Polymer Chemistry最新文献_第9页

Structure, humidity adaptivity, and elasticity of hydrogen-bonded complexes formed by self-assembly of a triblock copolymer and a homopolymer† 三嵌段共聚物和均聚物自组装形成的氢键复合物的结构、湿度适应性和弹性

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-02 DOI: 10.1039/d4py00959b

Weijie Wang , Hanxin Jian , Hao Huang , Fengfeng Feng , Qingye Meng , Yuli Li , Gang Chen , Shuguang Yang

Specific aggregation structures largely influence the macro-physical performances of materials. Small changes in molecular components, conformation, crystallisation and microphase transitions can dramatically alter material properties. Here, we combine the triblock copolymer polystyrene-b-poly(ethylene oxide)-b-polystyrene (SES) with the homopolymer poly(acrylic acid) (PAA), fabricating elastomers with multi-hierarchical architectures. Unlike the single molecular chain of traditional elastomers, the flexible domain of these elastomers is formed via hydrogen bonding of the complex chains (A/E) of poly(ethylene oxide) (PEO) and PAA. The polystyrene (PS) blocks are microphase-separated and hydrophobically associated, providing physical crosslinks among the flexible complex chains and enhancing the strength of the elastomers. The influence of the molecular weight of the PS blocks, molecular chain length of PAA, and relative humidity on the elastomer's macro-physical properties was revealed using small-angle X-ray scattering, transmission electron microscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, and tensile stress–strain measurements. The PS block forms a hard spherical domain that affects the hydrogen-bonding complex behaviours of the PAA and PEO segments. Enlarging the PS sphere would hinder the formation of the PAA/PEO complex, but this trend is mitigated by shortening the PAA chain length. Hydrophobic steric hindrance by the PS sphere disturbs the association behaviours of the PAA and PEO segments. These structural differences result in different mechanical properties of the elastomers. Moreover, the elastomers adapt to changes in the relative humidity and show an obvious humidity-induced glass transition. The elastomers possess good elasticity properties under low and high humidity conditions. The methods and ideas presented in this study will enable the construction of new types of elastomers.

特定的聚集结构在很大程度上影响着材料的宏观物理性能。分子成分、构象、结晶和微相转变的微小变化都会极大地改变材料的性能。在这里，我们将三嵌段共聚物聚苯乙烯-b-聚环氧乙烷-b-聚苯乙烯（SES）与均聚物聚丙烯酸（PAA）相结合，制造出具有多层结构的弹性体。与传统弹性体的单分子链不同，这些弹性体的柔性域是通过聚（环氧乙烷）（PEO）和 PAA 的复合链 (A/E) 的氢键作用形成的。聚苯乙烯（PS）块具有微相分离和亲水性，可在柔性复合链之间产生物理交联，从而增强弹性体的强度。利用小角 X 射线散射、透射电子显微镜、差示扫描量热仪、傅立叶变换红外光谱和拉伸应力应变测量法，研究了 PS 块的分子量、PAA 分子链长和相对湿度对弹性体宏观物理性质的影响。PS 块形成了一个坚硬的球形域，影响 PAA 和 PEO 段的氢键复合行为。增大 PS 球体会阻碍 PAA/PEO 复合物的形成，但缩短 PAA 链长可以缓解这一趋势。PS 球体的疏水立体阻碍干扰了 PAA 和 PEO 段的结合行为。这些结构差异导致弹性体具有不同的机械性能。此外，弹性体还能适应相对湿度的变化，并表现出明显的湿度诱导玻璃化转变。在较低和较高湿度条件下，弹性体都具有良好的弹性特性。本研究提出的方法和观点将有助于制造新型弹性体。

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引用次数: 0

Constructing self-healing flexible supercapacitors using a graphene oxide synergistic multi-network polymer-supramolecular hydrogel electrolyte† 通过氧化石墨烯协同多网络聚合物-超分子水凝胶电解质构建自修复柔性超级电容器

