European Polymer Journal最新文献_第3页

Ecofriendly bioplastics from biowaste: Antimicrobial and functional enhancements for sustainable packaging 从生物废弃物中提取生态友好型生物塑料：用于可持续包装的抗菌剂和功能增强剂

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-05 DOI: 10.1016/j.eurpolymj.2024.113557

Dilip Kumar Chandra , Awanish Kumar, Chinmaya Mahapatra

Food waste exacerbates greenhouse gas emissions and environmental degradation, while the prevalent use of conventional plastics in food packaging, characterized by their cost-efficiency, lightweight nature, and durability, has intensified environmental concerns through increased greenhouse gas emissions and waste accumulation. In response, the utilization of biowaste-derived biopolymers for bioplastic production has emerged as a promising strategy within the framework of the circular economy. Although these bioplastics offer advantages such as biodegradability and bio-based origins, early formulations were constrained by suboptimal mechanical strength, hydrophilicity, and barrier properties, necessitating the incorporation of advanced additives. Recent advancements have centred on improving the functionality of bioplastics derived from biowaste through the integration of specialized additives. These enhancements, including the incorporation of functional fillers and reinforcement agents, have significantly augmented the tensile strength, Young’s modulus, thermal stability, and water vapor barrier performance of bioplastics. Additionally, these additives impart notable antimicrobial and antioxidant properties, which enhance food safety and extend shelf life while maintaining eco-friendly characteristics. This review comprehensively examines the latest innovations in biowaste-to-bioplastics technologies, focusing on the integration of antimicrobial, antioxidant, and physiochemical enhancements. By highlighting these advancements, the review emphasizes the transformative potential of biowaste-derived bioplastics in developing sustainable food packaging solutions and advancing a circular economy.

食品废弃物加剧了温室气体排放和环境退化，而食品包装中普遍使用的传统塑料具有成本效益高、重量轻和耐用的特点，但却增加了温室气体排放和废弃物积累，从而加剧了对环境的担忧。为此，在循环经济的框架下，利用生物废弃物衍生的生物聚合物生产生物塑料已成为一项前景广阔的战略。虽然这些生物塑料具有生物可降解性和生物基来源等优势，但早期的配方受到机械强度、亲水性和阻隔性能不理想的限制，因此必须加入先进的添加剂。最近的进展主要集中在通过添加特殊添加剂来提高从生物废弃物中提取的生物塑料的功能性。这些改进包括加入功能性填料和增强剂，大大提高了生物塑料的拉伸强度、杨氏模量、热稳定性和水蒸气阻隔性能。此外，这些添加剂还具有显著的抗菌和抗氧化性能，可提高食品安全性，延长保质期，同时保持环保特性。本综述全面探讨了生物废弃物转化为生物塑料技术的最新创新，重点关注抗菌、抗氧化和理化增强功能的整合。通过重点介绍这些先进技术，综述强调了生物废弃物衍生生物塑料在开发可持续食品包装解决方案和推进循环经济方面的变革潜力。

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引用次数: 0

Antimicrobial peptide-based pH-responsive Polyvinyl alcohol hydrogel artificial vascular grafts with excellent antimicrobial and hematologic compatibility 基于抗菌肽的 pH 响应型聚乙烯醇水凝胶人工血管移植物具有优异的抗菌性和血液相容性

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-05 DOI: 10.1016/j.eurpolymj.2024.113554

Ying Liu , Qingyun Ma , Zhixuan Wang , Xinxin Shang , Yuting Lan , Guoping Guan , Lu Wang

