IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-12 DOI: 10.1016/j.polymer.2024.127825

Xiaoqin Cao, Yujun Feng, Hongyao Yin

We report a novel multicomponent initiators-based copolymerization strategy for synthesizing of acrylamide (AM) and 2-acrylamide-2-methylpropane sulfonic acid (AMPS) copolymers, denoted by P(AM-co-AMPS), with an ultra-high content of AMPS (≥50 mol%) and an ultra-high molecular weight (>10⁷ g/mol), while achieving a high conversion rate of monomer (∼100.0 %). The multicomponent initiators contain a redox couple, an azo compound, and a catalyst. Our investigation into the mechanism suggested that the synergistic effect in different rate constant for initiator decomposition between redox and azo initiators was responsible for actualizing ultra-high molecular weight copolymers with high conversion rates of monomer. Moreover, copolymers with 75 mol% and 100 mol% of AMPS were synthesized to verify the advantage of the multicomponent initiators-based strategy, both of which exhibited ultra-high molecular weights and ultra-high monomer conversion rates. This study fills a long-standing gap in research on the polyacrylamide family by providing highly functionalized P(AM-co-AMPS) with an ultra-high molecular weight. Moreover, it reveals how multicomponent initiators reconcile the contradiction between the ultra-high molecular weight and the high conversion rate in copolymerization.

我们报告了一种基于多组分引发剂的新型共聚策略，用于合成丙烯酰胺（AM）和 2-丙烯酰胺-2-甲基丙烷磺酸（AMPS）共聚物（以 P(AM-co-AMPS)表示），该共聚物具有超高的 AMPS 含量（≥ 50 mol%）和超高分子量（> 107 g/mol），同时实现了较高的单体转化率（∼100.0%）。多组分引发剂包含氧化还原偶联物、偶氮化合物和催化剂。我们对其机理的研究表明，氧化还原引发剂和偶氮化合物引发剂在引发剂分解的不同速率常数上的协同效应是实现高单体转化率的超高分子量共聚物的原因。此外，为了验证基于多组分引发剂策略的优势，还合成了含 75 摩尔% 和 100 摩尔%AMPS 的共聚物，这两种共聚物均表现出超高分子量和超高单体转化率。这项研究提供了具有超高分子量的高官能化 P(AM-co-AMPS)，填补了聚丙烯酰胺家族研究领域的长期空白。此外，它还揭示了多组分引发剂如何在共聚过程中协调超高分子量和高转化率之间的矛盾。

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引用次数: 0

Electrospun hydrophilic PAN/CO/TA composite nanofibrous membrane for adsorbing Cu(II) in water 用于吸附水中铜（II）的电纺亲水性 PAN/CO/TA 复合纳米纤维膜

IF 4.6 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-12 DOI: 10.1016/j.polymer.2024.127829

Baiqing Yu, Yanling Xu, Jianliang Nie, Dingfan Li, Zijuan Su, Zhi Huang, Xiaocan Zhang, Weibin Wu, Hai Li, Wuyi Zhou, Wenxu Zheng

In this paper, a novel polyacrylonitrile (PAN)/collagen (CO)/tannic acid (TA) composite nanofiber membrane for the adsorption of Cu(II) in water was prepared. The nanofibrous membranes were characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), thermogravimetric (TG), and water contact angle (WCA) techniques, and their adsorption performance on Cu(II) in water was tested. The results showed that incorporating CO improved the hydrophilic performance of the membranes, and the contact angle of PAN/CO decreased from 60.57° to 39.16° with the increase of CO content, which exhibited good hydrophilicity. Moreover, CO effectively crosslinked TA, so that TA was well fixed on the surface of the fiber membrane, and the resulting PAN/CO/TA composite nanofiber membrane had good fiber morphology, uniform fiber diameter distribution, with an average diameter of 292.22 nm, and good adsorption performance for Cu(II), up to 133.26 mg/g. The adsorption kinetics fitting showed that the adsorption mechanism was mainly electrostatic adsorption and chelation of Cu(II) by phenoxy anion. PAN/CO/TA and PAN/CO/TA/Cu nanofiber membranes showed bacteriostatic effects on E. coli and S. aureus, with PAN/CO/TA/Cu nanofiber membranes being particularly effective, with the average inhibition bands for E. coli and S. aureus being 7.50 mm and 10.05 mm, respectively. The distribution of the electric field during the spinning process was also simulated by finite element analysis in this study. Since TA is a natural polymer of plant origin and CO is of animal origin, it provides an environmentally friendly and cost-effective method to remove Cu(II) from water.

