European Polymer Journal最新文献_第6页

Sustainable recovery of monomers from PET and PC waste via Thermocatalytic depolymerization for synthesis of polycarbonates and co-polycarbonates 通过热催化解聚从 PET 和 PC 废弃物中可持续回收单体，用于合成聚碳酸酯和共聚碳酸酯

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-22 DOI: 10.1016/j.eurpolymj.2024.113516

Loganathan M , Rajendraprasad M , A. Murugesan , Ju Yi Lee , Kiran B Manjappa

The increasing global demand for sustainable plastics recycling methods has propelled the research and development of innovative depolymerization processes. The Thermocatalytic depolymerization (TCDP) of polyethylene terephthalate (PET) and polycarbonate (PC) has been performed at 200 ℃. Ethylene glycol (EG) is used as a reactant and as well a polymer bond-cleaving agent and Yttrium Oxide (Y₂O₃) is used as an effective catalyst. Y₂O₃ acted as a dual role during depolymerization reaction, which converts EG into cyclic ethylene oxide (CEO) and as well as to break the ester and carbonate bonds in the polymer structure of PET and PC respectively. The TCDP reaction conditions were optimized and the maximum quantity of Bis(2-hydroxyethyl) terephthalate (BHET) (80%) and (Bisphenol A (BPA)) (83%) has been recovered by TCDP reaction of PET and PC respectively. The polycarbonate and co-polycarbonate (Co-PC) were synthesized using recovered BPA and BHET with triphosgene via polycondensation reaction. The structure of monomers and polymers was confirmed by existing analytical (FTIR, NMR, XRD and GPC) techniques. The thermal properties of PC and Co-PC were performed by TG analysis. The TGA results reveal that the degradation temperature (T_d) of PC and Co-PC are observed at 420.5 and 442.8 °C respectively, which shows that the T_d of Co-PC has been increased by 22 ℃ than PC. The TCDP process is an effective method to recover specific value-added products from waste plastics, which could be made into a new versatile material for different applications. This research finding will provide a new direction to convert plastic waste into useful chemicals, which could reduce waste plastic and their carbon footprint and contribute to a more sustainable future by reusing plastic materials and achieving a circular economy.

全球对可持续塑料回收方法的需求日益增长，推动了创新型解聚工艺的研究和开发。聚对苯二甲酸乙二酯（PET）和聚碳酸酯（PC）的热催化解聚（TCDP）在 200 ℃ 下进行。乙二醇（EG）用作反应物和聚合物键裂解剂，氧化钇（Y2O3）用作有效催化剂。Y2O3 在解聚反应中起着双重作用，既能将 EG 转化为环氧乙烷 (CEO)，又能分别断开 PET 和 PC 聚合物结构中的酯键和碳酸键。通过优化 TCDP 反应条件，PET 和 PC 的 TCDP 反应分别回收了 80% 的对苯二甲酸二（2-羟乙基）酯 (BHET) 和 83% 的双酚 A (BPA)。利用回收的双酚 A 和 BHET 与三光气通过缩聚反应合成了聚碳酸酯和共聚碳酸酯（Co-PC）。单体和聚合物的结构通过现有的分析（傅立叶变换红外光谱、核磁共振、X 射线衍射和 GPC）技术得到了确认。PC 和 Co-PC 的热性能是通过 TG 分析得出的。TGA 分析结果显示，PC 和 Co-PC 的降解温度（Td）分别为 420.5 ℃ 和 442.8 ℃，这表明 Co-PC 的 Td 比 PC 提高了 22 ℃。TCDP 工艺是一种从废塑料中回收特定高附加值产品的有效方法，可将其制成不同用途的新型多功能材料。这项研究成果将为把废塑料转化为有用的化学品提供一个新方向，从而减少废塑料及其碳足迹，并通过重复使用塑料材料和实现循环经济，为更可持续的未来做出贡献。

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引用次数: 0

Water-based synthesis of dextran-methacrylate and its use to design hydrogels for biomedical applications 葡聚糖-甲基丙烯酸酯的水基合成及其用于设计生物医学应用的水凝胶