Thrombosis and infection are the primary challenges limiting the clinical application of small-diameter artificial blood vessels. Numerous studies have focused on improving the hemocompatibility of artificial vascular materials, addressing properties such as anticoagulant activity, antithrombogenicity, low hemolysis rates, and reduced platelet adhesion. However, there has been comparatively less attention given to the antibacterial properties of these materials. This study utilizes polyester braided tubes and PVA/PAAm hydrogel materials, combined with surface modification techniques, to develop a pH-responsive antibacterial hydrogel artificial blood vessel graft. The hydrogel surface was grafted with a polymer brush hierarchical structure, and antimicrobial peptide MLT was immobilized to confer antibacterial properties. Additionally, 2,3-dimethylmaleic anhydride (DMMA) was covalently attached as a shielding group to achieve an environment-responsive strategy. The research demonstrates that this artificial blood vessel graft exhibits structural stability, excellent mechanical properties, and good cellular and hemocompatibility. Furthermore, it exhibits pH-responsive capabilities, triggering efficient antibacterial activity in low pH environments. The modified antibacterial hydrogel artificial blood vessel material shows low hemolysis rates, excellent anticoagulant properties, and reduced platelet adhesion. Therefore, the strategy of combining MLT with DMMA may effectively enhance the hemocompatibility and responsive antibacterial performance of artificial blood vessel materials.

血栓形成和感染是限制小直径人造血管临床应用的主要挑战。大量研究都集中在改善人造血管材料的血液相容性，解决抗凝活性、抗血栓形成、低溶血率和减少血小板粘附等特性。然而，人们对这些材料的抗菌性能关注相对较少。本研究利用聚酯编织管和 PVA/PAAm 水凝胶材料，结合表面改性技术，开发出一种 pH 值响应型抗菌水凝胶人工血管移植材料。水凝胶表面接枝了聚合物刷分层结构，并固定了抗菌肽 MLT 以赋予其抗菌特性。此外，还共价连接了 2,3-二甲基马来酸酐（DMMA）作为屏蔽基团，以实现环境响应策略。研究表明，这种人造血管移植物具有结构稳定性、优异的机械性能以及良好的细胞和血液相容性。此外，它还具有 pH 值响应能力，能在低 pH 值环境中激发高效的抗菌活性。改性抗菌水凝胶人工血管材料溶血率低、抗凝血性能优异、血小板粘附性降低。因此，将 MLT 与 DMMA 结合的策略可有效提高人造血管材料的血液相容性和响应性抗菌性能。

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引用次数: 0

Solid-state solvatochromism of oxazolidine in multi-functionalized copolymer nanoparticles: Development of advanced materials with multi-color fluorescence 草唑烷在多功能共聚物纳米颗粒中的固态溶解变色：开发具有多色荧光的先进材料

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-05 DOI: 10.1016/j.eurpolymj.2024.113555

Amin Abdollahi , Younes Habibi , Bita Ghasemi , Zahra Mohamadnia

Investigating the solvatochromism of stimuli-chromic compounds such as oxazolidine in polymer matrices with various polarities or functionalities is a unique approach to developing advanced materials for anticounterfeiting, sensor, optoelectronic, and displayers. In a novel strategy, multi-functionalized copolymer nanoparticles were synthesized by copolymerization of methyl methacrylate (MMA) with various functional comonomers in emulsion media for post-polymerization modification with oxazolidine and investigation of its solvatochromism in both colloidal solution and solid phase. The particle size and morphology of nanoparticles were influenced significantly by the polarity of functional groups, and the morphology evolution from sphere to anisotropic shapes was observed by increasing the polarity of functional groups. Investigation of oxazolidine solvatochromism in colloidal solution and solid polymer powders indicated different mechanisms for solvatochromism, in which the polarity of media is the main effective parameter in colloidal solution and the polarity of functional groups in the polymer structure is the main effective parameter in solid polymer phase. The solvatochromism of oxazolidine was confirmed by observed red shift and blue shift in UV–Vis and fluorescence spectra, in which the intensity of absorbance and emission peaks was changed as a function of the polarity of functional groups. Solvatochromic photoluminescent polymer nanoparticles were used for several advanced applications such as solid anticounterfeiting inks to information encryption, dual-mode visualization of latent fingerprints, and also development of organic light-emitting diodes (OLEDs). For the first time, the results indicate a significant effect of polymer chain local polarity induced by functional groups on the tuning of optical properties of the oxazolidine by the solid-state solvatochromic phenomenon. Solvatochromism of oxazolidine in functionalized polymer nanoparticles is an interesting approach to developing novel intelligent materials that have advanced applications in different fields such as anticounterfeiting and information encryption, optoelectronic, polarity sensor, and visualization of latent fingerprints.