本文制备了一种新型聚丙烯腈（PAN）/胶原蛋白（CO）/单宁酸（TA）复合纳米纤维膜，用于吸附水中的铜（II）。通过傅立叶变换红外（FTIR）、扫描电子显微镜（SEM）、热重（TG）和水接触角（WCA）技术对纳米纤维膜进行了表征，并测试了它们对水中 Cu（II）的吸附性能。结果表明，CO 的加入提高了膜的亲水性能，随着 CO 含量的增加，PAN/CO 的接触角从 60.57°降至 39.16°，表现出良好的亲水性。此外，CO 能有效交联 TA，使 TA 很好地固定在纤维膜表面，得到的 PAN/CO/TA 复合纳米纤维膜具有良好的纤维形貌，纤维直径分布均匀，平均直径为 292.22 nm，对 Cu(II) 的吸附性能良好，最高可达 133.26 mg/g。吸附动力学拟合结果表明，吸附机理主要是静电吸附和苯氧基阴离子对 Cu（II）的螯合作用。PAN/CO/TA 和 PAN/CO/TA/Cu 纳米纤维膜对大肠杆菌和金黄色葡萄球菌有抑菌作用，其中 PAN/CO/TA/Cu 纳米纤维膜的抑菌效果尤为显著，对大肠杆菌和金黄色葡萄球菌的平均抑菌带分别为 7.50 mm 和 10.05 mm。本研究还通过有限元分析模拟了纺丝过程中的电场分布。由于 TA 是源于植物的天然聚合物，而 CO 是源于动物的天然聚合物，因此它为去除水中的 Cu（II）提供了一种环境友好且经济有效的方法。

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引用次数: 0

PCTFE microporous membrane with high corrosion-resistance and ultra-fast oil/water separation performances 具有高耐腐蚀性和超快油水分离性能的 PCTFE 微孔膜

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-10 DOI: 10.1016/j.polymer.2024.127789

Lu He , Jingxian Qin , Wanli Zhang , Weiwei Zhu , Jiang Li , Shaoyun Guo , Jiabin Shen

Membrane separation technology is a promising choice for treating oily water from industrial and domestic sewage. The elaborate design of pore structure can realize a good trade-off between separation flux and efficiency, thus taking the full advantages of membrane separation. Herein, polychlorotrifluoroethylene (PCTFE) microporous membrane with tunable pore structure was fabricated via a sacrificial template method. Fluoroelastomer (FR), serving as sacrificial template, was incorporated into PCTFE via a solvent-assisted method, forming PCTFE/FR blending films. After removing FR via solvent-dissolving, porous PCTFE membrane was obtained. More important, the gradual increment of FR loading made the morphology of PCTFE/FR blending films realize the transformation from “sea-island” to bicontinuous structure, thus endowing the membranes with tunable pore structure, surface wettability, as well as mechanical properties. Among the candidates, 50FR membranes possessed good flexibility, twist-resistance, as well as excellent creep-resistance and can efficiently separate oil from various water/oil mixtures. The oil (dichloromethane) permeability, separation efficiency, and filtrated oil purity were high up ∼10000 L/(m²⋅h), ∼99 %, and ∼99.92 wt%, respectively. Additionally, although undergoing 25 separation cycles or being immersed into various highly-corrosive liquid (including 1 M HCl, 1 M NaOH, DMF, ethanediamine, and concentrated HNO₃) for 7 days, the properties of the membrane changed little. These features suggested a great potential for preparing PCTFE membranes used for oil/water separation in various harsh environment.