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-02 DOI: 10.1039/d4py00809j

Xiaoyan Li , Xiuting Shi , Anbai Li , Mengmeng Xun , Shuzhen Cui , Kanjun Sun , Hui Peng , Guofu Ma , Yuxi Xu

Hydrogels are attracting increasing interest and have great potential as electrolytes for flexible supercapacitors (FSCs) in wearable and portable electronic devices. However, for practical applications, hydrogel electrolytes are hampered by factors such as their unsatisfactory temperature tolerance, poor mechanical properties and no self-healing properties. Herein, a novel self-healing and wide temperature-resistant graphene oxide synergistic multi-network polymer-supramolecular (PAM/CMCS/PEG/GO) hydrogel electrolyte is prepared using a one-step radical polymerization method. The design of the cross-linked network structure introduces reversible dynamic interactions that allow the hydrogel electrolyte to have excellent mechanical properties and high self-healing capability. The strong hydrogen bonding in the hydrogel network significantly lowers the freezing point of water and slows down the evaporation of water at high temperatures, thus leading to reliable temperature resistance (−10–90 °C). Meanwhile, the assembled PAM/CMCS/PEG/GO hydrogel electrolyte-based FSC has a high capacitance retention rate; the capacity retention is 83.3% after 6000 charge/discharge cycles, and the capacitance of the FSC retains 92.3% of its original state after 5 cycles of cutting/self-healing.

水凝胶作为可穿戴和便携式电子设备中柔性超级电容器（FSC）的电解质，越来越受到人们的关注，并具有巨大的潜力。然而，水凝胶电解质在实际应用中受到一些因素的阻碍，例如其耐温性能不尽人意、机械性能较差以及没有自愈合特性。本文采用一步自由基聚合法制备了一种新型自愈合和宽耐温氧化石墨烯协同多网络聚合物超分子（PAM/CMCS/PEG/GO）水凝胶电解质。交联网络结构的设计引入了可逆的动态相互作用，使水凝胶电解质具有优异的机械性能和较高的自愈能力。水凝胶网络中的强氢键大大降低了水的凝固点，减缓了水在高温下的蒸发，因此具有可靠的耐温性（-10~90 °C）。同时，组装好的基于 PAM/CMCS/PEG/GO 水凝胶电解质的 FSC 具有很高的电容保持率，经过 6000 次充放电循环后，电容保持率达到 83.3%，并且在经过 5 次切割/自愈循环后，FSC 的电容保持率达到 92.3%。

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引用次数: 0

Synthesis of asymmetric imine polymers for highly selective sorting of semiconducting single-walled carbon nanotubes by a two-in-one strategy† 通过二合一策略合成用于高选择性分选半导体单壁碳纳米管的不对称亚胺聚合物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-02 DOI: 10.1039/d4py00607k

Ying Zhang , Yu Li , Yuchi Wan , Jun-Hao Wang , Yunzhen Chang , Sheng Zhu , Lan Bai , Yu Cao , Xuelei Liang , Gaoyi Han

Using a two-in-one strategy, we synthesize three polymers of fluorene derivative with asymmetric structure functionalized with two types of arenes with different orientations and electronic properties. The polymers are connected by an imine bond, hanging on two sides of fluorene with different orientations, one is fluorene–C–N and the other one is fluorene–N–C. In such asymmetric polymers, electron density, conjugation degree, and even the stability of the imine bond can be finely tuned. demonstrates ultra-high selectivity towards s-SWCNTs and can be easily removed for releasing bare s-SWCNTs under acid stimuli. The theory calculation and photophysical experiments help us gain a better understanding of the relationship between polymer structure and separation ability towards s-SWCNTs.