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-22 DOI: 10.1016/j.eurpolymj.2024.113515

Bastien Darmau , Antoine Hoang , Andrew J. Gross , Isabelle Texier

Polysaccharide-based hydrogels are desirable for biomedical applications owing to their biocompatibility and physicochemical tunability. The chemical modification of polysaccharides with photo-sensitive groups, such as methacrylates is a common method to obtain new hydrogel materials. This study introduces a non-toxic water-based method to effectively functionalize dextran with methacrylate groups. The methacrylation reaction with methacrylic anhydride in water in the presence of NaOH was rapid and efficient (85 %−92 % yield), permitting degrees of substitution (DS) up to 62 % within 60 min. An unconventional solid-state photo-crosslinking method was employed to form chemically crosslinked dextran-based hydrogels with LAP (lithium phenyl-2,4,6-trimethylbenzoylphosphinate) as the photoinitiator. By varying the polymer formulations (DS, polymer mass, LAP concentration), a wide range of hydrogels were obtained with various swelling ratios (40–250 %) and release kinetics of model drug and protein biomolecules. Compression modulus values ranged from 32 ± 1 to 342 ± 10 MPa (dry state) and 87 to 8500 kPa (swollen state). Cytotoxicity experiments indicated good biocompatibility for the crosslinked dextran hydrogels. The green synthesis protocols and obtained dextran-based hydrogels with high mechanical strength open up perspectives for applications from tissue engineering to the design of medical devices such as microneedles.

多糖类水凝胶具有生物相容性和理化可调性，因此是生物医学应用的理想材料。用甲基丙烯酸酯等光敏基团对多糖进行化学修饰是获得新型水凝胶材料的常用方法。本研究介绍了一种无毒的水基方法，可有效地用甲基丙烯酸酯基团对葡聚糖进行功能化。在 NaOH 存在下，甲基丙烯酸酐在水中的甲基丙烯酸化反应快速高效（产率为 85 %-92 %），60 分钟内取代度（DS）可达 62 %。以 LAP（苯基-2,4,6-三甲基苯甲酰膦酸锂）为光引发剂，采用非常规固态光交联法形成化学交联的葡聚糖基水凝胶。通过改变聚合物配方（DS、聚合物质量、LAP 浓度），获得了多种不同溶胀率（40%-250%）的水凝胶，以及模型药物和蛋白质生物大分子的释放动力学。压缩模量值范围为 32 ± 1 至 342 ± 10 兆帕（干燥状态）和 87 至 8500 千帕（膨胀状态）。细胞毒性实验表明，交联葡聚糖水凝胶具有良好的生物相容性。绿色合成方案和所获得的具有高机械强度的葡聚糖基水凝胶为组织工程和微针等医疗器械的设计等应用开辟了前景。

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引用次数: 0

Synthesis of low-entangled UHMWiPP using Hf-pyridyl amido catalyst activated by trityl tetrakis (pentafluorophenyl) borate 使用由四(五氟苯基)硼酸三甲苯酯活化的 Hf 吡啶氨基催化剂合成低缠结超高分子量聚丙烯 (UHMWiPP)

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-20 DOI: 10.1016/j.eurpolymj.2024.113513

Abdulaziz Alsubhi , Dario Romano , Fuhai Zhou , Sanjay Rastogi

Recently we demonstrated that low entangled ultra-high molecular weight isotactic polypropylene having molecular weight up to 2.4 million g/mol can be synthesized using a Hf-pyridyl amido catalyst activated by dimethylanilinium tetrakis (pentafluorophenyl)borate. Herein, we used an aprotic borate (trityl tetrakis(pentafluorophenyl)borate) to activate a Hf-pyridyl amido catalyst leading to a fast and ease catalyst activation even at lower temperatures, thus yielding exceptionally high molecular weight (up to 7.7 million g/mol) having improved tacticity (mmmm up to 98.5 %) and peak melting temperature (up to 165 °C). Thus synthesized polymers show extremely slow equilibration process by rheological characterization, indicating the low entangled state. These polymers can be processed in solid-state, without melting, into uniaxial drawn tapes having high tensile strength (1.46 N/tex) and tensile modulus (33 N/tex). The superior mechanical properties enable the tapes to be used as reinforcing material for commercial polypropylene grades, opening the possibilities of making one-component easy-to-recycle composites.