膜分离技术是处理工业和生活污水中含油水的一种很有前途的选择。对孔隙结构的精心设计可以在分离通量和分离效率之间实现良好的权衡，从而充分发挥膜分离的优势。本文通过牺牲模板法制备了孔结构可调的聚三氟氯乙烯（PCTFE）微孔膜。作为牺牲模板的氟橡胶（FR）通过溶剂辅助法与 PCTFE 结合，形成 PCTFE/FR 混合膜。通过溶剂溶解去除 FR 后，得到多孔 PCTFE 膜。更重要的是，随着 FR 负载的逐渐增加，PCTFE/FR 混合膜的形态实现了从 "海岛 "到双连续结构的转变，从而使膜具有可调的孔隙结构、表面润湿性和机械性能。其中，50FR 膜具有良好的柔韧性、抗扭曲性和优异的抗蠕变性，可从各种水/油混合物中有效分离油。油（二氯甲烷）渗透率、分离效率和滤油纯度分别高达 ∼10000 L/（m2-h）、∼99% 和 ∼99.92 wt%。此外，尽管经历了 25 次分离循环或在各种高腐蚀性液体（包括 1M HCl、1M NaOH、DMF、乙二胺和浓 HNO3）中浸泡 7 天，膜的性能变化不大。这些特点表明，制备在各种恶劣环境中用于油/水分离的 PCTFE 膜具有很大的潜力。

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引用次数: 0

Cis-1,4-specific polymerization of 1,3-conjugated dienes with bis(benzimidazole)NiCl2 catalyst system 双(苯并咪唑)NiCl2 催化剂体系对 1,3-共轭二烯的顺式-1,4-特异性聚合反应

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-09 DOI: 10.1016/j.polymer.2024.127806

Yasuyuki Ueda , Kakeru Tsukahara , Masahito Hasumi , Kohei Uyama , Hiroshi Yukawa , Takehito Kato , Tomoyuki Toda , Shun Ohta , Kei Nishii

We report herein that the catalytic system composed of a bis(benzimidazole)NiCl₂ complex (1, bis(benzimidazole) = phenylbis(benzimidazol-2-yl)methane), Al(C₈H₁₇)₃ (AlOct₃), and [Ph₃C][B(C₆F₅)₄] mediates highly cis-1,4-specific (up to 95 %) polymerization of isoprene (IP). This is the first nickel complex-based catalyst system that achieved the cis-1,4-specific IP polymerization with a selectivity of more than 90 %. The effects of AlR₃ (R = ⁱBu, Et, Me), AlEt₂Cl and activator ([PhNMe₂H][B(C₆F₅)₄], B(C₆F₅)₃, MAO) on the polymerization behavior were also investigated. The 1/AlOct₃/[Ph₃C][B(C₆F₅)₄] system also catalyzed the cis-1,4-specific polymerization of other 1,3-conjugated dienes such as 1,3-butadiene (BD), (E)-1,3-pentadiene (EPD) and β-myrcene (MY) (up to 92 % for BD, 84 % for EPD and 72 % for MY).

我们在此报告了由双(苯并咪唑)NiCl2 复合物（1，双(苯并咪唑)=苯基双(苯并咪唑-2-基)甲烷）、Al(C8H17)3 (AlOct3) 和 [Ph3C][B(C6F5)4] 组成的催化体系介导了异戊二烯（IP）的高度顺式-1,4-特异性聚合（高达 95%）。这是首个基于镍络合物的催化剂体系，它实现了选择性超过 90% 的顺式-1,4-特异性 IP 聚合。此外，还研究了 AlR3（R = iBu、Et、Me）、AlEt2Cl 和活化剂（[PhNMe2H][B(C6F5)4]、B(C6F5)3、MAO）对聚合行为的影响。1/AlOct3/[Ph3C][B(C6F5)4] 系统还催化了其他 1,3-共轭二烯（如 1,3-丁二烯 (BD)、(E)-1,3-戊二烯 (EPD) 和 β-月桂烯 (MY)）的顺式-1,4-特异性聚合（BD 达 92%，EPD 达 84%，MY 达 72%）。

