和可逆的开/关荧光。此外,利用香豆素基模型化合物研究了烷氧侧链位置对开环和闭环性能的影响。我们的研究涉及到在C4位置具有甲基、甲氧基和辛氧基基团的模型的合成,以及在C8位置的辛氧基链。结果表明,烷氧基链的位置直接影响香豆素单元的开环和闭环机理。此外,还考察了开环香豆素聚合物在碱性和酸性状态下的化学结构。在开环形式中,我们发现在FT-IR光谱中,内酯环上的C=O双键转变为COO -螯合结构,并且在XPS光谱中检测到钾。
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引用次数: 0
pH-and NIR-responsive sericin-coated magnetic graphene quantum dots for enhanced lung cancer therapy ph和nir响应丝胶涂层磁性石墨烯量子点增强肺癌治疗
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-30 DOI: 10.1016/j.eurpolymj.2025.114455
Farimah Alidousti , Habib Razmi , Homayon Ahmad Panahi , Elham Moniri
Erlotinib therapy for non-small cell lung cancer is limited by poor solubility and a lack of targeted delivery, leading to systemic adverse effects. To address this, a novel near-infrared (NIR) light-triggered nanoplatform was developed using a pH- and thermoresponsive polymer functionalized with sericin-grafted strontium hexaferrite/graphene quantum dots. The drug adsorption process was optimized using response surface methodology, and the Langmuir isotherm and pseudo-second-order kinetic models confirmed monolayer sorption on a homogeneous surface. Under acidic conditions at high temperature, the system demonstrated a controlled release of 63.10 % of the erlotinib, which was best described by the Korsmeyer-Peppas model, indicating a non-Fickian diffusion mechanism. The significance of this platform was highlighted by its dramatic response to external stimuli, achieving a 100 % drug release rate upon NIR laser irradiation for 45 min. This on-demand capability translated to potent biological effects, while the blank nanocarrier was non-cytotoxic, the erlotinib-loaded nanocomposite induced significant cell death in A549 lung cancer cells, with flow cytometry confirming an apoptosis/necrosis rate of 7.07 %. Biocompatibility of the novel nanocomposite has been extensively verified through platelet adhesion, hemolysis assay, and partial thromboplastin time test. This study presents a highly promising and stimuli-responsive strategy for the precise and effective delivery of erlotinib.
厄洛替尼治疗非小细胞肺癌受溶解度差和缺乏靶向递送的限制,导致全身不良反应。为了解决这个问题,研究人员利用丝胶接枝六铁体锶/石墨烯量子点功能化的pH和热响应聚合物,开发了一种新型的近红外(NIR)光触发纳米平台。利用响应面法优化了药物吸附过程,Langmuir等温线和拟二阶动力学模型证实了药物在均匀表面上的单层吸附。在高温酸性条件下,该体系的erlotinib控释量为63.10%,符合Korsmeyer-Peppas模型,为非菲克扩散机制。该平台的重要意义在于其对外部刺激的显著反应,在近红外激光照射45分钟后达到100%的药物释放率。这种按需能力转化为强大的生物效应,而空白纳米载体无细胞毒性,负载埃洛替尼的纳米复合材料在A549肺癌细胞中诱导了显著的细胞死亡,流式细胞术证实凋亡/坏死率为7.07%。新型纳米复合材料的生物相容性已通过血小板粘附、溶血试验和部分凝血活酶时间试验得到广泛验证。这项研究提出了一种非常有前途的刺激响应策略,用于精确和有效地递送厄洛替尼。
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引用次数: 0
Reprocessable and 3D-printable polyurethane thermosets with dynamic covalent urea networks 可再加工和3d打印聚氨酯热固性与动态共价尿素网络
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2025-12-30 DOI: 10.1016/j.eurpolymj.2025.114479
Baoyun Cao, Chuanzheng Ren, Jianjun Bao
Conventional photocurable polyurethanes possess permanently crosslinked networks that impede recyclability, thereby raising significant environmental concerns. In this work, a general molecular strategy is proposed to impart dynamic reversibility to photocurable systems by incorporating dynamic covalent bonds into both the prepolymer and crosslinker domains. Tert-Butylaminoethyl methacrylate (TBEMA) was utilized to construct a dynamic urea-based crosslinker (HTB) and to end-cap polyurethane prepolymers, ensuring chemical compatibility within the system. By combining these components with flexible (CTFA) or rigid (IBMA) active diluents, a series of UV-curable formulations suitable for digital light processing (DLP) were developed. The cured flexible and rigid resins exhibited tensile strengths of approximately 12 MPa and over 45 MPa, respectively, along with excellent printing fidelity. Rheological analysis revealed a persistent long relaxation process within the networks, which fundamentally governs their thermomechanical behavior and directly guided the selection of hot-pressing as the optimal reprocessing technique. Leveraging this dynamic character, the crosslinked networks were successfully reprocessed via hot-pressing. Furthermore, a practical recycling route for mixed polyurethane waste was established by blending the reprocessed resins with virgin thermoplastic polyurethane (TPU), affording homogeneous composites with well-preserved mechanical integrity. This study provides a versatile molecular design paradigm for recyclable thermosetting resins and contributes to advancing the sustainability of photocurable 3D printing materials.
