Polymer Chemistry最新文献_第7页

Temperature-triggered self-separating swelling poly(ionic liquid)s as efficient catalysts for CO2 cycloaddition reactions 温度触发自分离膨胀型聚离子液体作为CO2环加成反应的高效催化剂

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 DOI: 10.1039/d5py01097g

Jiayi Chen , Qing Sun , Haihong Zhao , Hao Chen

The cycloaddition reaction of CO₂ is one of the most promising pathways for CO₂ utilization due to its 100% atomic utilization rate and the generation of value-added carbonate products. However, it typically requires organic solvents, high temperatures, and elevated pressures. Swelling poly(ionic liquid)s (SPILs), capable of spontaneously forming porous structures under specific solvent and atmospheric conditions, are potential catalysts but face challenges in efficient catalyst–product separation. In this work, a thermosensitive SPIL catalyst, P-[VC₁₂Im]-C₁₂-Br, exhibiting temperature-responsive swelling behavior in the reaction substrate (epichlorohydrin), was designed and synthesized. When applied to CO₂ cycloaddition under solvent-free and atmospheric conditions at 80 °C, it achieved a 91.07% yield of the target product, chloromethyl oxazolidinone. Upon reaction completion, cooling to 25 °C triggered spontaneous catalyst contraction and separation from the product, enabling successful high-temperature catalysis and low-temperature separation. Moreover, P-[VC₁₂Im]-C₁₂-Br exhibited excellent recyclability (6 cycles) and broad substrate adaptability. The catalyst undergoes hydrogen bond-induced swelling at elevated temperatures, forming porous channels. The exposed active sites (Br⁻) facilitate epoxide ring-opening via nucleophilic attack, while the imidazolium rings assist in CO₂ capture and activation. These components synergistically catalyze the cycloaddition process. This study provides a novel strategy for efficient CO₂ conversion and also offers fundamental insights and practical guidance for developing a controllable SPIL catalyst.

CO2的环加成反应具有100%的原子利用率和生成高附加值碳酸盐产品的特点，是CO2利用最有前途的途径之一。然而，它通常需要有机溶剂、高温和高压。溶胀型聚离子液体（SPILs）在特定溶剂和大气条件下能够自发形成多孔结构，是潜在的催化剂，但在催化产物的高效分离方面面临挑战。本文设计并合成了一种热敏型SPIL催化剂P-[VC12Im]- c12 - br，该催化剂在反应底物（环氧氯丙烷）中具有温度响应性膨胀行为。在无溶剂和常压条件下，在80℃条件下进行CO2环加成，目标产物氯甲基恶唑烷酮的收率为91.07%。反应完成后，冷却至25℃触发催化剂自发收缩并与产物分离，实现了高温催化和低温分离的成功。此外，P-[VC12Im]- c12 - br具有良好的可回收性（6次循环）和广泛的底物适应性。催化剂在高温下发生氢键引起的膨胀，形成多孔通道。暴露的活性位点（Br-）通过亲核攻击促进环氧化物环打开，而咪唑环则有助于CO2的捕获和激活。这些组分协同催化环加成过程。该研究为CO2高效转化提供了一种新的策略，也为开发可控SPIL催化剂提供了基础见解和实践指导。

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引用次数: 0

PEG-based core-degradable nanoparticles via RAFT-mediated reverse-sequence PISA 基于聚乙二醇的核可降解纳米颗粒通过raft介导的逆向PISA

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-02-02 DOI: 10.1039/d5py01119a

Lei Lei , Thi Phuong Thu Nguyen , Yoann de Rancourt de Mimérand , Daniel Grande , Benjamin Le Droumaguet , Yves Gnanou , Benoit Couturaud

We report in this study the synthesis of core-degradable spherical nanoparticles via reverse-sequence polymerization-induced self-assembly (PISA) under aqueous conditions. A hydrophobic poly[(ethylene carbonate)-co-(ethylene oxide)] (PECEO) copolymer sample was utilized to synthesize the PECEO macro chain-transfer agent (PECEO macro-CTA), which was subsequently chain-extended with N,N′-dimethylacrylamide (DMAA) via reversible addition–fragmentation chain transfer (RAFT) polymerization, leading to the formation of stable spherical nanoparticles. In all cases, near-quantitative monomer conversion was achieved, as confirmed by ¹H NMR spectroscopy. Dynamic light scattering (DLS) analysis confirmed the formation of spherical nanoparticles with diameters in the 20–30 nm range. The incorporation of carbonate units within the polymer backbone conferred degradability to the nanoparticle, as further demonstrated by size exclusion chromatography (SEC) and ¹H NMR analyses when those nanoparticle suspensions were subjected to basic conditions.