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引用次数: 0

Conjugated tetraphenylethene-based polymers for supercapacitor 用于超级电容器的共轭四苯基乙烯基聚合物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-09 DOI: 10.1016/j.polymer.2024.127778

Abdelreheem Abdelfatah Saddik , Hani Nasser Abdelhamid

The synthesis of two conjugated polymers (P1 and P2) for supercapacitor application was reported. The materials were prepared using a condensation reaction between tetraphenylethene (TPE) with di-(TPE-2CHO) or tetra-carboxaldehyde (TPE-4CHO) derivatives and 1,5-diaminonaphthalene (1,5-DAN). The polymers were characterized using Fourier transforms infrared (FT-IR), solid-state ¹³C nuclear magnetic resonance (¹³C NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and diffuse reflectance spectroscopy (DRS). P1 and P2 polymers displayed a spherical shape, with particle sizes of 6.8 ± 1 μm and 0.97 ± 0.1 μm, respectively. In addition, P1 and P2 exhibited wide light absorption (200–466 nm), accompanied by a relatively low bandgap of 2.3 eV and 2.4 eV for P1 and P2 respectively. Electrochemical investigations of P1 and P2 revealed redox behavior observed in the cyclic voltammetry (CV) curves suggesting a faradaic charge storage mechanism. At a scan rate of 1 mV/s, P1 and P2 demonstrated specific capacitances of 274.8 F/g and 207.9 F/g, respectively. The electrochemical performance of both polymers was further analyzed using galvanostatic charge-discharge (GCD), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) using Nyquist plots. The observed decrease in charge transfer resistance for P1 and P2 can be ascribed to the conjugation within their chemical structures. The polymer can be recycled for 5000 cycles with <10 % loss of the polymer's efficiency.

报告了两种用于超级电容器的共轭聚合物（分别称为 P1 和 P2）的合成。这些材料以四苯基乙烯（TPE）与二（TPE-2CHO）/四甲醛（TPE-4CHO）衍生物和 1,5-二氨基萘（1,5-DAN）为单体，通过缩合反应制备而成。利用傅立叶变换红外光谱 (FT-IR)、固态 13C 核磁共振 (NMR)、扫描电子显微镜 (SEM)、X 射线衍射 (XRD) 和漫反射光谱 (DRS) 对聚合物进行了表征。P1 和 P2 聚合物呈球形，粒径分别为 6.8 ± 1 μm 和 0.97 ± 0.1 μm。此外，P1 和 P2 具有较宽的光吸收范围（200-466 纳米），带隙相对较低，分别为 2.3 eV 和 2.4 eV。P1 和 P2 的电化学研究表明，循环伏安曲线中观察到的氧化还原行为是可逆的，表明存在法拉第电荷存储机制。在 1 mV/s 的扫描速率下，P1 和 P2 的比电容分别为 274.8 F/g 和 207.9 F/g。使用电静态充放电（GCD）、线性扫描伏安法（LSV）和使用奈奎斯特图的电化学阻抗光谱法（EIS）进一步分析了这两种聚合物的电化学性能。观察到 P1 和 P2 的电荷转移电阻降低，这是因为它们的化学结构中存在共轭作用。这种聚合物可循环使用 5000 次，而其效率损失为 10%。

