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Self-initiated copolymer grafting on ground tire rubber for controlled interfacial properties 自引发共聚物接枝在地面轮胎橡胶的界面性能控制
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114497
Reymark D. Maalihan, Eugene B. Caldona
Ground tire rubber (GTR) is a plentiful secondary polymer resource, but its aged, nonpolar surface limits compatibility with polar matrices. This study presents a scalable “graft-from” copolymerization of acrylic acid (AA) and methyl methacrylate (MMA) onto cryo-milled GTR, initiated by mechanoradicals generated during milling, eliminating the need for external initiators. By varying the AA:MMA ratio, copolymer grafts with tunable polarity were obtained and correlated with surface and dispersion properties. Spectroscopy confirmed successful co-grafting, with compositional trends identified by principal component analysis. Electron paramagnetic resonance indicated near-complete radical consumption. Thermogravimetric analysis confirmed surface-limited modification. Increasing AA content transformed fractured carbon-rich surfaces into continuous oxygen-rich films, with greater surface roughness. Contact angle tests showed rapid wetting on AA-rich surfaces versus poor wetting on neat or MMA-rich samples. Dielectric measurements showed that permittivity increased from 4.36 for the neat GTR to ∼11 for AA-rich grafts. The 50:50 AA:MMA composition achieved ∼8.0 at 100 Hz. Kelvin probe force microscopy confirmed increasing surface potential with AA content. Dispersion tests in mixed polar solvents showed that 50:50 and 60:40 grafted GTR remained suspended for over 8 h, while other formulations showed partial stabilization or faster settling, with significantly shorter suspension times for neat or homopolymer-grafted samples. These findings demonstrate a tunable, initiator-free method to enhance interfacial polarity, dielectric response, and colloidal stability of GTR, enabling its use in coatings, adhesives, and dielectric elastomers.
地面轮胎橡胶是一种丰富的二次聚合物资源,但其老化的非极性表面限制了其与极性基质的相容性。该研究提出了一种可扩展的丙烯酸(AA)和甲基丙烯酸甲酯(MMA)在低温铣削GTR上的接枝共聚,由铣削过程中产生的机械自由基引发,无需外部引发剂。通过改变AA:MMA的比例,得到极性可调的接枝共聚物,并与表面和分散性能相关。光谱分析证实共接枝成功,主成分分析确定了成分趋势。电子顺磁共振显示自由基消耗接近完全。热重分析证实了表面限制改性。增加AA含量可使断裂的富碳表面转变为连续的富氧膜,表面粗糙度增大。接触角测试表明,在富含aa的表面快速润湿,而在整洁或富含mma的样品上润湿较差。介电测量表明,纯GTR的介电常数从4.36增加到富aa接枝的介电常数为~ 11。50:50 AA:MMA组合在100 Hz下达到了~ 8.0。开尔文探针力显微镜证实,表面电位随AA含量的增加而增加。在混合极性溶剂中的分散测试表明,50:50和60:40接枝的GTR悬浮时间超过8小时,而其他配方的GTR表现出部分稳定或更快的沉降,纯聚合物或均聚接枝的GTR悬浮时间明显缩短。这些发现证明了一种可调的、无引发剂的方法可以增强GTR的界面极性、介电响应和胶体稳定性,使其能够用于涂料、粘合剂和介电弹性体。
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引用次数: 0
Molecular engineering of fluorene–thiophene architectures toward enhanced conjugation-dependent electrochromic energy storage 面向增强偶联依赖性电致变色储能的芴-噻吩结构的分子工程
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2026-01-05 DOI: 10.1016/j.eurpolymj.2026.114498
Jianhua Lv , Yuting Song , Yunjiao Jiang , Zibo Wei , Cheng Liu , Wang Zhang , Jian Liu , Beili Lu , Biao Huang , Jiayu Tao
Electrochromic polymers capable of simultaneously delivering optical modulation and energy storage functions are of great interest for next-generation smart energy devices. In particular, precise molecular engineering of conjugated backbones offers an effective strategy to regulate electronic structure, ion transport, and charge storage behavior. A series of fluorene–thiophene conjugated polymers (P3TF, P2TF, and P2TTF) were designed and electrochemically synthesized to investigate the impact of molecular conjugation length and substitution position on electrochromic and energy storage performance. The UV–Vis absorption spectra of three monomers and their corresponding polymer films in the neutral state exhibited a consistent trend of gradual red-shift in the maximum absorption (P2TTF > P2TF > P3TF). This evolution reflects the intrinsic structural effect of increasing thiophene content and optimized substitution position, which collectively enhance the π-conjugation and reduce the electronic bandgap. Electrochromic studies showed that P3TF achieved a high optical contrast of 72 % at 1100 nm. Galvanostatic charge–discharge testing revealed significantly highiest areal capacitances for P2TTF (9.29 mF/cm2 at 0.8 mA/cm2) compared with P3TF and P2TF. Meanwhile, P2TTF shows superior stability in terms of both electrochromic and energy storage performance. The P2TTF-based electrochromic energy storage device, could power a LED light for over 15 s, maintaining over 86 % of its capacitance after 1500 cycles. These results highlight the critical role of molecular engineering in regulating conjugation and morphology to achieve synergistic electrochromic–energy storage performance.