在本研究中，我们报告了在水条件下通过逆向聚合诱导自组装（PISA）合成核心可降解的球形纳米颗粒。利用疏水聚[（碳酸乙烯）-co-（环氧乙烷）]（PECEO）共聚物样品合成PECEO宏观链转移剂（PECEO macro- cta），并通过可逆加成-断裂链转移（RAFT）聚合与N，N'-二甲基丙烯酰胺（DMAA）进行链扩展，形成稳定的球形纳米颗粒。在所有情况下，都实现了近定量的单体转化，如¹H核磁共振波谱所证实的那样。动态光散射（DLS）分析证实形成了直径在20 ~ 30 nm范围内的球形纳米颗粒。聚合物骨架内碳酸盐单元的掺入赋予纳米颗粒可降解性，当这些纳米颗粒悬浮液受到基本条件的影响时，尺寸排除色谱（SEC）和1h NMR分析进一步证明了这一点。

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引用次数: 0

Digital light processing 3D printable smart silicone-based elastomeric composites based on a synergistic dual-compatibilization strategy 基于协同双相容策略的数字光处理可3D打印智能硅基弹性复合材料

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-01-22 DOI: 10.1039/d5py01138h

Si-Ying Lan , Fu-Yue Tian , Xin-Yue Hao , Xin-Yu Li , Jing Bai , Nan-Ying Ning , Bing Yu , Ming Tian

Liquid silicone rubber (SiR) exhibits significant application value in medical devices, flexible electronics, and soft robotics due to its excellent biocompatibility, tunable mechanical properties, and chemical stability. The additive manufacturing of SiR via 3D printing technology enables the customized fabrication of complex structures, particularly in multidisciplinary fields that require personalized designs, such as biomedical implants, bioinspired flexible sensors, and dynamically responsive soft robots. Despite the high precision achievable through stereolithography (SLA) or digital light processing (DLP) photocuring techniques, the low modulus of SiR remains a challenge for high-precision 3D printing. Inspired by the concept of polymer composites, blending SiR with mechanically robust polycaprolactone (PCL, a biocompatible polymer) provides an effective strategy to address these limitations, but still faces the challenge caused by the poor compatibility between SiR and PCL. In this study, a synergistic dual-compatibilization strategy was designed, and amphiphilic compatibilizers (amino-functionalized carbon quantum dots, NH₂-CDs) and modified polycaprolactone (PCL-DA) were introduced to enhance interfacial compatibility between the two phases. The introduced NH₂-CDs, functioning as a nanoscale compatibilizer, effectively suppressed phase separation through interfacial Pickering stabilization, which resulted in a dramatic reduction of the dispersed SiR domain size from 25.94 ± 9.29 μm to 2.33 ± 0.55 μm, accompanied by the formation of a distinct interfacial layer (∼860 nm). The resulting SiR/PCL-DA/NH₂-CD composite fulfills the requirements for photocurable 3D printing, achieving high precision, multi-morphological adaptability, and considerable mechanical performance. It exhibits considerable mechanical performance with a tensile strength of 440.7 kPa and an elongation at break of 367%. Additionally, the incorporation of semi-crystalline PCL and NH₂-CDs endows the system with shape memory functionality (triggered at −5 °C and 60 °C) and fluorescence properties. This work presents a feasible approach for developing biocompatible, photocurable silicone elastomer-based composites via DLP 3D printing, offering broad prospects for advanced applications in smart materials and biomedical engineering.