{"title":"Conjugated tetraphenylethene-based polymers for supercapacitor","authors":"Abdelreheem Abdelfatah Saddik , Hani Nasser Abdelhamid","doi":"10.1016/j.polymer.2024.127778","DOIUrl":"10.1016/j.polymer.2024.127778","url":null,"abstract":"<div><div>The synthesis of two conjugated polymers (<strong>P1</strong> and <strong>P2</strong>) for supercapacitor application was reported. The materials were prepared using a condensation reaction between tetraphenylethene (<strong>TPE</strong>) with di-(<strong>TPE-2CHO</strong>) or tetra-carboxaldehyde (<strong>TPE-4CHO</strong>) derivatives and 1,5-diaminonaphthalene (<strong>1,5-DAN</strong>). The polymers were characterized using Fourier transforms infrared (FT-IR), solid-state <sup>13</sup>C nuclear magnetic resonance (<sup>13</sup>C NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and diffuse reflectance spectroscopy (DRS). <strong>P1</strong> and <strong>P2</strong> polymers displayed a spherical shape, with particle sizes of 6.8 ± 1 μm and 0.97 ± 0.1 μm, respectively. In addition, <strong>P1</strong> and <strong>P2</strong> exhibited wide light absorption (200–466 nm), accompanied by a relatively low bandgap of 2.3 eV and 2.4 eV for P1 and P2 respectively. Electrochemical investigations of <strong>P1</strong> and <strong>P2</strong> revealed redox behavior observed in the cyclic voltammetry (CV) curves suggesting a faradaic charge storage mechanism. At a scan rate of 1 mV/s, <strong>P1</strong> and <strong>P2</strong> demonstrated specific capacitances of 274.8 F/g and 207.9 F/g, respectively. The electrochemical performance of both polymers was further analyzed using galvanostatic charge-discharge (GCD), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) using Nyquist plots. The observed decrease in charge transfer resistance for <strong>P1</strong> and <strong>P2</strong> can be ascribed to the conjugation within their chemical structures. The polymer can be recycled for 5000 cycles with <10 % loss of the polymer's efficiency.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127778"},"PeriodicalIF":4.1,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597518","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

Polycondensation, cyclization and disproportionation of solid Poly(L-lactide) trifluoroethyl esters and the simultaneous formation of extended chain crystals and extended ring crystals 固体聚（L-内酯）三氟乙酯的缩聚、环化和歧化以及延伸链晶体和延伸环晶体的同时形成

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-09 DOI: 10.1016/j.polymer.2024.127800

Steffen M. Weidner , Felix Scheliga , Hans R. Kricheldorf

Two poly(L-lactide)s (PLAs) with a degree of polymerization (DP) of 20 or 100 were prepared by trifluoroethanol-initiated ring-opening polymerization (ROP) catalyzed by tin(II) 2-ethyl hexanoate (SnOct₂). These PLAs were annealed at 140 °C or at 160 °C in the presence of SnOct₂, and the changes in topology and molecular weight distribution (MWD) were monitored by matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC). For the PLA with a DP 20, the main reaction was polycondensation combined with higher dispersities. In the case of the DP 100, PLA polycondensation was combined with disproportionation and the formation of a new MWD maximum around m/z 3500. In addition, extensive cyclization occurred, and the resulting cyclic PLAs crystallized separately from the linear chains in the form of extended ring crystals. These results also suggest that both extended chain and extended ring crystals posses the same crystal thickness as a result of thermodynamically controlled transesterification in the solid state.

在 2- 乙基己酸锡（II）（SnOct2）催化下，通过三氟乙醇引发的开环聚合（ROP）制备了聚合度（DP）为 20 或 100 的两种聚乳酸（PLA）。这些聚乳酸在 SnOct2 的存在下于 140 ℃ 或 160 ℃ 退火，并通过基质辅助激光解吸/电离飞行时间（MALDI TOF）质谱法和凝胶渗透色谱法监测拓扑结构和分子量分布（MWD）的变化。对于 DP 20 的聚乳酸，主要反应是缩聚和较高的分散度。对于 DP 值为 100 的聚乳酸，缩聚反应与歧化反应相结合，并在 m/z 3 500 附近形成了新的最大截留分子量。此外，还出现了广泛的环化现象，由此产生的环状聚乳酸与线性链分开结晶，形成延伸的环状晶体。这些结果还表明，由于固态热力学控制的酯交换作用，延伸链和延伸环晶体具有相同的晶体厚度。