最近，我们证明了使用由二甲基苯胺四（五氟苯基）硼酸盐活化的 Hf-吡啶基氨基催化剂可以合成分子量高达 240 万 g/mol 的低缠结超高分子量同向聚丙烯。在这里，我们使用一种非烷基硼酸盐（四(五氟苯基)硼酸三丁酯）来活化 Hf-吡啶氨基催化剂，即使在较低温度下也能快速、轻松地活化催化剂，从而获得分子量极高（高达 770 万 g/mol）的聚合物，其触变性（mmmm 高达 98.5%）和峰值熔化温度（高达 165 ℃）均得到改善。通过流变特性分析，合成聚合物的平衡过程极为缓慢，表明其处于低缠结状态。这些聚合物在固态下无需熔化即可加工成单轴拉伸带，具有很高的拉伸强度（1.46 N/tex）和拉伸模量（33 N/tex）。卓越的机械性能使这种带材可用作商用聚丙烯牌号的增强材料，为制造单组分易回收复合材料提供了可能。

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引用次数: 0

Integration of two-dimensional MXene into polymeric-based nanocomposite hydrogels for various biomedical applications: Recent advances and future prospects 将二维 MXene 融入聚合物基纳米复合水凝胶，用于各种生物医学应用：最新进展与未来展望

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-20 DOI: 10.1016/j.eurpolymj.2024.113512

Khurram Shahzad , Muhammad Asim Raza , Abrar Hussain , Shiv Dutt Purohit , Kyong-Cheol Ko , Sung Soo Han , Sang Hyun Park

MXenes (viz., transition metal carbides, carbonitrides, and nitrides) are emerging two-dimensional materials (2DMats) with remarkable properties, such as excellent biocompatibility, surface hydrophilicity, easy surface modification, electrical conductivity, and mechanical properties. Including these materials in a polymer matrix makes it possible to produce hydrogels with functional properties applicable to various biomedical areas. This review provides a brief overview of the structure and properties of MXenes, their integration into polymer matrices to formulate emerging MXene-polymer-based nanocomposite hydrogels (CHGs), their multifunctional biomedical applications, machine learning-assisted design and applications, the associated challenges, and future outlooks.

MXenes（即过渡金属碳化物、碳氮化物和氮化物）是一种新兴的二维材料（2DMats），具有卓越的性能，如出色的生物相容性、表面亲水性、易表面改性、导电性和机械性能。在聚合物基质中加入这些材料，就有可能生产出具有适用于各种生物医学领域的功能特性的水凝胶。本综述简要概述了二甲氧苯的结构和特性、将二甲氧苯融入聚合物基质以配制新兴的二甲氧苯聚合物基纳米复合水凝胶（CHGs）、二甲氧苯的多功能生物医学应用、机器学习辅助设计和应用、相关挑战以及未来展望。

引用次数: 0

pH-induced morphological reversible transition from microparticles to vesicles for effective bacteria entrapment pH 值诱导微粒向囊泡的形态可逆转变，从而有效地截留细菌

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-19 DOI: 10.1016/j.eurpolymj.2024.113511

Vladimir Sincari , Svetlana Lukáš Petrova , Eliézer Jäger , Alessandro Jäger , Rafał Konefał , Veronika Gajdošová , Miroslav Šlouf , Hympánová Michaela , Jan Marek , Ondrej Soukup , Martin Hrubý