液体硅橡胶（SiR）由于其优异的生物相容性、可调的机械性能和化学稳定性，在医疗器械、柔性电子和软机器人领域具有重要的应用价值。SiR的增材制造通过3D打印技术实现了复杂结构的定制制造，特别是在需要个性化设计的多学科领域，如生物医学植入物、生物启发柔性传感器和动态响应软机器人。尽管通过立体光刻（SLA）或数字光处理（DLP）光固化技术可以实现高精度，但SiR的低模量仍然是高精度3D打印的一个挑战。受聚合物复合材料概念的启发，将SiR与机械坚固的聚己内酯（PCL，一种生物相容性聚合物）混合为解决这些限制提供了一种有效的策略，但SiR与PCL之间的兼容性差仍然面临着挑战。本研究设计了一种协同双相容策略，通过引入两亲性相容剂（氨基功能化碳量子点，NH2-CDs）和改性聚己内酯（PCL-DA）来增强两相之间的界面相容性。引入的NH2-CDs作为纳米级相容剂，通过界面Pickering稳定有效抑制相分离，使分散的SiR畴尺寸从25.94±9.29 μm大幅减小到2.33±0.55 μm，并形成明显的界面层（~860 nm）。由此产生的SiR/PCL-DA/NH2-CDs复合材料满足光固化3D打印的要求，具有高精度、多形态适应性和可观的机械性能。拉伸强度为440.7 kPa，断裂伸长率为367%，具有良好的力学性能。此外，半晶PCL和NH2-CDs的掺入使该体系具有形状记忆功能（在-5°C和60°C触发）和荧光特性。本研究提出了一种通过DLP 3D打印技术开发生物相容性、光固化性有机硅弹性体基复合材料的可行方法，为智能材料和生物医学工程的先进应用提供了广阔的前景。

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引用次数: 0

Poly(2-oxazoline)-based core crosslinked star polymers via a combined cationic ring opening polymerization and click chemistry approach 聚（2-恶唑啉）基核心交联星型聚合物通过阳离子开环聚合和点击化学的结合方法

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-02-02 DOI: 10.1039/d5py01158b

Natalia Oleszko-Torbus , Barbara Mendrek , Agnieszka Fus-Kujawa , Agnieszka Kowalczuk , Marcelina Bochenek

This study reports the synthesis of core crosslinked star-shaped poly(2-oxazoline)s (CC-sPOxs) via an “arm first” approach combining cationic ring opening polymerization (CROP) with a thiol–ene click reaction. The resulting polymers consist of hydrophilic poly(2-ethyl-2-oxazoline) (PEtOx) arms and a poly(2-(3-butenyl)-2-oxazoline) (PButEnOx) core. First, a series of linear block copolymers PEtOx-b-PButEnOx was synthesized by CROP. These copolymers were subsequently crosslinked through a thiol–ene reaction using the crosslinker 2,2′-(ethylenedioxy)diethanethiol, yielding CC-sPOxs. To optimize the formation of star-shaped polymers, the thiol–ene reaction was carried out with varying amounts of the crosslinking agent and different amounts of comonomers. The resulting polymers were characterized in terms of their molar mass, composition, and solution behaviour and their cytotoxicity was assessed, confirming their potential suitability in biology and medicine. A novel method for synthesizing non-toxic poly(2-oxazoline)s with a non-linear macromolecular topology, with a precisely defined molar mass and number of arms, is presented in this work.

本文报道了将阳离子开环聚合（CROP）与巯基咔嗒反应相结合，采用“臂优先”方法合成核心交联星形聚（2-恶唑啉）s （CC-sPOxs）。所得聚合物由亲水性聚（2-乙基-2-恶唑啉）（PEtOx）臂和聚（2-（3-丁烯基）-2-恶唑啉）（PButEnOx）核组成。首先，用CROP合成了一系列线性嵌段共聚物PEtOx-b-PButEnOx。这些共聚物随后通过使用交联剂2,2 ' -（乙烯二氧基）二乙基硫醇的硫烯反应交联，得到cc - spox。为了优化星形聚合物的形成，在不同交联剂用量和不同共聚单体用量的条件下进行了硫醇烯反应。所得到的聚合物在摩尔质量、组成和溶液行为方面进行了表征，并评估了它们的细胞毒性，证实了它们在生物学和医学上的潜在适用性。本文提出了一种合成无毒聚（2-恶唑啉）s的新方法，该方法具有非线性大分子拓扑结构，具有精确定义的摩尔质量和臂数。

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引用次数: 0

Glutathione-responsive degradable amphiphilic polyester-based nanocarriers for targeted drug delivery 谷胱甘肽反应性可降解两亲性聚酯基靶向药物递送纳米载体

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-01-22 DOI: 10.1039/d5py01148e