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引用次数: 0

Preparation of polyurethane complex microsphere and high performance for self-healing epoxy coatings 制备聚氨酯复合微球和高性能自修复环氧涂料

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-08 DOI: 10.1016/j.polymer.2024.127805

Fang Wang , Naipin Chen , Jiaqi Liu , Xinbao Zhu

The ability of an active protective organic coating to restore its protection functionality in the event of a coating defect is crucial for ensuring durable performance under harsh corrosive conditions. In the present work, a novel thermogenesis effect polyurethane complex microsphere with a particle size of approximately 430 nm was developed using CNCs and LNPs as Pickering emulsifiers. The obtained microspheres (4 wt%) were incorporated into epoxy-amine networks, resulting in improved toughness and bending strength. Additionally, tensile measurement results demonstrated that the composite resin exhibited a self-healing efficiency of 81.25 % at room temperature within 30 min. Meanwhile, for the NIR-triggered self-healing process, the damaged samples could be locally repaired quickly. Experiments also showed that the microspheres exhibited excellent anti-ultraviolet aging performance and satisfying storage stability for more than 20 days at room temperature. Importantly, the as-prepared epoxy complex resin served as an in-situ self-healing metal coating, confirming its long-lasting corrosion resistance. This work provides an efficient strategy for high-performance self-healing materials, particularly epoxy anti-corrosion coatings.

活性有机保护涂层在出现涂层缺陷时恢复其保护功能的能力对于确保在恶劣腐蚀条件下的持久性能至关重要。在本研究中，使用 CNCs 和 LNPs 作为 Pickering 乳化剂，开发了一种新型热生成效应聚氨酯复合物微球，其粒径约为 430 nm。获得的微球（4 wt%）与环氧胺网络结合，从而提高了韧性和弯曲强度。此外，拉伸测量结果表明，复合树脂在室温下 30 分钟内的自愈合效率为 81.25%。同时，在近红外触发的自愈合过程中，受损样品可迅速得到局部修复。实验还表明，微球具有优异的抗紫外线老化性能，在室温下可稳定贮存 20 天以上。重要的是，制备的环氧复合树脂可作为原位自修复金属涂层，具有持久的耐腐蚀性。这项研究为高性能自修复材料，尤其是环氧防腐涂层提供了一种有效的策略。

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引用次数: 0

Hierarchical arrangement of P(VDF-TrFE) copolymer crystals: A SAXS and AFM study P(VDF-TrFE)共聚物晶体的分层排列：SAXS 和原子力显微镜研究

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-08 DOI: 10.1016/j.polymer.2024.127818

Pedro M. Resende, Sara Zanchi, Jean-David Isasa, Raymond Khayat, Georges Hadziioannou, Guillaume Fleury

P(VDF-TrFE) copolymers are materials with high relevance in printed organic electronics. These copolymers easily crystallize into the ferroelectric phase without resorting to post-deposition treatments (thermal annealing, poling, or mechanical stretching). The detection of a morphotropic phase boundary further increased the interest in this copolymer system by demonstrating relaxor behavior for higher TrFE content. This prompted an in-depth analysis of the P(VDF-TrFE) chiral chain structure responsible for the relaxor properties. Nevertheless, the efficient application of these materials also depends heavily on the quality and morphology of the crystalline domains. In this work, we combine SAXS and AFM imaging to analyze the structure of the crystalline domains as a function of the TrFE content. The detection of different structural distributions revealed the presence of hierarchical arrangements within the crystalline domains. Furthermore, these hierarchical arrangements were observed to change with the TrFE monomer content, presenting distinct morphologies for low and high TrFE contents, in line with previous works on the morphotropic phase boundary in these systems.