研究噁唑烷等刺激变色化合物在具有不同极性或功能性的聚合物基质中的溶解变色性是开发用于防伪、传感器、光电和显示器的先进材料的一种独特方法。在一种新颖的策略中，通过在乳液介质中将甲基丙烯酸甲酯（MMA）与各种功能共聚单体共聚，合成了多功能共聚物纳米粒子，然后用恶唑烷对其进行聚合后改性，并研究了其在胶体溶液和固相中的溶解变色性。纳米粒子的粒度和形态受官能团极性的影响很大，随着官能团极性的增加，纳米粒子的形态也从球形演变为各向异性的形状。对恶唑烷在胶体溶液和固体聚合物粉末中溶解变色的研究表明，溶解变色的机理不同，在胶体溶液中，介质的极性是主要的有效参数，而在固体聚合物相中，聚合物结构中官能团的极性是主要的有效参数。通过观察紫外-可见光谱和荧光光谱中的红移和蓝移，证实了噁唑烷的溶解变色作用，其中吸收峰和发射峰的强度随官能团的极性而变化。溶变色光致发光聚合物纳米粒子被用于多种先进的应用领域，如信息加密的固体防伪油墨、潜伏指纹的双模式可视化，以及有机发光二极管（OLED）的开发。研究结果首次表明，官能团诱导的聚合物链局部极性对通过固态溶解变色现象调整恶唑烷的光学特性有显著影响。草唑烷在功能化聚合物纳米粒子中的溶解变色现象是开发新型智能材料的一种有趣方法，这种材料在防伪和信息加密、光电、极性传感器和潜伏指纹可视化等不同领域都有先进的应用。

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引用次数: 0

An overview on potential of novel photoinitiators for vat photopolymerization-based 3D/4D printing formulations 新型光引发剂在基于大桶光聚合的 3D/4D 打印配方中的应用潜力综述

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-05 DOI: 10.1016/j.eurpolymj.2024.113552

Amirhossein Enayati-Gerdroodbar , Amirreza Khayati , Mostafa Ahmadi , Behzad Pourabbas , M. Ali Aboudzadeh , Mehdi Salami-Kalajahi

In recent years, three-dimensional (3D) printing has emerged as an outstanding technique for creating intricate 3D structures with complex geometries. Additionally, four-dimensional (4D) printing technology has attracted attention due to its ability to reshape of 3D printed structures under external stimuli over time. The application of this technique in various fields such as polymer recycling, coating, energy storage systems, medical tools, and hydrogels is due to recent advances in functional materials. Vat photopolymerization-based 3D (VP-based 3D) printing relies on photopolymerization reactions, which are commonly used in techniques such as digital light processing (DLP) and stereolithography (SLA). These techniques are associated with critical parameters such as curing kinetics, printing speed, and resolution. Photoinitiators (PIs) as one of the components of the formulation of photo-resins and photo-inks can be very effective in optimizing these parameters. There are challenges in using common photoinitiators, such as yellowing effect, migration to the surface, toxicity, and bio-incompatibility. To address these challenges, recent researches have been directed towards the synthesis of new photoinitiators based on bio-inspired compounds, inorganic particles, aliphatic structures, transition metals, fluorescent compounds, photo-sensitizers, and macro-structure-based photoinitiators. This review article aims to explore recent studies on the synthesis of new photoinitiators in the application of 3D and 4D printing. Also, it examines various chemistries in the design of photoinitiators and describes the relationship between the curing kinetic, type of monomers, and printing speed. Moreover, it highlights the potential of synthesized photoinitiators in addressing challenges with mechanical properties, resolution, and transparency of the printed part. Furthermore, this article effectively categorizes various types of photoinitiators based on organic and inorganic compounds. Finally, the article aims to generate interest and stimulate more research in the use of new photoinitiators in industrial applications and formulation towards sustainable 3D and 4D printed structures.