Ankita Banerjee , Subhendu Biswas , Anindita Das

Disulfide bonds have been widely explored in cancer therapeutic applications due to their propensity to break in the presence of a tripeptide, glutathione (GSH), which is over-expressed in cancerous cells due to the upregulation of antioxidant defense pathways. Therefore, the incorporation of disulfide bonds into polymeric nanocarriers designed for anticancer drug delivery facilitates the degradation of the polymer backbone and promotes the release of the encapsulated drug in cancerous microenvironments. However, facile synthetic strategies that incorporate disulfide bonds into biodegradable and biocompatible amphiphilic polyesters for targeted delivery are limited. We have synthesized two such polyesters, and , integrating disulfide bonds into the polyester backbone through an organocatalyzed polycondensation reaction between a dipentafluorophenyl-activated ester and functionalized diols in N,N-dimethylformamide at 100 °C. Among these two, is a homopolyester comprising bis(2-hydroxyethyl) disulfide (HEDS), and is a copolyester comprising an additional biotin moiety for cancer cell selectivity and a fluorescent NMI-functionalized moiety for cellular trafficking, randomly distributed in the polymer chain as pendants, along with the disulfide bonds in the backbone. The time-dependent kinetics study during the polytransesterification reaction demonstrates complete monomer conversion within 24 hours. By virtue of its amphiphilic character, self-assembles into nanoaggregates in water with a size of ∼220 nm, and features the propensity to encapsulate the hydrophobic dye Nile red (NR). Degradation of the nanoaggregates and subsequent NR-dye release are illustrated in the presence of both GSH and lipase B. The self-assembled shows selective uptake towards cancerous HeLa cells compared to non-cancerous NIH 3T3 cells by biotin-receptor-mediated endocytosis, enabling its ability to selectively deliver the anticancerous drug, doxorubicin, resulting in decreased cellular viability, yielding an IC₅₀ value of 19 µg mL⁻¹ after 48 hours of incubation. These findings highlight the potential of this versatile methodology for designing structurally new degradable polyesters with tunable functionalities for other target-specific stimuli-responsive therapeutic applications.

二硫键在癌症治疗中的应用已被广泛探索，因为它们在三肽谷胱甘肽（GSH）存在下倾向于断裂，这是由于抗氧化防御途径的上调而在癌细胞中过度表达的。因此，将二硫键结合到设计用于抗癌药物递送的聚合物纳米载体上，有助于聚合物骨架的降解，并促进被封装药物在癌症微环境下的释放。然而，将二硫键结合到生物可降解和生物相容性的两亲聚酯中用于靶向递送的简易合成策略是有限的。我们已经合成了两种这样的聚酯，P1和P2，通过在N， N二甲基甲酰胺中，在100℃下，双五氟苯基活化酯和功能化二醇之间的有机催化缩聚反应，将二硫键整合到聚酯主链上。其中，P1是由双（2-羟乙基）二硫化物（HEDS）组成的均聚聚酯，P2是一种共聚酯，包括用于癌细胞选择性的额外生物素片段和用于细胞运输的荧光nmi功能化片段，随机分布在聚合物链上，作为垂链，以及主链上的二硫化物键。在多酯交换反应过程中的时间依赖动力学研究表明，在24小时内完成单体转化。由于其两亲性，P2在水中自组装成约220 nm的纳米聚集体，并具有包封疏水染料尼罗红（NR）的倾向。在GSH和脂肪酶b的存在下，纳米聚集体的降解和随后的nr染料释放已经被证明。与非癌变的NIH 3T3细胞相比，自组装的P2通过生物素受体介导的内吞作用，对癌变的HeLa细胞有选择性的摄取，使其能够选择性地递送抗癌药物阿霉素，导致细胞活力下降，孵卵48小时后的IC50值为19µg/mL。这些发现突出了这种通用方法在设计结构上具有可调功能的新型可降解聚酯的潜力，可用于其他目标特异性刺激反应治疗应用。

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引用次数: 0

A palindromic triplex architecture for DNA-templated synthesis designed for the core of a synthetic ribosome 为合成核糖体的核心设计的dna模板合成的回文三联体结构

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-01-26 DOI: 10.1039/d5py01159k

