Polymer最新文献_第7页

Probing the energy dissipation mechanisms of shear thickening gel at molecular level 从分子水平探讨剪切增稠凝胶的能量耗散机制

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-11 DOI: 10.1016/j.polymer.2026.129736

Yuan Yao , Bing Liu , Kang Wang , Yuxin Xia , Huaxia Deng , Xinglong Gong

Shear thickening gels (STGs) exhibit remarkable impact resistance and energy absorption properties owing to the non-linear and reversible mechanical properties. However, the molecular-level mechanisms underlying their dissipation behavior remain unclear due to the limited understanding of how crosslinking density and local coordination influence energy redistribution and structural relaxation during impact. In this work, we developed a coarse-grained molecular dynamics model to investigate the impact induced energy conversion in STGs with different Si/B molar ratios. The simulations were validated by rheological experiments and accurately reproduced the nonlinear viscoelastic and shear thickening responses of system. The results show that energy evolution revealed a rapid transformation of kinetic energy into potential and internal deformation energy, followed by relaxation driven stabilization. Three coupled molecular processes-reversible coordination, chain conformational change, and orientational relaxation-were identified as key pathways that govern the dissipation efficiency and reversibility by regulating the partitioning of mechanical energy is partitioned between elastic storage, structural reconfiguration, and irreversible deformation. This work modulates the balance between elastic energy storage and irreversible deformation, thereby establishing a unified molecular framework that links network architecture to macroscopic impact performance.

剪切增稠凝胶具有非线性和可逆的力学性能，具有良好的抗冲击和吸能性能。然而，由于对交联密度和局部配位如何影响碰撞过程中的能量再分配和结构松弛的理解有限，其耗散行为的分子水平机制仍然不清楚。在这项工作中，我们建立了一个粗粒度的分子动力学模型来研究不同Si/B摩尔比的STGs中撞击引起的能量转换。通过流变实验验证了仿真结果，准确再现了系统的非线性粘弹性和剪切增厚响应。结果表明：能量演化过程表现为动能快速转化为位能和内部变形能，随后出现松弛驱动稳定；三个耦合的分子过程——可逆配位、链构象变化和取向弛豫——通过调节机械能在弹性储存、结构重构和不可逆变形之间的分配来控制耗散效率和可逆性的关键途径。这项工作调节了弹性能量储存和不可逆变形之间的平衡，从而建立了一个统一的分子框架，将网络结构与宏观冲击性能联系起来。

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引用次数: 0

Synthesis and properties of fluorine-free polyimides with ultrahigh Tg and excellent transparency based on the synergistic regulation of fluorenyl and methyl groups 基于芴基和甲基协同调节的超高Tg、高透明度无氟聚酰亚胺的合成及性能

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-07 DOI: 10.1016/j.polymer.2026.129720

Tianci Ma , Lei Yang , Jinglei Xing , Long Wang , Guofei Chen

It is a new challenge to develop fluorine-free transparent polyimides due to the prohibition of perfluoroalkyl and polyfluoroalkyl substances (PFAS). Hence, a series of fluorine-free polyimides were synthesized by 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride (BPAF) with 3,3′-bis(methyl)-4,4′-benzidine (2,2′-DMBZ), 3,3′-bis(methyl)-4,4′-benzidine (3,3′-DMBZ), 1,4-diaminobenzene (p-PDA), 1,3-diaminobenzene (m-PDA), 2,6-toluenediamine (m-MPDA) and 2,4,6-trimethyl-1,3-phenylenediamine (m-TMPDA) through one-step and two-step methods. Then the corresponding polyimide films were obtained by solution casting. All polyimides exhibited high glass transition temperatures (T_gs) of 404-523 °C, coefficients of thermal expansion (CTEs) of 39-65 ppm/K, optical transmittances at 400 nm (T₄₀₀s) of 36-82 %, tensile strengths of 104.6-156.3 MPa, and tensile moduli of 2.6-4.3 GPa. The prepared fluorine-free polyimides had better performances than typical fluorine-containing polyimide derived from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,2′-bis(trifluoromethyl)-4,4′-benzidine (TFDB). In particular, PI-6 exhibited comprehensive properties with T_g of 523 °C, T₄₀₀ of 82%, and CTE of 42 ppm/K.