近年来，三维（3D）打印技术已成为制造复杂几何形状的三维结构的杰出技术。此外，四维（4D）打印技术因其能够在外部刺激下随时间重塑三维打印结构而备受关注。这种技术在聚合物回收、涂层、储能系统、医疗工具和水凝胶等多个领域的应用，得益于功能材料的最新进展。基于大桶光聚合的三维打印（VP-based 3D ）依赖于光聚合反应，而光聚合反应通常用于数字光处理（DLP）和立体光刻（SLA）等技术中。这些技术与固化动力学、打印速度和分辨率等关键参数有关。光引发剂（PI）作为光树脂和光墨水配方的成分之一，可以非常有效地优化这些参数。在使用普通光引发剂的过程中存在一些挑战，如黄化效应、向表面迁移、毒性和生物相容性。为了应对这些挑战，最近的研究方向是合成基于生物启发的化合物、无机颗粒、脂肪族结构、过渡金属、荧光化合物、光敏剂和基于宏观结构的光引发剂。这篇综述文章旨在探讨在三维和四维打印应用中合成新型光引发剂的最新研究。此外，文章还探讨了光引发剂设计中的各种化学成分，并描述了固化动力学、单体类型和打印速度之间的关系。此外，文章还强调了合成光引发剂在应对打印部件的机械性能、分辨率和透明度等挑战方面的潜力。此外，本文还根据有机和无机化合物对各类光引发剂进行了有效分类。最后，文章旨在激发人们对新型光引发剂在工业应用和配方中的使用的兴趣，并推动更多研究，以实现可持续的三维和四维打印结构。

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引用次数: 0

Frontal polymerization of acrylamide/GelMA/gelatin hydrogels with controlled mechanical properties and inherent self-recovery 正面聚合具有可控机械性能和固有自恢复能力的丙烯酰胺/GelMA/明胶水凝胶

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-04 DOI: 10.1016/j.eurpolymj.2024.113551

Luana Di Lisa , Mariangela Rea , Daniele Nuvoli , Maria Letizia Focarete , Cristiano Albonetti , Alberto Mariani

Low mechanical resistance represents one of the significant problems of hydrogels, limiting their applicability in many fields. One approach to overcome this issue is synthesizing interpenetrating polymeric networks. In this work, the frontal polymerization technique was used to synthesize two series of novel hydrogels: (i) poly(acrylamide) (PAAm)-based hydrogels copolymerized/crosslinked with methacrylate gelatin (GelMA) (AAm-GelMA copolymer networks), and (ii) semi-IPN made of AAm-GelMA copolymer networks and a physically crosslinked gelatin network. With the final objective of improving the rheological, mechanical, morphological, thermal, and swelling properties of PAAm hydrogels, GelMA with two different degrees of methacrylation (30 and 75 mol%) was used. Interactions between GelMA chains, which give rise to physical network formation (i.e., GelMA-GelMA interactions), resulted in very efficient crosslinking for PAAm-based hydrogels, requiring a significantly lower methacrylic group concentration (0.04 mol%) for hydrogel formation compared to N,N′-methylene-bis-acrylamide (1 mol%), which is the agent typically used as a crosslinker for PAAm. Furthermore, the degree of GelMA methacrylation markedly affected the properties of the hydrogels. For example, regarding the swelling degree, hydrogels containing 22 wt% of GELMA30 had an SR% of 2870, while those containing the same amount of GELMA75 swelled much less (870 %). The introduction of gelatin as a secondary network in semi-IPNs influenced the rheological and mechanical properties, resulting in increased hydrogel modulus and stiffness attributed to enhanced physical interactions within the network. Finally, dynamic rheological shear strain and cyclic loading compression tests demonstrated exceptional recovery capabilities in all hydrogel formulations: samples subjected to alternating low (0.1 %) and high (300 % or 10 %) shear strain demonstrated a complete and prompt recovery of G′ and G″ values.