通过 "二合一 "策略，我们得到了三种具有不对称结构的芴衍生物聚合物，它们分别与两种具有不同取向和电子特性的烷烃官能化。这些聚合物通过亚胺键连接，亚胺键悬挂在不同取向的芴的两侧，一个是芴-C-N，另一个是芴-N-C。在这种不对称聚合物中，电子密度、共轭度甚至亚胺键的稳定性都可以进行微调。P1 对 s-SWCNTs 具有极高的选择性，在酸性刺激下可以很容易地去除释放出的呲s-SWCNTs。理论计算和光物理实验有助于我们更好地理解聚合物结构与对 s-SWCNTs 的分离能力之间的关系。

引用次数: 0

Star copolymers with tunable clusteroluminescence† 具有可调簇发光的星形共聚物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-02 DOI: 10.1039/d4py01198h

Zixuan Zhou , Xiang Chen , Yang Wang , Ting Li , Xuhui Zhang , Bihua Xia , Shibo Wang , Weifu Dong , Jinliang Qiao

Clusteroluminescence (CL) has recently drawn more attention due to its unique photophysical behaviors that differ from traditional conjugated luminogens. However, the design of red emission from such systems is still challenging due to the intrinsic drawbacks of non-conjugated luminogens and the preliminary mechanisms. In this work, we synthesized four-armed star poly(maleic anhydride-alt-vinyl acetate) (SPMV) copolymers with different chain lengths through a reversible addition–fragmentation chain transfer (RAFT) polymerization method. By adjusting the amount of the chain transfer agent added, the chain lengths of the star copolymers could be transformed from long to short, regulating their fluorescence emission from blue to red. The emission wavelengths of the star copolymers with the shortest chain lengths are significantly red-shifted and concentrated in the red-orange region. The introduction of a star structure can enhance the flexibility of copolymer chains, thus promoting strong interchain interactions and the formation of more chromophores. Concurrently, the prepared star copolymer could be employed as a coating, endowing the substrate with excellent light transmittance and fluorescence properties. This study not only offers new insights into the CL mechanism but also presents a novel method to adjust the emission of anhydride copolymers, thereby expanding the applications of CLgens to unexplored fields.

簇状发光（CL）因其有别于传统共轭发光体的独特光物理行为，最近引起了越来越多的关注。然而，由于非共轭发光体的固有缺陷和初步机制，设计此类系统的红色发射仍具有挑战性。在这项工作中，我们通过可逆加成-断裂链转移（RAFT）聚合法合成了不同链长的四臂星型聚（马来酸酐-乙酸乙烯酯）（SPMV）。通过调节链转移剂的添加量，星型共聚物的链长可以由长变短，从而调节其荧光发射由蓝变红。链长最短的星形共聚物的发射波长明显红移，并集中在橘红色区域。星形结构的引入可增强共聚物链的柔韧性，从而促进链间的强烈相互作用，形成更多的发色团。同时，制备的星形共聚物可用作涂层，使基底具有优异的透光性和荧光特性。这项研究不仅为 CL 机制提供了新的见解，还提出了一种调整酸酐共聚物发射的新方法，从而将 CLgens 的应用扩展到了尚未开发的领域。

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引用次数: 0

Ethylene-bridged bisisoindigo-based conjugated polymers: influence of intramolecular CH⋯N hydrogen bonds† 乙烯-桥接双靛基共轭聚合物：分子内 CH-N 氢键的影响

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-01 DOI: 10.1039/d4py00745j

Keli Shi , Jing Lai , Qianqian Zhao , Weifeng Zhang , Qian Che , Jiadi Chen , Zhihui Chen , Liping Wang , Gui Yu

The synthesis and characterization of four ethylene-bridged bisisoindigo (NCCN and NNNN)-based conjugated polymers are reported. In these polymers, 2,2′-bithiophene or (E)-1,2-di(thiophen-2-yl)ethene (DTE) is used as the electron donor. Compared to NCCN, NNNN has two additional sp²-nitrogen atoms adjacent to its vinyl group. The sp²-nitrogen atoms endow the two NNNN-based polymers PNNNN-BT and PNNNN-DTE with not only improved backbone planarity due to the formation of intramolecular five-ring intramolecular CH⋯N hydrogen bonds, but also slightly lowered frontier orbital energy levels. Combined with the more rigid backbone of DTE, PNNNN-DTE showed the highest electron mobility (μ_e) of 1.64 cm² V⁻¹ s⁻¹ in 1,2-dichlorobenzene (DCB)-processed ambipolar field-effect transistors and even a slightly increased μ_e in its DCB/1-chloronaphthalene (with v/v of 99.2/0.8) bi-component solvent-processed ones. Microstructural analyses indicated that the PNNNN-DTE thin films have more ordered and denser molecular packing, which is well in accordance with the change tendency of the electron mobility of these bisisoindigo-based conjugated polymers.