由于全氟烷基和多氟烷基物质的禁用，开发无氟透明聚酰亚胺是一个新的挑战。因此，以9,9-二（3,4-二氧苯基）芴二酐（BPAF）为原料，采用一步法和两步法，以3,3'-二（甲基）-4,4'-联苯胺（2,2'-DMBZ）、3,3'-二（甲基）-4,4'-联苯胺（3,3'-DMBZ）、1,4-二氨基苯（p-PDA）、1,3-二氨基苯（m-PDA）、2,6-甲苯二胺（m-MPDA）和2,4,6-三甲基-1,3-苯二胺（m-TMPDA）为原料合成了一系列无氟聚酰亚胺。然后通过溶液铸造得到相应的PI膜。所有聚酰亚胺的玻璃化转变温度（Tgs）为404 ~ 523℃，热膨胀系数（CTEs）为39 ~ 65 ppm/K， 400 nm光透射率（T400s）为36 ~ 82%，拉伸强度为104.6 ~ 156.3 MPa，拉伸模量为2.6 ~ 4.3 GPa。制备的无氟PI性能优于典型的4,4′-（六氟异丙基）二苯二酸酐（6FDA）和2,2′-双（三氟甲基）-4,4′-联苯胺（TFDB）衍生的含氟聚酰亚胺。其中，PI-6表现出综合性能，Tg为523℃，T400为82%，CTE为42 ppm/K。

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引用次数: 0

Twisted non-coplanar benzimidazole diamines enabling colorless, high-Tg polyimide films for flexible displays 扭曲非共面苯并咪唑二胺使无色，高tg聚酰亚胺薄膜柔性显示

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-07 DOI: 10.1016/j.polymer.2026.129719

Peng Yue , Dandan Li , Wei Wang , Youhai Yu , Guangtao Qian , Chunhai Chen

To achieve high-performance colorless polyimide (CPI) films, this study employed a molecular structure design strategy aimed at suppressing the charge transfer complex (CTC) effect between molecular chains by introducing twisted and non-coplanar structure into the polymer backbone. Drawing inspiration from previous research, three benzimidazole-based diamine monomers with twisted non-coplanar structures were designed and synthesized by modulating the relative positions of amino groups and the structures of substituents. These monomers were subsequently polymerized with two dianhydrides, namely 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), yielding two series of polybenzimidazole-imides (PBIIs): semi-aromatic and fully aromatic polymers, respectively. The resulting semi-aromatic polymer films demonstrated a combination of excellent thermal resistance, with glass transition temperature (T_g) exceeding 400 °C, and high optical transparency, exhibiting over 80% transmittance at 400 nm (T₄₀₀). This work not only provides an effective molecular design strategy for developing high-performance CPI materials but also expands the application prospects of PBII materials in the field of high-temperature optical devices.

为了获得高性能无色聚酰亚胺（CPI）薄膜，本研究采用了一种分子结构设计策略，旨在通过在聚合物主链中引入扭曲和非共面结构来抑制分子链之间的电荷转移络合物（CTC）效应。借鉴前人的研究成果，通过调节氨基的相对位置和取代基的结构，设计并合成了三种具有扭曲非共面结构的苯并咪唑基二胺单体。这些单体随后与两种二酐，即1,2,4,5-环己四羧酸二酐（HPMDA）和4,4'-（六氟异丙基）二苯二酸酐（6FDA）聚合，得到两个系列的聚苯并咪唑亚胺（PBIIs）：分别为半芳和全芳聚合物。所得的半芳香族聚合物薄膜具有优异的耐热性，玻璃化转变温度（Tg）超过400°C，高光学透明度，在400 nm处透光率超过80% （T400）。本工作不仅为开发高性能CPI材料提供了有效的分子设计策略，而且拓展了PBII材料在高温光学器件领域的应用前景。

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引用次数: 0

Additive Manufacturing of UV Cured Dual-Network Silicone Elastomer with 3D Multifunctional Structure 具有三维多功能结构的UV固化双网状有机硅弹性体的增材制造

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-08 DOI: 10.1016/j.polymer.2026.129703