低机械阻力是水凝胶的主要问题之一，限制了其在许多领域的应用。克服这一问题的方法之一是合成互穿聚合物网络。本研究采用正面聚合技术合成了两个系列的新型水凝胶：(i) 与甲基丙烯酸明胶（GelMA）共聚/交联的聚（丙烯酰胺）（PAAm）基水凝胶（AAm-GelMA 共聚物网络），以及 (ii) 由 AAm-GelMA 共聚物网络和物理交联明胶网络组成的半 IPN。为了改善 PAAm 水凝胶的流变、机械、形态、热和膨胀特性，我们使用了两种不同甲基丙烯酸化程度（30 和 75 摩尔%）的 GelMA。与通常用作 PAAm 交联剂的 N,N′-亚甲基双丙烯酰胺（1 摩尔%）相比，形成水凝胶所需的甲基丙烯酸基团浓度（0.04 摩尔%）要低得多。此外，GelMA 甲基丙烯酸化程度对水凝胶的性能也有明显影响。例如，在溶胀度方面，含有 22 wt% GELMA30 的水凝胶的 SR% 为 2870，而含有相同数量 GELMA75 的水凝胶的溶胀度要低得多（870%）。在半 IPN 中引入明胶作为辅助网络会影响流变和机械性能，导致水凝胶模量和硬度增加，这归因于网络内物理相互作用的增强。最后，动态流变剪切应变和循环加载压缩测试表明，所有水凝胶配方都具有卓越的恢复能力：交替承受低（0.1%）和高（300% 或 10%）剪切应变的样品都能迅速完全恢复 G′和 G″值。

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引用次数: 0

A novel bio-based autocatalytic amide-type phthalonitrile monomer: Synthesis, curing kinetics and thermal properties 一种新型生物基自催化酰胺型邻苯二腈单体：合成、固化动力学和热性能

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-04 DOI: 10.1016/j.eurpolymj.2024.113550

Zhiyi Guo, Qiufei Chen, Zhicheng Wang, Athar Ali Khan Gorar, Zhongcheng Pan, Jun Wang, Wenbin Liu

A bio-based bisphenol compound (DFA) was prepared using bisphenolic acid and furfurylamine in biomass as raw materials. Then, a bio-based amide phthalonitrile monomer (DFAP) was obtained in an environmentally friendly solvent. Nuclear magnetic resonance and Fourier transform infrared spectroscopy (FT-IR) proved the successful synthesis of DFA and DFAP. The curing behavior and curing kinetics of the polymer were studied using FT-IR and differential scanning calorimetry. Calculate the activation energy using the isoconversion method. The SB(m, n) autocatalytic reaction model describing the curing process of poly(DFAP) was modified and fitted by introducing the variable activation energy model. The thermal stability, thermomechanical properties and processing properties of the resin were studied using technologies such as thermogravimetric analyzer, dynamic mechanical analyzer and rheometer. The results show that the prepolymer has a wide processing window and a low melt viscosity. Poly(DFAP) has a high glass transition temperature and excellent thermal stability.

以生物质中的双酚酸和糠胺为原料，制备了一种生物基双酚化合物（DFA）。然后，在一种环境友好型溶剂中获得了一种生物基酰胺邻苯二腈单体（DFAP）。核磁共振和傅立叶变换红外光谱（FT-IR）证明了 DFA 和 DFAP 的成功合成。利用傅立叶变换红外光谱和差示扫描量热法研究了聚合物的固化行为和固化动力学。使用等转化法计算活化能。通过引入可变活化能模型，对描述聚（DFAP）固化过程的 SB（m，n）自催化反应模型进行了修改和拟合。利用热重分析仪、动态机械分析仪和流变仪等技术对树脂的热稳定性、热机械性能和加工性能进行了研究。结果表明，该预聚物具有较宽的加工窗口和较低的熔体粘度。聚（DFAP）具有较高的玻璃化转变温度和出色的热稳定性。

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引用次数: 0

Green synthesis of lignin-based non-isocyanate polyurethanes as reusable, self-healable and removable adhesives 绿色合成木质素基非异氰酸酯聚氨酯，作为可重复使用、自愈合和可移除的粘合剂