Rana Abdul Razzak , Jonathan Bath , Rachel K. O'Reilly , Andrew J. Turberfield

We demonstrate a triplex-based architecture for DNA-templated synthesis. This study is motivated by progress towards the development of a synthetic ribosome – autonomous, genetically programmable, molecular machinery for synthesis. Such schemes for the creation and evolution of chemically diverse DNA-tagged chemical libraries rely on hybridization reactions of oligonucleotide adapters to control sequential, DNA-templated reactions of covalently attached building blocks. To enable parallel one-pot library synthesis it is desirable that any building block can be incorporated at any position in a product oligomer: this is incompatible with geometries commonly used for DNA-templated synthesis which require alternate reactants to be attached to 3′ and 5′ termini of their adapters. Our triplex-based architecture overcomes this problem by templating reactions between building blocks attached to adapters with identical structures. It is intended to form the core of programmable molecular machinery for multistep synthesis. Here, we use single-step coupling reactions to characterize the triplex reaction template.

我们展示了一个基于三重结构的dna模板合成。这项研究的动机是朝着合成核糖体的发展进展-自主的，遗传可编程的，分子机器的合成。这种化学多样性dna标记化学文库的创建和进化方案依赖于寡核苷酸适配器的杂交反应来控制共价连接构建块的顺序dna模板反应。为了实现平行的一锅库合成，任何构建块都可以在产物低聚物的任何位置上结合，这与通常用于dna模板合成的几何形状不兼容，因为dna模板合成需要将替代反应物连接到其适配器的3‘和5’端。我们基于三重结构的体系结构通过在连接到具有相同结构的适配器的构建块之间构建反应的模板来克服这个问题。它旨在形成多步骤合成的可编程分子机器的核心。在这里，我们使用单步偶联反应来表征三重反应模板。

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引用次数: 0

Synthesis of glycerol-based (co)polyethers via ring-opening polymerization of glycidyl butyrate catalyzed by a one-component phosphonium tetraborane Lewis pair 单组分磷酸四硼烷路易斯对†催化丁酸缩水甘油开环聚合合成甘油基（co）聚醚

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-27 Epub Date: 2026-01-22 DOI: 10.1039/d5py01129a

Longfei Li , Minghao Liu , Zehao Wang , Xiaowu Wang , Zhibo Li

Linear polyglycerol (linPGC)-based functionalized polyethers exhibit superior water solubility and biocompatibility compared to traditional polyethylene glycol (PEG). However, their efficient and straightforward synthesis remains a significant challenge. Herein, we report a one-component phosphonium tetraborane Lewis pair () obtained via a three-step synthesis and demonstrate that enables the ring-opening polymerization (ROP) of commercially available (R)-(−)-glycidyl butyrate (RGB) at room temperature with a turnover number (TON) of 200, yielding α-Br/ω-OH and α-OH/ω-OH terminated poly(glycidyl butyrate) (PRGB). Kinetic studies reveal a pseudo-zero-order dependence on the monomer concentration and a first-order dependence on the catalyst concentration. An intramolecular synergistic catalysis mode is proposed. The deprotection of PRGB via alcoholysis releases pendant hydroxyl groups to form linPGC. Furthermore, RGB can be copolymerized with propylene oxide (PO), 1,2-butylene oxide (BO), allyl glycidyl ether (AGE), and tert-butyl glycidyl ether (t-BGE) to prepare linPGC-based functionalized polyethers with diverse sequence structures. This work provides a practical approach for obtaining various linPGC derivatives.

与传统聚乙二醇（PEG）相比，线性聚甘油（linPGC）基功能化聚醚具有优越的水溶性和生物相容性。然而，它们的高效和直接合成仍然是一个重大挑战。本文报道了一种单组分磷酸四硼烷路易斯对（P4B-Br）的三步合成方法，并证明了P4B-Br在室温下可实现(R)-(-)-丁酸甘油酯（RGB）的开环聚合（ROP），翻转数（TON）为200，得到α-Br/ω-OH和α-OH/ω-OH端接聚（丁酸甘油酯）（PRGB）。动力学研究表明，反应对单体浓度有准零级依赖，对催化剂浓度有一级依赖。提出了一种分子内协同催化模式。通过醇解解除PRGB的保护，释放出悬垂的羟基，形成linPGC。此外，RGB还可以与环氧丙烷（PO）、1,2-环氧丁烯（BO）、烯丙基缩水甘油醚（AGE）和叔丁基缩水甘油醚（t-BGE）共聚，制备具有不同序列结构的基于linpgc的功能化聚醚。这项工作为各种linPGC衍生物提供了一种实用的方法。