Yanan Sun , Zhuoming Duan , Kexin Huan , Minhua Li , Yanli Shi , Weili Gao , Haifeng Jia , Yuetao Liu

UV-curable silicone rubber exhibits promising prospects in fields such as flexible electronics and advanced coatings due to its high processing efficiency and patternability. This study developed a synergistic crosslinking strategy that combines Michael addition and UV curing to prepare high-performance dual network silicone rubber and achieve curing within seconds. The system comprised key components: trifluoropropyl-grafted acrylic silicone resin (PAT-SR), pentaerythritol tetraacrylate (PET4A), and aminopropyl silicone oil (ASO). Initially, the primary amine groups of ASO underwent a catalyst-free Michael addition with the acrylate groups in PAT-SR and PET4A, forming a malleable, partially cross-linked prepolymer. Subsequently, the material was cured within seconds via free radical polymerization of the residual acrylate groups upon UV irradiation. The trifluoropropyl group imparted outstanding hydrophobicity and chemical resistance to the material. PET4A, acting as a rigid cross-linking center, significantly enhanced the mechanical strength; the sample ASO_0.7/PA_0.4-FSR achieved a tensile strength of 0.92 MPa and an elongation at break of 612%. Furthermore, the material demonstrated good interfacial compatibility with various functional fillers. This research provides a simple and efficient novel strategy for preparing high-performance dual-network silicone rubber materials that combine excellent comprehensive properties with high processability, holding broad application potential in areas such as anti-fouling, protective coatings, and flexible electronics.

紫外光固化硅橡胶因其加工效率高、可定型性好，在柔性电子、高级涂料等领域具有广阔的应用前景。本研究开发了一种将Michael添加和UV固化相结合的协同交联策略，制备了高性能双网络硅橡胶，并实现了秒内固化。该体系由三氟丙基接枝丙烯酸有机硅树脂（PAT-SR）、季戊四醇四丙烯酸酯（PET4A）和氨基丙基硅油（ASO）组成。最初，ASO的伯胺基团与PAT-SR和PET4A中的丙烯酸酯基团进行无催化剂的Michael加成，形成具有延展性的部分交联预聚物。随后，该材料在紫外线照射下通过残留丙烯酸酯基团的自由基聚合在几秒钟内固化。三氟丙基赋予材料出色的疏水性和耐化学性。PET4A作为刚性交联中心，显著提高了材料的机械强度；样品ASO0.7/PA0.4-FSR的抗拉强度为0.92 MPa，断裂伸长率为612%。此外，该材料与各种功能填料表现出良好的界面相容性。本研究为制备高性能双网硅橡胶材料提供了一种简单高效的新策略，该材料具有优异的综合性能和高可加工性，在防污、保护涂层和柔性电子等领域具有广泛的应用潜力。

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引用次数: 0

Nanostructures of tetra-arm Poly(ethylene glycol) networks by Iron(III)-Catechol coordinative crosslinking units 铁(III)-儿茶酚配位交联单元制备四臂聚乙二醇网络的纳米结构

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-04 DOI: 10.1016/j.polymer.2026.129700

Jungju Ryu , Anna V. Sokolova , Minjeong Kang , Yoolee Lee , Ngoc Nguyen Quang , Daun Seol , Sanghoon Cho , Hoeil Chung , Daewon Sohn

The internal structure of tetra-arm poly(ethylene glycol) networks crosslinked via coordination bonds was investigated to understand the structural aspects of these networks, which are connected by finite polymer units. In tetra-arm poly(ethylene glycol) modified with catechol moieties (4-PCA), the networks were preserved by coordination bonds of catechol-Fe(III) ions using optimal quantitative ratios (R_CA/Fe) that form bis and tris-complexes depending on pH values. The network is established with finite units associated with changes in geometrical connections. This research focuses on the structural aspects composed of controllable coordination bonding units. The samples were investigated using small-angle X-ray scattering (SAXS) and neutron scattering (SANS) measurements. The apparent correlation lengths of the gels were discussed as the presence of nano-defects. The contrast variation SANS results support the presence of nano-defects, R_g ∼3 nm. The defects are incorporated by partial irregularity of missing linkages and subsequent distortion of the topology. The rapid and sensitive controls using metal-mediated coordination bond may generate defects in the polymer network. It suggests that diverse strategies for metal-mediated hydrogels can be found by monitoring their nanostructures.