报告了四种乙烯桥双靛蓝（NCCN 和 NNNN）基共轭聚合物的合成和表征。在这些聚合物中，2,2'-联噻吩或(E)-1,2-二（噻吩-2-基）乙烯（DTE）被用作电子供体。与 NCCN 相比，NNNN 的乙烯基旁多了两个 sp2 氮原子。sp2-氮原子使两种基于 NNNN 的聚合物 PNNNN-BT 和 PNNNN-DTE 不仅由于形成了分子内五环分子内 CH-N 氢键而提高了骨架平面度，而且还略微降低了前沿轨道能级。结合 DTE 更坚硬的骨架，PNNNN-DTE 在 1,2-二羟基苯（DCB）加工的伏极场效应晶体管中显示出最高的电子迁移率（μe），达到 1.64 cm^2 V^-1 s^-1，甚至在其 DCB/1-氯萘（v/v 为 99.2/0.8）双组分溶剂加工的晶体管中也略微提高了μe。微观结构分析表明，PNNNN-DTE 薄膜的分子堆积更有序、更致密，这与这些双靛基共轭聚合物电子迁移率的变化趋势十分吻合。

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引用次数: 0

N-Heterocyclic carbene-initiated epoxide/anhydride ring-opening copolymerization: effective and selective organoinitiators for the production of various polyesters† N-Heterocyclic Carbene-Initiated Epoxide/Anhydride Ring-Opening Copolymerization：生产各种聚酯的有效和选择性有机引发剂

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-01 DOI: 10.1039/d4py00778f

Gaël Printz , Redoy Gazi Shuvo , Antoine Schweizer , Dmytro Ryzhakov , Christophe Gourlaouen , Lielou Lantigner , Béatrice Jacques , Samir Messaoudi , Franck Le Bideau , Samuel Dagorne

The present report describes the first use of unprotected and “free” N-heterocyclic carbenes (NHCs), such as IMes, IPr and air-stable Cl-IPr carbenes, as single component initiators for the alternating ring-opening co-polymerization (ROCOP) of cyclic anhydrides (phthalic anhydride, PA; succinic anhydride, SA) and various epoxides to efficiently and selectively access the corresponding polyesters in a well-defined manner and as metal-free materials. In the case of ROCOP runs with PA as the anhydride source, control experiments are in line with an initiation via ring-opening of PA by the NHC moiety, as established with the synthesis and structural characterization of the IMes-PA ring-opened product 1. The present NHC systems were further exploited as ROCOP initiators of PA and bio-sourced epoxides such as eugenyl glycidyl ether (EGE) and safrole glycidylether (SO) yielding the production of regioregular p(PA-alt-EGE) polyester, as well as p(PA-alt-SO), a novel polyester material.

本报告首次将未受保护的 "游离 "N-杂环碳烯（NHC）（如 IMes、IPr 和空气稳定的 Cl-IPr 碳烯）作为单组分引发剂，用于环状酸酐（邻苯二甲酸酐，PA；琥珀酸酐，SA）和各种环氧化物的交替开环共聚（ROCOP），从而以明确定义的方式高效、选择性地获得相应的聚酯，并将其作为无金属材料。在以 PA 为酸酐源进行 ROCOP 的情况下，控制实验结果与 NHC 分子通过 PA 的开环起始作用相吻合，IMes-PA 开环产物 1 的合成和结构表征也证实了这一点。目前的 NHC 系统被进一步用作 PA 和生物来源环氧化物（如丁香基缩水甘油醚 (EGE) 和黄樟素缩水甘油醚 (SO)）的 ROCOP 起始剂，生产出了多规 p(PA-alt-EGE) 聚酯以及新型聚酯材料 p(PA-alt-SO)。