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-04 DOI: 10.1016/j.eurpolymj.2024.113553

Dou Li , Bailiang Xue , Qinyu Zhao , Wenliang Wang , Xinping Li , Jialong Wen , Zhiwen Wang , Wei Zhao

Lignin-based non-isocyanate polyurethanes (LNIPUs) represent a class of polymers synthesized from lignin—an abundant, renewable polymer found in the cell walls of plants—without the use of toxic isocyanates. This makes LNIPUs an eco-friendly alternative to traditional petroleum-based polyurethanes. Despite their advantages, the synthesis of LNIPUs often entails complex processes, the use of additional catalysts, and highly polar solvents, which largely restrict their accessibility and practical applications. In this study, we present an higly efficient, catalyst-free, and solvent-free methodology for synthesizing LNIPUs. A series of novel LNIPUs were successfully prepared through a one-pot, catalyst-free and solvent-free polymerization reaction involving aminated fractionated lignin (ALF_E) and bis(6-membered cyclic carbonate) (6CC). We systematically investigated the properties of the resulting LNIPUs, with a particular focus on the adhesion performance. The incorporation of ALF_E significantly enhanced the adhesive properties of the resultant LNIPUs on aluminum, wood, and plastic substrates, achieving a maximum bonding strength of 3.09 MPa on aluminum. Furthermore, LNIPUs exhibit exceptional functionalities, including reusability, self-healing capabilities, and removability, along with improved thermal stability and photothermal properties.

木质素基非异氰酸酯聚氨酯（LNIPUs）是一类在不使用有毒异氰酸酯的情况下，从木质素（一种存在于植物细胞壁中的丰富的可再生聚合物）中合成的聚合物。这使得 LNIPU 成为传统石油基聚氨酯的环保型替代品。尽管 LNIPUs 具有诸多优点，但其合成过程通常比较复杂，需要使用额外的催化剂和高极性溶剂，这在很大程度上限制了其可获得性和实际应用。在本研究中，我们提出了一种高效、无催化剂和无溶剂的 LNIPU 合成方法。通过涉及胺化分馏木质素（ALFE）和双（6 元环碳酸酯）（6CC）的一锅式、无催化剂和无溶剂聚合反应，我们成功制备了一系列新型 LNIPU。我们系统地研究了所得 LNIPU 的特性，尤其关注其粘附性能。加入 ALFE 后，生成的 LNIPU 在铝、木材和塑料基材上的粘合性能明显增强，在铝基材上的最大粘合强度达到 3.09 兆帕。此外，LNIPU 还表现出卓越的功能性，包括可重复使用性、自愈能力和可移除性，以及更好的热稳定性和光热性能。

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引用次数: 0

The intramolecular aggregation of phosphaphenanthrene groups and benzene-terminated effect within linear phosphonate oligomers effectively enhanced the flame retardancy and toughness of epoxy resin 线性膦酸盐低聚物中的磷菲基团和苯端效应的分子内聚集可有效提高环氧树脂的阻燃性和韧性

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-04 DOI: 10.1016/j.eurpolymj.2024.113558

Xiao Wu , Lijun Qian , Juan Li , Wang Xi , Yong Qiu

To explore the potential of a flame retardant molecular structure that simultaneously enhances the flame retardancy and physical properties of epoxy resin (EP), benzene-terminated linear phosphonate oligomers Bz-DQPC-n were synthesized. Compared with the previously prepared linear bisphenol phosphonate oligomers DQPC-n, the benzene-terminated effect of Bz-DQPC-n molecules endows EP composites with better flame retardancy and toughness. In the vertical combustion (UL 94) test, Bz-DQPC-n/EP reached a V-0 rating. For the Bz-DQPC-2 molecule, the results revealed that under the same phosphorus contents, the limiting oxygen index (LOI) value of the Bz-DQPC-2/EP reached 38.2 %, which was higher than that of DQPC-2/EP. Furthermore, the peak heat release rate (pk-HRR) and total heat release rate (THR) of Bz-DQPC-2/EP were 677 kW/m² and 83 MJ/m². These values decreased by 54.7 % and 27.2 % in comparison to pure EP, respectively. In addition, the incorporation of Bz-DQPC-n can enhance the glass transition temperature (T_g) of EP composites. The flame retardant mechanism research demonstrated that Bz-DQPC-n molecules produced phosphorus-containing free radicals and aromatic compound fragments during gas-phase pyrolysis. These phosphorus-containing free radicals can interrupt or inhibit the combustion chain reaction process. A proportion of the aggregated phosphaphenanthrene groups decomposed to produce aromatic compounds that remained in the condensed phase, thereby enhancing the quality of the char layer. The investigation of the impact of the end-capping effect within Bz-DQPC-n molecules on the flame retardant behavior of EP composites offers a valuable reference for designing phosphaphenanthrene compounds with high flame retardant efficiency.