能够同时提供光调制和能量存储功能的电致变色聚合物是下一代智能能源设备的重要研究方向。特别是,共轭骨架的精确分子工程提供了一种有效的策略来调节电子结构、离子传输和电荷存储行为。设计并合成了一系列芴-噻吩共轭聚合物(P3TF、P2TF和P2TTF),研究了分子共轭长度和取代位置对电致变色性能和储能性能的影响。三种单体及其相应的中性态聚合物膜的紫外-可见吸收光谱在最大吸收(P2TTF > P2TF > P3TF)处表现出一致的逐渐红移趋势。这种演变反映了增加噻吩含量和优化取代位置的内在结构效应,共同增强了π共轭性,减小了电子带隙。电致变色研究表明,P3TF在1100nm处实现了72%的高光学对比度。恒流充放电测试显示,与P3TF和P2TF相比,P2TTF在0.8 mA/cm2时的面电容显著高于P2TF (9.29 mF/cm2)。同时,P2TTF在电致变色性能和储能性能方面均表现出优异的稳定性。基于p2ttf的电致变色储能装置可以为LED灯供电超过15秒,在1500次循环后保持超过86%的电容。这些结果强调了分子工程在调节共轭和形态以实现协同电致变色储能性能方面的关键作用。
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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 : 2026-01-02 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
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 : 2026-01-02 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
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 : 2026-01-02 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。
{"title":"Nonconventional fluorescent copolymers synthesized from cyclic carbonates and diazoacetates via a post-addition strategy","authors":"Xiang-Xiang Jia,&nbsp;Hong-Lei Li,&nbsp;Xiao-Jie Lu,&nbsp;Xiao-Chi Li,&nbsp;Zhi-Ling Ye,&nbsp;Xu Wang,&nbsp;Jun-Chuan Wang,&nbsp;Hui Wang,&nbsp;Xiang-Feng Wu","doi":"10.1016/j.eurpolymj.2025.114492","DOIUrl":"10.1016/j.eurpolymj.2025.114492","url":null,"abstract":"<div><div>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)<sub>2</sub>. 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.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"243 ","pages":"Article 114492"},"PeriodicalIF":6.3,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939773","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 review on regulating the mechanical properties and phase transition temperature of UCST hydrogels UCST水凝胶力学性能和相变温度的调控研究进展
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-12-31 DOI: 10.1016/j.eurpolymj.2025.114482
Mengqi Chen , Rong Liu , Yongyi Yang , Qihao Bai , Li Xie , Huang Zhu
Hydrogels formed by polymers with upper critical solution temperature (UCST) exhibit delicate thermos- responsiveness, being highly susceptible to subtle variations in chain structures and environmental conditions, which are particularly suitable for precision-demanding applications. This unique characteristic has consequently garnered significant interdisciplinary research attention in recent years. UCST hydrogels exhibit the advantageous property of tunable phase transition temperatures, however, their practical applications are often constrained by inadequate mechanical strength. Here, this review systematically explores the mechanical property and phase transition temperature modulation strategies, as well as underlying regulatory mechanisms of UCST hydrogels, while critically assessing their emerging commercial applications. Through this comprehensive analysis, we aim to advance the rational design of UCST-based hydrogel systems and thereby facilitate their commercial transformation.