传统的光固化聚氨酯具有永久交联的网络,阻碍了可回收性,从而引起了重大的环境问题。在这项工作中,提出了一种一般的分子策略,通过将动态共价键结合到预聚体和交联剂域中来赋予光固化系统动态可逆性。利用甲基丙烯酸叔丁基氨基乙酯(TBEMA)构建动态脲基交联剂(HTB)和端盖聚氨酯预聚物,确保系统内的化学相容性。通过将这些成分与柔性(CTFA)或刚性(IBMA)活性稀释剂相结合,开发出一系列适合数字光处理(DLP)的紫外光固化配方。固化后的柔性树脂和刚性树脂的抗拉强度分别约为12兆帕和45兆帕以上,同时具有优异的打印保真度。流变学分析表明,网络内部存在一个持续的长松弛过程,这从根本上决定了网络的热力学行为,并直接指导了热压作为最佳再加工技术的选择。利用这种动态特性,通过热压成功地对交联网络进行了再加工。此外,建立了一条实用的混合聚氨酯废物回收路线,将再加工树脂与原始热塑性聚氨酯(TPU)共混,获得了具有良好机械完整性的均质复合材料。该研究为可回收热固性树脂提供了一个通用的分子设计范例,并有助于推进光固化3D打印材料的可持续性。
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引用次数: 0
Nonconventional fluorescent copolymers synthesized from cyclic carbonates and diazoacetates via a post-addition strategy 由环碳酸盐和重氮乙酸酯通过加成策略合成的非常规荧光共聚物
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-02 DOI: 10.1016/j.eurpolymj.2025.114492
Xiang-Xiang Jia, Hong-Lei Li, Xiao-Jie Lu, Xiao-Chi Li, Zhi-Ling Ye, Xu Wang, Jun-Chuan Wang, Hui Wang, Xiang-Feng Wu
Aliphatic polycarbonates have attracted significant attention for their biodegradability and biocompatibility, yet there are also limitations impacting their applications, which usually need to be further optimized by post modification. Carbene polymerization of diazocompounds is an alternative method to undergo further modification for the aliphatic polycarbonates, due to its unique advantage of synthesizing highly functionalized polymers. In this work, the copolymerization of cyclic carbonates with diazoacetates was achieved through a post-addition strategy with the sequence of “cyclic monomer first added, followed by diazoacetate” catalyzed by Sn(Oct)2. Notably, the resulting nonconventional cyclic carbonate-diazoacetate copolymers exhibit novel fluorescence property despite lacking traditionally known conjugated fluorescent chromophores. In addition, its thermal stability can also be adjusted conveniently via multiple approaches by varying the monomers, or altering the feed ratio of the two kinds of monomers, or regulating the molecular weight of the copolymers.
脂肪族聚碳酸酯的生物可降解性和生物相容性引起了广泛的关注,但也存在影响其应用的局限性,通常需要通过后修饰进一步优化。重氮化合物羰基聚合是对脂肪族聚碳酸酯进行进一步改性的一种替代方法,由于其合成高功能化聚合物的独特优势。在这项工作中,通过Sn(Oct)2催化的“先加入环单体,然后再加入重氮乙酸酯”的后加成策略,实现了环碳酸盐与重氮乙酸酯的共聚。值得注意的是,尽管缺乏传统上已知的共轭荧光发色团,所得到的非常规环碳酸酯-重氮乙酸共聚物仍表现出新的荧光特性。此外,它的热稳定性也可以通过改变单体,或改变两种单体的投料比,或调节共聚物的分子量等多种途径来方便地调节。
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引用次数: 0
Corrigendum to “Fabrication of injectable dexamethasone-loaded hydrogel microparticle via microfluidic technique for biomedical applications” [Eur. Polym. J. 225 (2025) 113740] “通过生物医学应用的微流体技术制备可注射地塞米松负载的水凝胶微粒”的勘误表[欧洲]。变异较大。J. 225 (2025) 113740]
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-02-11 Epub Date: 2026-01-16 DOI: 10.1016/j.eurpolymj.2026.114513
Sanaz Alizadeh , Saber Ezzatpour , Ibrahim Zarkesh , Heber Vazquez , Gino Lopez , Marjan Mirsalehi , Mosleh Kadkhoda-Mohammadi , Zohreh Bagher , Seyed Mohammad Davachi
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European Polymer Journal
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