研究了通过配位键交联的四臂聚乙二醇网络的内部结构，以了解这些由有限聚合物单元连接的网络的结构方面。在用儿茶酚基团修饰的四臂聚乙二醇（4-PCA）中，网络通过儿茶酚-Fe（III）离子的配位键保存，使用最佳定量比（RCA/Fe），根据pH值形成双和三络合物。该网络由有限单元建立，这些单元与几何连接的变化有关。本研究的重点是可控配位键合单元组成的结构方面。采用小角x射线散射（SAXS）和中子散射（SANS）测量对样品进行了研究。讨论了纳米缺陷存在时凝胶的表观相关长度。对比变化的SNAS结果支持纳米缺陷的存在，Rg ~ 3nm。缺陷是由缺失连杆的部分不规则性和随后的拓扑畸变引起的。利用金属介导的配位键进行快速灵敏的控制，可能会在聚合物网络中产生缺陷。这表明，通过监测金属介导的水凝胶的纳米结构，可以找到不同的策略。

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引用次数: 0

Mechanisms of polymer-surfactant synergy for enhanced salt-tolerance in CO2 foams 聚合物-表面活性剂协同增强CO2泡沫耐盐性的机理

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-06 DOI: 10.1016/j.polymer.2026.129678

Jun Zhao , Yangyang Yu , Kejing Wu , Yingying Liu , Yingming Zhu , Houfang Lu , Hairong Yue , Bin Liang

The presence of salt ions significantly enhances the stability of polymer/surfactant composite foam systems, offering great potential for optimizing CO₂ foam flooding performance in high-salinity reservoirs. However, the molecular-level mechanism underlying this “salt ion-induced enhancement” effect remains unclear. This study systematically investigates the evolution of foam performance and the synergistic salt-tolerance mechanism of a polymer/surfactant system across a wide salinity range (0∼20 × 10⁴ mg/L) through interface/bulk characterization combined with molecular dynamics simulations. Research demonstrates that salt ions weaken polymer/surfactant-H₂O interactions through competitive hydration, while simultaneously promoting hydrogen bonds between the polymer/surfactant interface to form a highly elastic interfacial film. Additionally, the “salt thickening” effect of the foam base-fluid drives to form a supramolecular network, which is a key mechanism behind the enhanced viscoelasticity. Compared to a salt-free system, high salinity (20 × 10⁴ mg/L) delays foam drainage (the drainage activation energy increases to 51.46 kJ/mol) and suppresses coarsening (Ostwald ripening rate decreases by 57.4%), thereby enhancing the foam comprehensive index by 1.78 times. This study elucidates the key pathways for salt ion-induced synergistic salt-tolerance in polymer/surfactant composite systems, providing theoretical support for constructing green, efficient CO₂ foam systems adapted to high-salinity environments.

盐离子的存在显著提高了聚合物/表面活性剂复合泡沫体系的稳定性，为优化高矿化度油藏的CO2泡沫驱性能提供了巨大的潜力。然而，这种“盐离子诱导增强”效应的分子水平机制尚不清楚。本研究通过界面/体积表征结合分子动力学模拟，系统地研究了聚合物/表面活性剂体系在宽盐度范围（0 ~ 20×104 mg/L）内泡沫性能的演变和协同耐盐机制。研究表明，盐离子通过竞争性水化削弱聚合物/表面活性剂- h2o相互作用，同时促进聚合物/表面活性剂界面之间的氢键形成高弹性界面膜。此外，泡沫基流体的“盐增稠”效应驱动形成超分子网络，这是增强粘弹性的关键机制。与无盐体系相比，高盐度（20×104 mg/L）可延缓泡沫排水（排水活化能提高至51.46 kJ/mol），抑制泡沫粗化（Ostwald熟化率降低57.4%），从而使泡沫综合指数提高1.78倍。本研究阐明了盐离子诱导聚合物/表面活性剂复合体系协同耐盐的关键途径，为构建适应高盐度环境的绿色高效CO2泡沫体系提供了理论支持。