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引用次数: 0

Controlled synthesis and post-modification of polypentafluorostyrene in continuous flow 聚五氟苯乙烯连续流控制合成及后改性研究

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-19 Epub Date: 2026-01-12 DOI: 10.1039/d5py01142f

Alexander P. Grimm , Amna B. Asghar , Björn Schmidt , Christian W. Schmitt , Dominik Voll , Tanja Junkers , Patrick Théato

The establishment of automation of laboratory research over the past years has rapidly advanced all fields of chemical science including polymer synthesis. However, automated synthesis of polymers is largely limited to non-functional materials and post-polymerisation modification (PPM) remains underrepresented in flow polymer science. Herein, the polymerisation and PPM of pentafluorostyrene (PFSty), an established precursor polymer for PPM via para-fluoro-thiol-reaction (PFTR), in continuous flow is reported for the first time. The kinetic behaviour of the reversible addition–fragmentation chain transfer (RAFT) polymerisation of PFSty via transient timesweeping is demonstrated, yielding apparent polymerisation rate coefficients of 1.18 × 10⁻³ to 1.13 × 10⁻² s⁻¹ at 70–90 °C with 2-cyano-2-propyldodecyltrithiocarbonate (CPDT) as RAFT agent. Consequently, the PFTR of poly(PFSty) in continuous flow is investigated using 1-dodecanethiol (DT), 4-fluorobenzyl mercaptan (FBM), and 4-trifluoromethylbenzyl mercaptan (TFBM) showing quantitative conversion of FBM and TFBM after 6 min at 60 °C while DT does not exceed 53% modification of poly(PFSty) at 70 °C. Finally, a mixed flow-PFTR concept enables predictable copolymer modification with thiol mixtures through direct syringe pump control, achieving up to 99% precision depending on thiol reactivity. The proposed strategy offers a versatile approach for the continuous-flow synthesis and modification of reactive polymers, expanding the library of functional polymers for high-throughput methodologies.

在过去的几年里，实验室研究自动化的建立迅速推动了化学科学的各个领域，包括聚合物合成。然而，聚合物的自动合成在很大程度上局限于非功能材料，聚合后改性（PPM）在流动聚合物科学中仍然缺乏代表性。本文首次报道了五氟苯乙烯（PFSty）的连续聚合和PPM， PFSty是一种通过对氟硫醇反应（PFTR）进行PPM的前体聚合物。在70 ~ 90℃条件下，以2-氰基-2-丙基十二烷基三硫代羰基（CPDT）为RAFT催化剂进行了PFSty可逆加成-破碎链转移（RAFT）聚合反应，聚合速率系数为1.18·10-3 ~ 1.13·10-2 s-1。因此，使用1-十二硫醇（DT）、4-氟苄基硫醇（FBM）和4-三氟甲基苄基硫醇（TFBM）研究了poly（PFSty）在连续流动中的PFTR，结果显示FBM和TFBM在60°C下6 min后的定量转化，而DT在70°C下的改性不超过53%聚（PFSty）。最后，混合流- pftr概念通过直接注射泵控制，可预测共聚物与硫醇混合物的改性，根据硫醇反应性达到99%的精度。所提出的策略为反应性聚合物的连续流合成和改性提供了一种通用的方法，扩大了高通量方法的功能聚合物库。

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引用次数: 0

Direct arylation post-polymerization for Click-generated 1,2,3-triazole 点击生成1,2,3-三唑的直接芳基化后聚合

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-19 Epub Date: 2026-01-23 DOI: 10.1039/d6py00016a