为了探索同时提高环氧树脂（EP）阻燃性和物理性能的阻燃分子结构的潜力，合成了苯封端的线性膦酸盐低聚物 Bz-DQPC-n。与之前制备的线性双酚膦酸酯低聚物 DQPC-n 相比，Bz-DQPC-n 分子的苯端效应赋予 EP 复合材料更好的阻燃性和韧性。在垂直燃烧（UL 94）测试中，Bz-DQPC-n/EP 达到了 V-0 级。对于 Bz-DQPC-2 分子，研究结果表明，在磷含量相同的情况下，Bz-DQPC-2/EP 的极限氧指数（LOI）值达到 38.2%，高于 DQPC-2/EP。此外，Bz-DQPC-2/EP 的峰值放热率（pk-HRR）和总放热率（THR）分别为 677 kW/m2 和 83 MJ/m2。与纯 EP 相比，这些数值分别降低了 54.7% 和 27.2%。此外，Bz-DQPC-n 的加入还能提高 EP 复合材料的玻璃化转变温度（Tg）。阻燃机理研究表明，Bz-DQPC-n 分子在气相热解过程中会产生含磷自由基和芳香族化合物碎片。这些含磷自由基可打断或抑制燃烧链反应过程。一部分聚集的磷菲基团分解后产生的芳香族化合物留在凝结相中，从而提高了炭层的质量。研究 Bz-DQPC-n 分子内的端封效应对 EP 复合材料阻燃性能的影响，为设计具有高阻燃效率的磷菲化合物提供了宝贵的参考。

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引用次数: 0

Synthesis of miktoarm star-shaped polymers with polyoxazoline arms and macrocyclic calix[8]arene branching center 合成具有聚恶唑啉臂和大环钙[8]炔支链中心的米克托臂星形聚合物

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-11-01 DOI: 10.1016/j.eurpolymj.2024.113547

N.D. Kozina, T.U. Kirila, A.N. Blokhin, A.P. Filippov, A.V. Tenkovtsev

A novel approach to the synthesis of miktoarm star-shaped poly(2-alkyl-2-oxazolines) with calix[8]arene core was developed using a combination of the “core first” (grafting from) and “grafting onto” methods. The star-shaped polymers of A₈B₈ type with grafted poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) arms were obtained using calix[8]arene based multifunctional branching center with sulfonyl chloride initiating moieties and as well as acyl hydrazide termination ones. The polymer structure has been confirmed by ¹H NMR spectroscopy and UV spectroscopy. The molar mass characteristics of the samples were determined by size-exclusion chromatographic and light scattering. It was experimentally confirmed that all synthesized polymers had the target arm number, namely 8 or 16. The obtained miktoarm stars were characterized by narrow molar mass distributions, and the polymerization degree of the arms was 15. The synthesized stars had a high intramolecular density, which increased with the arm number. It is shown that the thermoresponsiveness of the studied stars depends on the number and structure of arms and on intramolecular density, while molecular mass is not a decisive factor determining their LCST behavior.

For miktoarm stars, phase separation temperatures do not depend on the grafting configuration of poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) on the upper or lower rim of calix[8]arene.