Polymer particles with stimuli-responsive properties offer promising applications in healthcare, chemical reactors, development of artificial cells and organelles, as well as in the entrapment of bacteria. In this study, a novel biocompatible, biodegradable, and pH-responsive diblock copolymer based on polylactide (PLA) and poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) was synthesized via a metal-free one-pot/simultaneous ring-opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) approach (ROP/RAFT). This copolymer was then employed to produce highly monodisperse microparticles using microfluidics droplet generation technique. Utilizing confocal microscopy imaging, a reversible pH-induced morphological transition from microparticles to vesicle-like structures was observed at pH 5.1. The reversible shift in morphology from microparticles to giant vesicles (Vs) in acidic environments is triggered by the protonation of amino groups of the PDPA block, rendering vesicle surfaces positively charged − an advantageous feature for attracting and engulfing negatively charged bacteria. Initial validation involved electrostatic interactions with negatively charged latex resin beads followed by assessing interaction capabilities with gram-negative bacteria, Escherichia coli (E. coli). Additionally, the reversible morphological transition of microparticles-to-vesicles was employed to study drug release at different pHs. This approach proven to be a promising strategy for targeted drug delivery and bacteria entrapment using smart pH-responsive microparticles.

具有刺激响应特性的聚合物颗粒在医疗保健、化学反应器、人造细胞和细胞器的开发以及细菌诱捕等方面具有广阔的应用前景。本研究通过无金属一锅/同时开环聚合（ROP）和可逆加成-断裂链转移（RAFT）方法（ROP/RAFT）合成了一种新型生物相容性、可生物降解和 pH 值响应型二元共聚物，该共聚物基于聚乳酸（PLA）和聚（2-(二异丙基氨基)乙基甲基丙烯酸酯）（PDPA）。这种共聚物随后被用于利用微流控液滴生成技术生产高度单分散的微颗粒。利用共聚焦显微镜成像技术，在 pH 值为 5.1 时观察到了由 pH 值诱导的从微颗粒到类囊体结构的可逆形态转变。在酸性环境中，PDPA 嵌段的氨基发生质子化，使囊泡表面带正电--这是吸引和吞噬带负电细菌的有利特征，从而引发了从微颗粒到巨囊泡（Vs）的可逆形态转变。初步验证包括与带负电荷的乳胶树脂珠的静电相互作用，然后评估与革兰氏阴性细菌大肠杆菌（E. coli）的相互作用能力。此外，还利用微颗粒到囊泡的可逆形态转变来研究药物在不同 pH 值下的释放情况。这种方法被证明是利用智能 pH 响应微颗粒进行靶向给药和细菌截留的一种有前途的策略。

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引用次数: 0

Development and 4D printing of magneto-responsive PMMA/TPU/Fe3O4 nanocomposites with superior shape memory and toughness properties 具有优异形状记忆和韧性特性的磁响应 PMMA/TPU/Fe3O4 纳米复合材料的开发与 4D 印刷

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-19 DOI: 10.1016/j.eurpolymj.2024.113495

Afshin Ahangari , Hossein Doostmohammadi , Majid Baniassadi , Mahdi Bodaghi , Mostafa Baghani

This paper introduces 4D printing of composites of polymethyl methacrylate (PMMA) and thermoplastic polyurethane (TPU) reinforced with Fe₃O₄ particles for the first time. PMMA/TPU blends with 70/30 wt% are selected as matrix with the best compatibility based on dynamic mechanical thermal analysis. Fe₃O₄ nanoparticles are added to the blends with 10 %, 15 % and 20 % weight ratios. Their addition enables remote actuation of the materials in a high frequency alternating magnetic field. Field emission scanning microscopic images confirms a full dispersion of nanoparticles inside the polymeric matrix. Nanocomposites with 20 wt% of Fe₃O₄ can perfectly recover the permanent shape within 1.5 min in the magnetic field. They also reveal perfect shape memory properties in the hot water. Moreover, all samples display a perfect shape fixity ratio. The addition of TPU significantly enhances the toughness and flexibility of the PMMA matrix. It is found that Fe₃O₄ nanoparticles further enhance the mechanical strength by 10 % to 15 %, although they reduce the strain at break from 17 % to 14 %. Finally, a gripper is 4D printed and its excellent performance in the magnetic field is demonstrated.