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引用次数: 0

Synthesis of poly(l-lactide)-b-poly(amino acid) block copolymers by noncovalent protection of hetero-initiators† 通过对杂质引发剂进行非共价保护合成聚(L-内酰胺)-b-聚(氨基酸)嵌段共聚物

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-01 DOI: 10.1039/d4py00739e

Siheng Zhang , Jianda Niu , Enci Hu , Liguo Xu , Zhixian Dong , Jinbao Xu , Caihong Lei

The synthesis of poly(l-lactide)-b-poly(amino acid) (PLA-b-PAA) block copolymers is of great interest in biomedicine due to their pronounced biodegradability and biocompatibility. However, the traditional method for preparing the functional block copolymers generally involves a tedious protection and deprotection process by covalent bonding, which may not only degrade the PLA segment during the process but also eliminate the precision in controlling the ROP of NCA. In light of this, in this study, PLA-b-PAAs were directly synthesized by the noncovalent protection between triethylborane (Et₃B) and an amino alcohol initiator during the ring-opening polymerization (ROP) process of LA under mild reaction conditions, which produced amino-terminated PLA (PLA-NH₂) avoiding the tedious process of the traditional method. Subsequently, the PLA-NH₂ macroinitiator was employed to initiate the ROP of N-carboxyanhydride, thereby forming the well-defined PLA-b-PAA block copolymers. The noncovalent protection of hetero-initiators provides a promising platform for the design of PLA-b-PAA polymeric materials with tailored functionalities for biomedical applications.

在三乙基硼烷存在下，使用有机催化剂对异质引发剂 2-氨基乙醇进行非共价保护，合成了聚(L-内酰胺)-b-聚(γ-苄基谷氨酸)嵌段共聚物。这种共聚物可以在温和的条件下高效率地直接制备，避免了通过传统方法设计氨基封端聚乳酸时繁琐的保护和脱保护过程。

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引用次数: 0

Radical promoted cationic RAFT polymerization by photo electron transfer reaction† 通过光电子转移反应进行自由基促进阳离子 RAFT 聚合反应

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-10-01 DOI: 10.1039/d4py00774c

Shiliang He , Xinrui Yang , Yabing Zhao , Yang Liu , Bowen Zhao , Xiangqiang Pan , Jiajia Li , Jian Zhu , Na Li

The application of cationic RAFT polymerization in photocuring has enabled the fabrication of stimuli-responsive materials. However, these systems mainly rely on UV light, limiting their broader application. Herein, we developed a radical promoted cationic RAFT (RPC-RAFT) polymerization system utilizing a photoredox catalyst via a photo electron transfer reaction, extending the usable light wavelength to blue and red light. The well-defined polymerization of various vinyl ethers was achieved with controlled molecular weights and narrow molecular weight distributions. Moreover, we achieved successful photocuring using this system for the polymerization of a bifunctional vinyl ether monomer, offering a convenient approach for in-depth photocuring.

阳离子 RAFT 聚合在光固化中的应用使刺激响应材料的制造成为可能。然而，这些系统主要依赖紫外线，限制了其更广泛的应用。在此，我们开发了一种自由基促进阳离子 RAFT（RPC-RAFT）聚合体系，利用光氧化催化剂通过光电子转移反应，将可用光波长扩展到蓝光和红光。我们实现了各种乙烯基醚的明确聚合，并控制了分子量和窄分子量分布。此外，我们还利用该系统成功实现了双官能团乙烯基醚单体的光固化聚合，为深度光固化提供了一种便捷的方法。

引用次数: 0

Synthesis of nitrile-containing ortho-amide benzoxazines for achieving thermosets with low curing temperature and superior performance† 合成含腈正交酰胺苯并噁嗪，实现低固化温度和卓越性能的热固性塑料