采用 "先接芯"（从芯接枝）和 "接枝到芯 "相结合的方法，开发了一种合成以钙钛矿[8]炔为芯的米克托臂星形聚（2-烷基-2-噁唑啉）的新方法。利用萼[8]炔基多功能支化中心、磺酰氯引发分子和酰肼终止分子，获得了具有接枝聚（2-乙基-2-噁唑啉）和聚（2-异丙基-2-噁唑啉）臂的 A8B8 型星形聚合物。1H NMR 光谱和紫外光谱证实了聚合物的结构。样品的摩尔质量特性是通过尺寸排阻色谱法和光散射法测定的。实验证实，所有合成聚合物都具有目标臂数，即 8 或 16。获得的米克托臂星形物具有摩尔质量分布窄的特点，臂的聚合度为 15。合成的星形物具有较高的分子内密度，并随着臂数的增加而增加。对于米克托臂星体，相分离温度并不取决于聚（2-乙基-2-噁唑啉）和聚（2-异丙基-2-噁唑啉）在卡利克[8]炔上缘或下缘的接枝构型。

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引用次数: 0

Bottlebrush polymers via ring-opening metathesis polymerization (ROMP): Synthesis, properties and applications 通过开环偏聚聚合（ROMP）制备的瓶坯聚合物：合成、性能和应用

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-31 DOI: 10.1016/j.eurpolymj.2024.113546

Smruti Rekha Rout , Gowtham Kenguva , Shaaba Mansuri , Manu KR , Rambabu Dandela , Nabendu B. Pramanik

Bottlebrush polymers (BBPs) are a class of branch or graft macromolecules with polymeric side chains attached to linear backbone leading to cylindrical or worm like structures. Due to their unique architecture of polymers with long and densely grafted side chains, BBPs have attracted notable numbers of novel and unique properties useful for various applications from tissue engineering to photonics. Their unique structures characterized by densely-grafted side chains, allows for precise control of their properties and reduces issues with entanglements. This review delineates the recent advances in the synthesis of BBPs via living Ring-Opening Metathesis Polymerization (ROMP) and their properties, applications, highlighting the challenges and solutions in controlling their chemical structures, compositions and uses. Notably, the development of ROMP has transformed the polymer synthesis, specially the synthesis of bottlebrush polymers. ROMP is very powerful technique for achieving very high conversion of macromonomer for a range of concentrations and molecular weights of macromonomer leading to formation of BBPs with systemically varying backbone and side-chain lengths. The combination of BBPs’ versatility with ROMP’s precision in controlling the polymer’s size, shape, and functionality offers significant advantages in materials synthesis. By integrating these approaches, researchers can create customized bottlebrush polymeric materials with tailored properties, enhancing advancements in nanotechnology, energy storage and biomedical engineering. To the best of our knowledge there is no review reported on the synthesis of BBPs via ROMP.

Bottlebrush 聚合物（BBPs）是一类分支或接枝高分子，其聚合物侧链附着在线性骨架上，形成圆柱形或蠕虫状结构。由于其独特的聚合物结构具有长而密集的接枝侧链，BBPs 具有大量新颖独特的特性，可用于组织工程和光子学等各种应用领域。以密集接枝侧链为特征的独特结构可以精确控制其特性，并减少缠结问题。本综述介绍了通过活环开环元合成聚合法（ROMP）合成 BBPs 的最新进展及其特性和应用，重点介绍了在控制其化学结构、组成和用途方面所面临的挑战和解决方案。值得注意的是，ROMP 的发展改变了聚合物合成，特别是瓶丛聚合物的合成。ROMP 是一种非常强大的技术，可在各种浓度和分子量的大单体中实现非常高的大单体转化率，从而形成具有系统性不同骨架和侧链长度的 BBPs。BBPs 的多功能性与 ROMP 在控制聚合物大小、形状和功能方面的精确性相结合，为材料合成提供了显著优势。通过整合这些方法，研究人员可以制造出具有定制特性的瓶绒聚合物材料，从而推动纳米技术、能量存储和生物医学工程的发展。据我们所知，目前还没有关于通过 ROMP 合成 BBPs 的综述。

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引用次数: 0