本文首次介绍了用Fe3O4颗粒增强聚甲基丙烯酸甲酯（PMMA）和热塑性聚氨酯（TPU）复合材料的4D打印技术。根据动态机械热分析，70/30 wt% 的 PMMA/TPU 混合物被选为相容性最好的基体。Fe3O4纳米颗粒以10%、15%和20%的重量比添加到混合物中。加入这些纳米粒子后，材料可在高频交变磁场中远程驱动。场发射扫描显微镜图像证实，纳米颗粒完全分散在聚合物基体中。含有 20 wt% Fe3O4 的纳米复合材料可在磁场中 1.5 分钟内完全恢复永久形状。它们在热水中也显示出完美的形状记忆特性。此外，所有样品都显示出完美的形状固定率。添加 TPU 后，PMMA 基体的韧性和柔韧性明显增强。研究发现，Fe3O4 纳米粒子可将机械强度进一步提高 10% 至 15%，但会将断裂应变从 17% 降低到 14%。最后，4D 打印出了一个抓手，并展示了其在磁场中的优异性能。

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引用次数: 0

The influence of myrcene on anionic copolymerization of 1,3-pentadiene and styrene 月桂烯对 1,3-戊二烯和苯乙烯阴离子共聚的影响

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-16 DOI: 10.1016/j.eurpolymj.2024.113507

Yawen Fu , Qiqi Dai , Haoyun Tan , Xupeng Han , Bingbing Zhang , Qiaoqiao Xiong , Wenjun Yi , Zan Yang , Lijun Li , Kun Liu

C5-dienes including 1,3-pentadiene (PD) and isoprene (IP) as by-products of naphtha cracking are important industrial raw materials for the production of thermoplastic elastomers, synthetic rubber and resins. The research on living anionic polymerization (LAP) of myrcene (MY) is also of great significance for the development of new bio-based materials and products. Focusing on the optimal utilization of C5 resources and the high-value utilization of biomass resources and the realization of green chemical production, this article reports the synthesizing of a novel terpolymer by LAP of PD, styrene (ST) and the biomass monomer MY. The discovery of the alternating sequence structure of ST and PD inspires us to further explore the development of copolymers containing this unique sequence structure. The special long branched side chain of MY and its low glass transition temperature are also conducive to the synthesis of new integrated rubbers. The ¹H NMR tracking analysis indicates that the polymerization pattern changes from alternating sequence to gradient block sequence with the increase of MY content. Combined with FTIR analysis, the PD monomeric units are mainly trans-1,4 structure and MY monomeric units are predominant cis-1,4 structure. Considering the extremely high polymerization activity of MY compared to ST and PD, the copolymerization rate is significantly dependent on the concentration of the PD monomer. Despite this, due to the interactions between ST and PD ([ST¦PD] intermediate), ST still tends to form alternating segments with PD. The ternary copolymerization can be viewed as a “binary gradient copolymerization” of [ST¦PD] and MY (r_MY > r_[ST¦PD]).

石脑油裂解的副产品 C5-二烯（包括 1,3-戊二烯 (PD) 和异戊二烯 (IP)）是生产热塑性弹性体、合成橡胶和树脂的重要工业原料。对月桂烯（MY）活阴离子聚合（LAP）的研究对于开发新的生物基材料和产品也具有重要意义。本文以 C5 资源的优化利用和生物质资源的高值化利用以及实现绿色化工生产为重点，报道了活阴离子聚合（LAP）法合成 PD、苯乙烯（ST）和生物质单体 MY 的新型三元共聚物。ST 和 PD 的交替序列结构的发现启发我们进一步探索含有这种独特序列结构的共聚物的开发。MY 特殊的长支链侧链及其较低的玻璃化转变温度也有利于合成新型集成橡胶。1H NMR 跟踪分析表明，随着 MY 含量的增加，聚合模式从交替序列变为梯度嵌段序列。结合傅立叶变换红外光谱分析，PD 单体单元主要是反式-1,4 结构，而 MY 单体单元主要是顺式-1,4 结构。考虑到与 ST 和 PD 相比，MY 的聚合活性极高，因此共聚率在很大程度上取决于 PD 单体的浓度。尽管如此，由于 ST 和 PD 之间的相互作用（[ST¦PD] 中间体），ST 仍倾向于与 PD 形成交替段。三元共聚可以看作是[ST¦PD]和 MY 的 "二元梯度共聚"（rMY > r[ST¦PD]）。