P(VDF-TrFE)共聚物是与印刷有机电子产品高度相关的材料。这些共聚物很容易结晶成铁电相，无需进行沉积后处理（热退火、极化或机械拉伸）。形态各向同性相界的检测进一步提高了人们对这种共聚物体系的兴趣，因为它显示了较高 TrFE 含量下的弛豫行为。这促使我们对产生弛豫特性的 P（VDF-TrFE）手性链结构进行深入分析。然而，这些材料的有效应用还在很大程度上取决于结晶畴的质量和形态。在这项工作中，我们结合 SAXS 和原子力显微镜成像技术，分析了结晶畴结构与 TrFE 含量的函数关系。对不同结构分布的检测表明，结晶畴内存在分层排列。此外，还观察到这些分层排列随 TrFE 单体含量的变化而变化，在低和高 TrFE 含量下呈现出不同的形态，这与之前关于这些体系中各向异性相界的研究结果一致。

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引用次数: 0

Environmental modification of cellulose fibers for reducing dye diffusion rate by anionic polyacrylamide 利用阴离子聚丙烯酰胺对纤维素纤维进行环境改性以降低染料扩散率

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-08 DOI: 10.1016/j.polymer.2024.127814

Liujun Pei , Simin Sun , Jingyuan Yi , Jifang Shen , Yuanyuan An , Gang Sun , Jiping Wang

Reactive dyeing is the primary method for coloring cellulose fibers due to its vibrant colors, various hues, excellent colorfastness, and cost-effectiveness. However, this process consumes a large amount of water and chemicals, leading to significant environmental concerns due to the wastewater. Non-aqueous media/less water dyeing has emerged as a cleaner alternative, showing promising results in dyeing cotton fibers with reactive dyes. Nevertheless, the rapid adsorption rate of dyes can impact the evenness of dyeing. This study explores the use of anionic polyacrylamide (APAM) in the modification bath to reduce dye adsorption rate and enhance dye desorption during cellulose fibers dyeing. Fourier transform infrared spectroscopy (FT-IR) and field-emission scanning electron microscope (FSEM) analysis revealed effective interaction between APAM and cellulose fibers. Thermal gravimetric analysis (TGA), X-ray diffraction (XRD), and breaking strength tests indicated minimal impact on the thermal stability and physical properties of cellulose fibers with APAM modification. Zeta potential testing demonstrated that APAM modification reduced the surface potential of cellulose fibers and increased their negative charge. The adsorption rate of reactive dye decreased with APAM modification, while dye fixation, washing, and rubbing fastness remained largely unaffected. Adsorption isotherm results supported the weakening of the affinity between dyes and fibers after APAM treatment. Furthermore, the electrostatic potentials of fibers decreased after APAM modification. Compared to salt-free dyeing in non-aqueous media dyeing systems, anionic polymer modification not only improves the level dyeing performance of cotton fiber and reduces 0.9 % in dyeing costs, but also increases production efficiency.

反应染色是纤维素纤维着色的主要方法，因为它色彩鲜艳、色调多样、色牢度极佳，而且成本效益高。然而，这种工艺需要消耗大量的水和化学品，产生的废水会对环境造成严重影响。非水介质/无水染色已成为一种更清洁的替代方法，在用活性染料对棉纤维进行染色方面取得了可喜的成果。然而，染料的快速吸附率会影响染色的匀染性。本研究探讨了在改性浴中使用阴离子聚丙烯酰胺（APAM）来降低染料吸附率，并增强纤维素纤维染色过程中的染料解吸。傅立叶变换红外光谱（FT-IR）和场发射扫描电子显微镜（FSEM）分析表明了 APAM 与纤维素纤维之间的有效相互作用。热重分析（TGA）、X 射线衍射（XRD）和断裂强度测试表明，APAM 改性对纤维素纤维的热稳定性和物理性能影响极小。Zeta 电位测试表明，APAM 改性降低了纤维素纤维的表面电位，增加了其负电荷。活性染料的吸附率随着 APAM 改性而降低，而染料固着、洗涤和摩擦牢度则基本不受影响。吸附等温线结果表明，APAM 处理后染料与纤维之间的亲和力减弱。此外，APAM 改性后纤维的静电电位降低。与非水介质染色体系中的无盐染色相比，阴离子聚合物改性不仅能改善棉纤维的匀染性能，降低 0.9% 的染色成本，还能提高生产效率。