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引用次数: 0

c-4CzTPN porous carbon-doped crosslinked rubbery PEG/PPG membranes synthesized via ROMP for enhanced CO2 separation 通过ROMP合成c-4CzTPN多孔碳掺杂交联橡胶PEG/PPG膜，增强CO2分离

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-09 DOI: 10.1016/j.polymer.2026.129707

Md. Homayun Kabir , Kavya Adot Veetil , Senthil Kannan , Ook Choi , Tae-Hyun Kim

A series of crosslinked rubbery polymer membranes based on poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG) and doped with varying amounts of poly[2,3,5,6-tetra(carbazol-9-yl)terephthalonitrile] (p-4CzTPN)-derived porous carbon (c-4CzTPN) were fabricated via ring-opening metathesis polymerization (ROMP) to enhance their gas permeability and improve CO₂ transport across the network of the PEG/PPG polymer matrix. The incorporation of c-4CzTPN significantly increased the gas diffusivity, facilitating the permeation of gas molecules, particularly CO₂, across the polymer matrix. The membranes exhibit good CO₂ separation performance, with CO₂ permeabilities ranging from 442.92 to 558.35 Barrer and CO₂/N₂ and CO₂/CH₄ selectivities of 41.87–48.67 and 14.77–15.91, respectively. The PEG/PPG-c-4CzTPN-0.5 membrane demonstrates excellent performance, exceeding Robeson's 2008 upper bound for CO₂/N₂ separation. It also shows strong resistance to plasticization under a feed gas pressure up to 10 atm and maintains excellent anti-aging stability over 236 days.

以聚乙二醇/聚丙二醇（PEG/PPG）为基材，通过开环分解聚合（ROMP）法制备了一系列掺杂不同量聚[2,3,5,6-四（咔唑-9-基）对苯二甲酸]（p-4CzTPN）衍生多孔碳（c-4CzTPN）的交联橡胶聚合物膜，以提高其透气性和改善二氧化碳在PEG/PPG聚合物基体网络中的传输。c-4CzTPN的掺入显著提高了气体的扩散率，促进了气体分子，特别是二氧化碳在聚合物基体上的渗透。该膜具有良好的CO2分离性能，CO2的渗透率为442.92 ~ 558.35 Barrer， CO2/N2和CO2/CH4的选择性分别为41.87 ~ 48.67和14.77 ~ 15.91。PEG/PPG-c-4CzTPN-0.5膜表现出优异的性能，超过了Robeson 2008年提出的CO2/N2分离上限。在高达10atm的进料气压力下，它也表现出很强的抗塑化能力，并在236天内保持优异的抗老化稳定性。

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引用次数: 0

Chemical and microstructure correlation towards optimisation of thermal behaviour of boric acid crosslinked PVA-cellulose nanofiber composite 硼酸交联聚乙烯醇-纤维素纳米纤维复合材料热性能优化的化学和微观结构相关性

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-03 DOI: 10.1016/j.polymer.2026.129654

Sreedevi T. , Franck Ducos , Jesiya Susan George , Jyotishkumar Parameswaranpillai , Asha Bhanu A.V. , Henri Vahabi , Poornima Vijayan P.

Poly(vinyl alcohol) (PVA) as a superior biodegradable polymer, it requires structural modifications using crosslinking agents and nanofillers to assure thermal integrity. PVA-cellulose nanofiber (CNF) composite films were fabricated by solvent casting with boric acid as crosslinking agent (named PVA-BA-CNF composite). Chemical interactions established between components of the composite film was characterised by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Newly formed B–O–C linkages were evident from chemical structure evaluation. Surface morphology of the film was evaluated using atomic force microscopy (AFM) and optical microscopy (OM). Morphological studies revealed a uniform dispersion of CNF in a PVA-BA crosslinked matrix especially at low boric acid content. Changes in crystallinity and crystalline size with extent of crosslinking in the composites has been evaluated using X-Ray diffraction (XRD) studies. Those parameters were correlated with melting temperature (T_m) of the composites obtained from differential scanning calorimetry (DSC). The higher glass transition temperature (T_g) recorded for PVA-BA-CNF composite films were correlated with increased crosslinking. The effect of boric acid content on thermal stability, degradation kinetics and the processing window for PVA-BA-CNF composites have been evaluated using thermogravimetric analysis (TGA). The apparent activation energy for thermal degradation was calculated using the Coats-Redfern method. Vertical flammability test was conducted to study flammability of composite films. The PVA-BA-CNF composites exhibit enhanced thermal properties making them as a potential candidate for applications where higher thermal resistance and processability are required.