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引用次数: 0

Kinetics and scale inhibition application studies towards bulk and RAFT copolymerization of maleic anhydride and acrylic acid 马来酸酐和丙烯酸的散装和 RAFT 共聚动力学和阻垢应用研究

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-12 DOI: 10.1016/j.eurpolymj.2024.113504

Mengyu Cao , Lei Wang , Aihua Li, Xiaolong Yang, Xiaole Gong, Jiang-Tao Xu, Jingquan Liu

Poly(maleic anhydride) (PMA) is commonly reckoned as a better water scale inhibitor than poly(acrylic acid) (PAA) since each maleic anhydride unit can supply two carboxylic acid groups. However, pure PMA is difficult to achieve because the steric effect of its monomer MA. Herein, we synthesize copoly(MA-AA) copolymer by bulk polymerization method (bulk-copoly(MA-AA)), which avoids the use of any solvents which have to be removed afterwards. In addition, we also synthesize copoly(MA-AA) by reversible addition-fragmentation chain transfer (RAFT) polymerization method to afford RAFT-copoly(MA-AA) with low polydispersity index (PDI) less than 1.2, and the performance of RAFT-copoly(MA-AA) in water scale inhibition is more excellent relative to bulk-copoly(MA-AA). We also synthesize other copoly(MA-AA) copolymers by varying the molar ratio of MA to AA to study the polymerization mechanism. Through the static scale inhibition experiment, it is concluded that when the concentration of copoly(MA-AA) is 80 mg/L, the scale inhibition performance of RAFT-copoly(MA-AA) can reach 96.50 % which is the best among the control samples. It is also found that only 1:1 alternating copolymerization of MA and AA could be achieved as demonstrated by ¹H nuclear magnetic resonance spectra of the copolymers, evidencing the strong steric hindrance of MA for its homo-polymerization.

聚（马来酸酐）（PMA）通常被认为是比聚（丙烯酸）（PAA）更好的水垢抑制剂，因为每个马来酸酐单元可以提供两个羧酸基团。然而，由于单体 MA 的立体效应，纯 PMA 很难实现。在此，我们采用体聚合法（bulk-copoly(MA-AA)）合成了共聚（MA-AA）共聚物，这种方法避免了使用任何溶剂，因为溶剂必须在聚合后清除。此外，我们还采用可逆加成-断裂链转移（RAFT）聚合法合成了共聚物（MA-AA），得到了聚分散指数（PDI）小于 1.2 的 RAFT-共聚物（MA-AA），RAFT-共聚物（MA-AA）的阻水垢性能相对于 bulk-共聚物（MA-AA）更为优异。我们还通过改变 MA 与 AA 的摩尔比合成了其他共聚（MA-AA）共聚物，以研究其聚合机理。通过静态阻垢实验得出结论：当共聚(MA-AA)的浓度为 80 mg/L 时，RAFT-共聚(MA-AA)的阻垢性能可达 96.50%，是对照样品中最好的。通过共聚物的 1H 核磁共振谱还发现，MA 和 AA 只能实现 1:1 的交替共聚，这证明 MA 对其均聚具有很强的立体阻碍作用。

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引用次数: 0

High fire-safety epoxy resin with functional polymer/metal–organic framework hybrids 含功能聚合物/金属有机框架杂化物的高防火安全性环氧树脂

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-12 DOI: 10.1016/j.eurpolymj.2024.113505

Peiwen Xu , Chongyang Gao , Junchi Ma , Yuan Fang , Zhaodi Wang , Zongfu An , Uiseok Hwang , Xin Yang , Yahong Xu , Soochan Kim

Petroleum-derived bisphenol A-type epoxy resins are highly flammable and vulnerable to fires, limiting their wide applications. The addition of inorganic flame retardants to the epoxy resin improves the flame retardancy of the epoxy resin, but it is difficult to distribute them evenly in the polymer matrix. Here, we introduce flame-retardant epoxy resins supported by the functional polymer/metal–organic framework hybrids. The hybrids, consisted of polyaniline, poly (4-styrenesulfonic acid), and Zr-based organic frameworks, demonstrate effective flame-retardant effects with homogeneous distribution in the epoxy based on their synergistic effects of each material. Compared with pure epoxy resin, the presence of 1 wt% of hybrid flam-retardant remarkably decreases the combustion, the heat release, and the smoke production.