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引用次数: 0

A novel melt extrusion method for efficient and large-scale in-situ exfoliation of boron nitride to prepare high performance thermal conductive polymer composite 一种新型熔融挤压法，用于高效、大规模地原位剥离氮化硼以制备高性能导热聚合物复合材料

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2024-11-08 DOI: 10.1016/j.polymer.2024.127809

Lingcao Tan , Jingjun Zhong , Wenshuai Guo , Qi Gao , Jiqian Li , Yue He , Jiarong Huang , Wenhua Xu , Shuping Xiao , Huiwen Yu , Baiping Xu

The polymer/hexagonal boron nitride (h-BN) thermal conductive composite an excellent candidate for thermal management materials due to its insulation properties. However, it is a challenge to achieve efficient large-scale exfoliation of h-BN through melt blending to balance thermal conductivity and mechanical properties. In this work, an innovative melt mixing strategy using the co-rotating non-twin screw extruder (NTSE) was developed to prepare the high-density polyethylene (HDPE)/h-BN composites with excellent overall performance. The results were well compared with those of conventional twin screw extruder (TSE). The NTSE triggers chaotic mixing and provides a strong elongation flow field capable of h-BN efficiently exfoliating into a few layers, while simultaneously ensuring uniform dispersion and distribution within HDPE. The in-plane thermal conductivity and elongation at break of the NTSE composite with 10 wt% h-BN addition were 7.63 W∙m⁻¹ K⁻¹ and 653.1 %, which were 74.7 % and 70.3 % higher than those prepared by TSE, while the enhancement rates rose to 174.6 % and 74.4 % when 30 wt% h-BN was added, respectively. The in-plane thermal conductivity enhancement ratio of NTSE was more than 3000 % when the h-BN content was higher than 10 wt%. Besides, the thermal stability, crystallinity, and thermal diffusion of the NTSE composites were also enhanced to different degrees. This strategy is efficient to coordinating the conflicting between the comprehensive performance and large-scale preparation of thermally conductive polymer composites.

聚合物/六方氮化硼（h-BN）导热复合材料因其绝缘性能而成为热管理材料的绝佳候选材料。然而，如何通过熔融混合实现 h-BN 的高效大规模剥离，以平衡导热性和机械性能，是一项挑战。本研究开发了一种创新的熔体混合策略，使用同向旋转非双螺杆挤出机（NTSE）制备出综合性能优异的高密度聚乙烯（HDPE）/h-BN 复合材料。其结果与传统双螺杆挤出机（TSE）的结果进行了很好的比较。NTSE 能引发混沌混合，提供强大的伸长流场，使 h-BN 有效地剥离成几层，同时确保在高密度聚乙烯中的均匀分散和分布。添加 10 wt% h-BN 的 NTSE 复合材料的面内热导率和断裂伸长率分别为 7.63 W∙m-1 K-1 和 653.1%，比 TSE 制备的复合材料分别高 74.7% 和 70.3%，而当添加 30 wt% h-BN 时，增强率分别上升到 174.6% 和 74.4%。当 h-BN 含量高于 10 wt% 时，NTSE 的面内热导率增强率超过 3000%。此外，NTSE 复合材料的热稳定性、结晶度和热扩散性能也有不同程度的提高。该策略有效地协调了导热聚合物复合材料综合性能与大规模制备之间的矛盾。

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