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-09-24 DOI: 10.1039/d4py00777h

Yin Lu , Jiaqi Wang , Yi Yang , Yichen Jing , Kan Zhang

In this work, a molecular design strategy by incorporating nitrile into ortho-amide benzoxazines was employed for achieving promising high performance thermsosets. We conducted a systematic investigation into the influence of additional nitrile moieties on the properties of ortho-amide benzoxazines. Initially, structural characterization of benzoxazines was performed using NMR and FT-IR spectroscopy, followed by DSC analysis and in situ FT-IR spectroscopy to study the polymerization mechanisms of each benzoxazine monomer. Notably, the thermoset derived from ortho-amide benzoxazine bearing two nitrile groups exhibited exceptional thermal stability (T_d5 of 392.5 °C) and high glass transition temperature (T_g of 331 °C), alongside preferable flame retardancy (THR = 3.9 kJ g⁻¹).This approach resulted in a new series of thermosetting resins with low curing temperature and improved comprehensive properties, thereby offering significant potential for the development of advanced thermoset materials with a wide range of intelligent applications.

在这项研究中，我们采用了一种分子设计策略，通过在原酰胺苯并噁嗪中加入腈来获得超高性能的热固性塑料。我们系统地研究了附加腈分子对原酰胺苯并噁嗪特性的影响。首先，我们使用核磁共振和傅立叶变换红外光谱对苯并噁嗪进行了结构表征，然后使用 DSC 分析和原位傅立叶变换红外光谱研究了每种苯并噁嗪单体的聚合机理。值得注意的是，由带有两个腈基的正酰胺苯并恶嗪衍生的热固性树脂具有优异的热稳定性（Td5 为 392.5 ℃）和较高的玻璃化转变温度（Tg 为 331 ℃），以及出色的阻燃性（THR = 3.9 kJ g-1）。

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引用次数: 0

“Diluting branches” put to work: from synthesis to properties control of multifunctional polymers derived from triphenylamine, fluorene and thiophene† "稀释分支 "的应用：从三苯胺、芴和噻吩衍生多功能聚合物的合成到特性控制

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry

Pub Date : 2024-09-24 DOI: 10.1039/d4py00720d

Ioana-Alexandra Trofin , Catalin-Paul Constantin , Mariana-Dana Damaceanu , Radu-Dan Rusu

A series of highly branched polymers was synthesized by Suzuki polycondensation of thiophene-, fluorene-, and triphenylamine-based monomers, following the “A₂ + B₂ + C₃” pathway. A “dilution of branches” approach allows branching density management and generates conjugated frameworks with linear, alkyl-decorated segments of various lengths. This strategy affects solubility, morphology, and thermal features and allows further control options. The building blocks are involved individually or in combinations in the main electronic transitions and charge and energy transfer processes, as confirmed by computational and experimental UV–vis and photoluminescence studies. The absorption and emission profiles are influenced by branching density, solvent, or the sample's physical state. The structural units’ particular arrangement in each branched construct regulates the redox patterns and electrochemical parameters. The polymers’ overall features and their variation with structure and branching density assemble the foundation for engaging conjugated materials for (opto)electronic applications.

通过噻吩、芴和三苯胺基单体的铃木缩聚反应，按照 "A2 + B2 + C3 "途径合成了一系列高支化聚合物。通过 "稀释分支 "的方法，可以对分支密度进行管理，并生成具有不同长度的线性烷基装饰段的共轭框架。这种策略会影响溶解度、形态和热特性，并允许进一步的控制选项。计算和实验性紫外可见光和光致发光研究证实，这些构件可单独或组合参与主要的电子跃迁以及电荷和能量转移过程。吸收和发射曲线受支化密度、溶剂或样品物理状态的影响。氧化还原模式和电化学参数受结构单元在每个支化结构中的特定排列的调节。聚合物的整体特征及其随结构和支化密度的变化，为共轭材料在（光）电子领域的应用奠定了基础。

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引用次数: 0