从石油中提取的双酚 A 型环氧树脂极易燃烧，容易引发火灾，因此限制了其广泛应用。在环氧树脂中添加无机阻燃剂可提高环氧树脂的阻燃性，但很难将其均匀分布在聚合物基体中。在此，我们介绍了由功能聚合物/金属有机框架杂化物支撑的阻燃环氧树脂。这些杂化物由聚苯胺、聚（4-苯乙烯磺酸）和锆基有机框架组成，基于每种材料的协同作用，它们在环氧树脂中均匀分布，表现出有效的阻燃效果。与纯环氧树脂相比，1 wt%的混合阻燃剂可显著减少燃烧、热释放和烟雾产生。

引用次数: 0

Chain relaxation of carborane segments with tailored chain length at high temperatures 高温下具有定制链长的碳化硼段的链松弛

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2024-10-12 DOI: 10.1016/j.eurpolymj.2024.113509

Chongwen Yu , Jiaqi Sun , Xuejie Wang , Xingyao Liu , Tianhao Li , Xiao Hu , Gang Shao , Liu He , Jian Xu , Yujie Song

High-performance thermoset polymers have good thermal stability due to their highly crosslinked network, while also represent topological constraints that restrict cooperative segmental motion, making it difficult to relax stresses even at high temperatures. Failure of most thermoset polymers at high temperatures is due to ineffective stress relaxation, which limits the use of thermoset polymers in harsh environments. Herein, we employed a cyclosiloxane hybrid polymer (CHP) containing o-carborane segments with tailored carbon chain length to relieve internal stress. The introduction of o-carborane and lengthening of carbon chain both increased the CHP fractional free volume, and reduced the activation energy required in the later stages of the curing process. The carbon chain changed the conformation to achieve chain relaxation by stretching and rotating the carbon–carbon bonds at high temperatures, which avoided cracking and increased the failure temperature of the CHP. Furthermore, the adhesion strength of the o-carborane modified CHP reached a maximum of 2.15 MPa, surpassing 1.23 MPa of the neat CHP. The o-carborane modified CHP with the longest carbon chain exhibited good stability while supporting 1 kg load for 5 min when subjected to ablation, whereas the neat CHP failed after only 47 s. The o-carborane-modified CHP exhibited enhanced high-temperature properties through chain relaxation to inhibit cracking and in situ generation of boron oxide at high temperatures to protect the resin matrix.

高性能热固性聚合物因其高度交联的网络而具有良好的热稳定性，但同时也存在拓扑约束，限制了分段的协同运动，因此即使在高温下也很难松弛应力。大多数热固性聚合物在高温下失效的原因是应力松弛效果不佳，这限制了热固性聚合物在恶劣环境中的应用。在此，我们采用了一种环硅氧烷杂化聚合物（CHP），其中含有碳链长度可调的邻碳硼烷段，以缓解内应力。邻碳硼烷的引入和碳链的延长都增加了 CHP 的自由体积分数，并降低了固化过程后期所需的活化能。碳链改变了构象，在高温下通过碳碳键的拉伸和旋转实现了链松弛，从而避免了开裂，提高了 CHP 的失效温度。此外，邻碳硼烷改性 CHP 的粘合强度最大达到 2.15 兆帕，超过了纯 CHP 的 1.23 兆帕。碳链最长的邻碳硼烷改性热电联产在承受烧蚀 5 分钟 1 千克载荷时表现出良好的稳定性，而纯热电联产仅在 47 秒后就失效了。邻碳硼烷改性热电联产通过链松弛抑制开裂，并在高温下原位生成氧化硼保护树脂基体，从而增强了高温性能。

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引用次数: 0