由具有较高临界溶液温度(UCST)的聚合物形成的水凝胶表现出微妙的热响应性,极易受到链结构和环境条件的细微变化的影响,特别适用于精度要求高的应用。近年来,这一独特的特征引起了跨学科研究的广泛关注。UCST水凝胶具有相变温度可调的优点,但其实际应用往往受到机械强度不足的限制。本文系统地探讨了UCST水凝胶的力学性能、相变温度调节策略以及潜在的调节机制,同时对其新兴的商业应用进行了批判性评估。通过这一综合分析,我们旨在推动基于ucst的水凝胶体系的合理设计,从而促进其商业转化。
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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 : 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
Corrigendum to “Overcoming the PEG dilemma with Poly(2-ethyl-2-oxazoline) lipids in lipid nanoparticle formulations”. [Eur. Polym. J. 241 (2025) 114392] “在脂质纳米颗粒配方中克服聚乙二醇困境(2-乙基-2-恶唑啉)脂质”的勘误表。(欧元。变异较大。J. 241 (2025) 114392]
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-12-30 DOI: 10.1016/j.eurpolymj.2025.114467
Randall W. Moreadith, Wookhyun Kim, Kelley Smith, Kunsang Yoon, Rebecca Weimer, Zhihao Fang
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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 : 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
Optimization of intermolecular interactions in poly(propylene 2,4-furanoate) copolymers: an ecodesign case study towards high-performance, biobased, biodegradable food packaging 聚(2,4-呋喃酸丙烯)共聚物分子间相互作用的优化:面向高性能、生物基、可生物降解食品包装的生态设计案例研究
IF 6.3 2区 化学 Q1 POLYMER SCIENCE Pub Date : 2025-12-30 DOI: 10.1016/j.eurpolymj.2025.114480
Enrico Bianchi , Michelina Soccio , Valentina Siracusa , Shanmugam Thiyagarajan , Nadia Lotti
Biobased 2,4-furandicarboxylic acid (2,4-FDCA), a structural isomer of 2,5-FDCA, has recently led to the synthesis of high molecular weight polyesters with promising properties for food packaging. Among them, poly(propylene 2,4-furanoate) (2,4-PPF), the only polymer in the glassy state at room temperature, showed limited functional performance, attributed to its reduced macromolecular mobility. To address this, 2,4-PPF was copolymerized with biobased poly(propylene succinate) (PPS) via reactive blending, aiming to optimize Tg and chain flexibility. A physical blend, block and random copolymers were processed into freestanding films and thoroughly characterized (NMR, GPC, WAXD, DSC, TGA, tensile and gas permeability tests). Block and random copolymers showed excellent mechanical properties, including elongation at break exceeding 2400%, and outstanding gas barrier, competitive with commercial poly(ethylene vinyl alcohol). These enhancements are attributed to the predicted enhancement intermolecular interactions caused by the Tg close to room temperature, which increased chain mobility, thus optimized interchain hydrogen bonding and π–π interactions. Biodegradation under composting conditions was also assessed. Gravimetric, NMR, GPC, DSC, and WAXD analyses revealed preferential degradation of PPS segments and significant molecular weight reduction in the copolymers. Overall, our results demonstrate the potential of copolymers based on 2,4-PPF as biobased, flexible, monolayer and partially biodegradable materials for sustainable food packaging. Most importantly, this work highlights the critical importance of intermolecular interactions as a tool for the ecodesign of furan-based polymers, to unlock higher levels of functional and sustainable performance.
生物基2,4-呋喃二羧酸(2,4- fdca)是2,5- fdca的一种结构异构体,近年来合成了具有良好食品包装性能的高分子量聚酯。其中,聚(2,4-呋喃酸丙烯)(2,4- ppf)是唯一在室温下处于玻璃态的聚合物,由于其大分子迁移率降低,其功能性能有限。为了解决这个问题,2,4- ppf通过反应共混与生物基聚琥珀酸丙烯(PPS)共聚,旨在优化Tg和链的柔韧性。将物理共混、嵌段和无规共聚物加工成独立薄膜,并进行全面表征(NMR、GPC、WAXD、DSC、TGA、拉伸和透气性测试)。嵌段共聚物和无规共聚物表现出优异的力学性能,断裂伸长率超过2400%,具有优异的气体阻隔性,可与商业聚乙烯醇相媲美。这些增强是由于Tg在接近室温时引起的分子间相互作用增强,从而提高了链的迁移率,从而优化了链间氢键和π -π相互作用。并对堆肥条件下的生物降解进行了评价。重量、核磁共振、GPC、DSC和WAXD分析显示PPS片段优先降解,共聚物的分子量显著降低。总的来说,我们的研究结果证明了基于2,4- ppf的共聚物作为生物基、柔性、单层和部分可生物降解的可持续食品包装材料的潜力。最重要的是,这项工作强调了分子间相互作用作为呋喃基聚合物生态设计工具的重要性,以解锁更高水平的功能和可持续性能。
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引用次数: 0
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European Polymer Journal
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