聚乙烯醇（PVA）作为一种优良的可生物降解聚合物，需要使用交联剂和纳米填料对其进行结构改性以保证其热完整性。以硼酸为交联剂，采用溶剂铸造法制备了PVA-BA-CNF复合膜（PVA-BA-CNF复合膜）。利用傅里叶变换红外光谱（FTIR）和x射线光电子能谱（XPS）表征了复合膜组分之间的化学相互作用。新形成的B-O-C键在化学结构评价中很明显。利用原子力显微镜（AFM）和光学显微镜（OM）对膜的表面形貌进行了评价。形态学研究显示CNF在PVA-BA交联基质中均匀分散，特别是在低硼酸含量时。利用x射线衍射（XRD）研究了复合材料中结晶度和晶粒尺寸随交联程度的变化。这些参数与差示扫描量热法（DSC）测得的复合材料熔化温度（Tm）相关。PVA-BA-CNF复合膜的玻璃化转变温度（Tg）越高，交联越强。采用热重分析方法评价了硼酸含量对PVA-BA-CNF复合材料热稳定性、降解动力学和加工窗口的影响。采用coats-Redfern法计算了热降解表观活化能。采用垂直可燃性试验研究复合材料薄膜的可燃性。PVA-BA-CNF复合材料具有增强的热性能，使其成为需要更高热阻和可加工性的应用的潜在候选材料。

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引用次数: 0

Biodegradable poly(ε-caprolactone)/poly(silyl fumarate) shape memory scaffolds 可生物降解聚（ε-己内酯）/聚（富马酸硅酯）形状记忆支架

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-05 DOI: 10.1016/j.polymer.2026.129694

Jenlyan Negrón Hernández , Kaley Beach , Paola Chavarria , Melissa A. Grunlan

Biodegradable shape memory scaffolds have the unique potential to heal irregularly shaped craniomaxillofacial (CMF) defects through conformal ‘self-fitting’. These have been previously prepared from poly(ε-caprolactone) diacrylate (PCL-DA), but the slow biodegradation rate of PCL is expected to limit neotissue formation. Subsequently, telechelic siloxane macromers polydimethylsiloxane-dimethacrylate (PDMS-DMA) and polymethylhydrosiloxane-DMA (PMHS-DMA) were combined with PCL-DA at varying weight (wt)% ratios, resulting in PCL/PDMS and PCL/PMHS co-network scaffolds with accelerated degradation rates owing to phase separation that increased water uptake. Still, these siloxane macromers lack a hydrolytically unstable backbone thus limiting degradation. Herein, poly(silyl fumarate) (PSF) was synthesized as a hybrid siloxane macromer with a hydrolytically unstable backbone as well as interchain crosslinkability. PCL/PSF scaffolds were prepared at 90:10, 75:25, 60:40, and 50:50 wt% of PCL-DA to PSF via solvent-casting particulate leaching (SCPL) with a fused salt template. Despite a reduction in PCL crystallinity (i.e., switching segments) with 40 and 50 wt% PSF, all scaffolds maintained excellent shape memory behavior. PCL/PSF scaffolds with 10 and 25 wt% PSF also maintained the modulus of the PCL-only scaffold as well as the corresponding PCL/PDMS and PCL/PMHS scaffolds. In vitro degradation under basic conditions revealed that PCL/PSF scaffolds with just 10 wt% PSF degraded faster than the PCL-only scaffold and further increased with 25 wt% PSF to surpass that of the corresponding PCL/PDMS scaffold. A lack of phases separation was observed, and thus indicated that faster degradation was achieved by the hydrolytic instability of the PSF.