Yuki Kitagawa , Shotaro Hayashi

Post-polymerization/functionalization approaches are promising tools for diversifying polymer synthesis. Herein, we report a combination of Cu-catalyzed azide–alkyne cycloaddition (CuAAC, Click reaction) and direct (C–H) arylation (DA) as post-polymerization strategies applied to the side chains of polystyrene. The Click reaction between azide-functionalized polystyrene (polymer ) and an alkyne afforded a polystyrene derivative () bearing a 1,2,3-triazole moiety on its side chain. The triazole unit introduced via the Click reaction serves as a reactive site for subsequent C–H activation in the DA process. Post-polymerization of with a bromoarene under optimized conditions enabled successful arylation, despite the generally low reactivity and selectivity associated with triazole C–H activation. Optimization was crucial to overcoming these challenges. The use of carboxylate ligands with bulky alkyl groups in the catalytic system significantly enhanced the reaction efficiency. The DA post-polymerization proceeded smoothly under a catalytic system composed of PdCl₂, K₂CO₃, and a bulky carboxylic acid additive (isostearic acid) in N,N-dimethylformamide (DMF) at 100 °C, affording the arylated product () in quantitative yield without side reactions that typically lead to polymer insolubilization. To further expand this approach, we applied the Click reaction to azide-terminated polystyrene, generating a polymer with a reactive 1,2,3-triazole end group. Subsequent DA with a bromoarene led to a dual-functionalized polymer end. This Click-induced, 1,2,3-triazole-based building block strategy demonstrates potential for polycondensation and post-polymerization of functional polymers.

聚合后/功能化方法是多样化聚合物合成的有前途的工具。本文报道了cu催化叠氮-炔环加成（CuAAC， Click反应）和直接（C-H）芳基化（DA）作为聚合后策略应用于聚苯乙烯侧链的组合。叠氮化物功能化聚苯乙烯（聚合物1）与炔之间的咔嗒反应产生了聚苯乙烯衍生物(2)，其侧链上有1,2,3-三唑基团。通过Click反应引入的三唑单元作为DA过程中后续C-H活化的反应位点。在优化的条件下，2与溴芳烃聚合后，成功实现了芳基化，尽管与三唑C-H活化相关的反应性和选择性普遍较低。优化对于克服这些挑战至关重要。在催化体系中使用具有大体积烷基的羧酸配体可显著提高反应效率。在由PdCl2、K2CO3和大量羧酸添加剂（异硬脂酸）组成的催化体系下，在100 °C的N，N-二甲基甲酰胺（DMF）中进行DA后聚合，获得了定量产率的芳基化产物(3)，没有通常导致聚合物不溶解的副反应。为了进一步扩展这种方法，我们将Click反应应用于叠氮端聚苯乙烯，生成了具有活性的1,2,3-三唑端基的聚合物。随后与溴芳烃的DA导致双官能化聚合物端。这种基于1,2,3-三唑的点击诱导构建块策略显示了功能聚合物的缩聚和后聚合的潜力。

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引用次数: 0

Facile preparation of polyester–polyglutamate diblock copolymers through regioselective polymerization of N-carboxyanhydride n -羧基氢化物区域选择性聚合制备聚酯-谷氨酸二嵌段共聚物

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2026-01-19 DOI: 10.1039/d5py01194a

Wanying Wang , Pengfei Li , Yue Xu , Shiqi Wei , Xiangdie Hou , Ning Li , Zhichao Zhou , Xiaohong Li , Ziyuan Song

Polyester–polypeptide block copolymers have shown great potential as biomaterials by combining the properties and advantages of both polymers. The preparation of the hybrid materials, however, is limited by the tedious protection/deprotection of chain-ends. Herein, we report the facile preparation of polyester–polyglutamate from bifunctional aminoalkyl alcohols, which regioselectively initiate the polymerization of N-carboxyanhydrides (NCAs) from the amino groups with negligible interference from the hydroxyl groups. Hydroxyl-capped polypeptide macroinitiators were then used for the preparation of diblock copolymers by skipping the conventional protection/deprotection steps. We believe that this work provides new insights into NCA stability against hydroxyl molecules, allowing for the preparation of well-defined polyester–polyglutamate copolymers in an efficient manner.

聚酯-多肽嵌段共聚物结合了这两种聚合物的特性和优点，作为生物材料显示出巨大的潜力。然而，杂化材料的制备受到链端繁琐的保护/去保护的限制。本文报道了用双功能氨基烷基醇制备聚谷氨酸聚酯的方法，该方法可以选择性地引发n -羧基氢化物（NCAs）与氨基的聚合，而羟基的干扰可以忽略不计。然后将羟基覆盖多肽marco引发剂用于制备二嵌段共聚物，跳过常规的保护/去保护步骤。我们相信这项工作为NCA对羟基分子的稳定性提供了新的见解，允许以有效的方式制备定义良好的聚酯-聚谷氨酸盐。

引用次数: 0