可生物降解的形状记忆支架具有独特的潜力，可以通过适形的“自适应”来修复不规则形状的颅颌面（CMF）缺陷。以前已经用聚（ε-己内酯）二丙烯酸酯（PCL- da）制备了这些材料，但PCL缓慢的生物降解速度预计会限制新组织的形成。随后，将远旋硅氧烷大分子聚二甲基硅氧烷-二甲基丙烯酸酯（PDMS- dma）和聚甲基氢硅氧烷- dma （PMHS- dma）以不同重量（wt）%的比例与PCL- da结合，得到PCL/PDMS和PCL/PMHS共网络支架，由于相分离增加了吸水量，降解率加快。然而，这些硅氧烷大分子缺乏水解不稳定的主链，因此限制了降解。本文合成了聚富马酸硅基（PSF）作为一种具有水解不稳定主链和链间交联性的杂化硅氧烷大分子。采用熔融盐模板溶剂铸造颗粒浸出（SCPL）法制备PCL- da与PSF的比例为90:10、75:25、60:40和50:50 wt%的PCL/PSF支架。尽管含有40%和50% PSF的PCL结晶度（即开关段）降低，但所有支架都保持了出色的形状记忆行为。添加10%和25% PSF的PCL/PSF支架也保持了纯PCL支架以及相应的PCL/PDMS和PCL/PMHS支架的模量。在基本条件下的体外降解实验表明，仅含10 wt% PSF的PCL/PSF支架的降解速度快于仅含PCL的支架，并且当含25 wt% PSF时，降解速度进一步提高，超过了相应的PCL/PDMS支架。观察到缺乏相分离，因此表明PSF的水解不稳定性实现了更快的降解。

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引用次数: 0

Metal-based ionic liquids as new catalyst of covalent adaptable networks based on poly(ethylene terephthalate) from textile grade 金属基离子液体作为纺织级聚对苯二甲酸乙酯共价自适应网络的新型催化剂

IF 4.5 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2026-03-19 Epub Date: 2026-02-10 DOI: 10.1016/j.polymer.2026.129721

Matheus H. Nachbar, Marion Colella, Sébastien Livi, Jannick D. Rumeau

The textile industry has recently been identified as a major contributor to plastic production and environmental pollution. The rising consumption of clothing with shorter lifespans, driven by fast fashion, has led to a significant increase in the production of synthetic fibers. Among these, poly(ethylene terephthalate) (PET) is the most widely used on the market. In this study, we propose a promising upcycling strategy for textile-grade PET via reactive extrusion to obtain covalent adaptable networks (CANs). A comparative study was performed using a conventional catalyst, Zn(acac)₂ and a metallic ionic liquid (MIL). The use of ionic liquids as transesterification catalysts demonstrated promising results and represents a compelling alternative to traditional metal-organic catalysts, owing to their lower toxicity and superior thermal stability. The resulting CAN systems exhibited high gel fractions and fast relaxation, regardless of the catalyst employed. Notably, faster relaxation times were achieved with the MIL catalyst, attributed to increased PET chain scission during the extrusion process. This work highlights the potential of ionic liquids as catalysts in PET-based CANs and emphasizes the importance of balancing catalyst loading to optimize final material properties while minimizing chain degradation during processing.

纺织业最近被确定为塑料生产和环境污染的主要贡献者。在快时尚的推动下，寿命较短的服装消费量不断增加，导致合成纤维的产量大幅增加。其中，市场上应用最广泛的是聚对苯二甲酸乙酯（PET）。在这项研究中，我们提出了一种有前途的纺织品级PET升级回收策略，通过反应挤出获得共价自适应网络（can）。采用传统催化剂Zn(acac)2和金属离子液体（MIL）进行了对比研究。离子液体作为酯交换催化剂的使用显示出良好的效果，并且由于其毒性较低和优越的热稳定性，它代表了传统金属有机催化剂的令人信服的替代品。所得的CAN体系表现出高凝胶分数和快速弛豫，无论使用哪种催化剂。值得注意的是，MIL催化剂实现了更快的松弛时间，这归因于挤出过程中PET链断裂的增加。这项工作强调了离子液体作为pet基can催化剂的潜力，并强调了平衡催化剂负载以优化最终材料性能的重要性，同时最大限度地减少加工过程中的链降解。

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