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2021, 39(5): 0-0.
[Abstract](110) [FullText HTML] (79) [PDF 37678KB](0)
Benzothiadiazole-based Conjugated Polymers for Organic Solar Cells
Chao Wang, Feng Liu, Qiao-Mei Chen, Cheng-Yi Xiao, Yong-Gang Wu, Wei-Wei Li
2021, 39(5): 525-536. doi: 10.1007/s10118-021-2537-8
[Abstract](512) [FullText HTML] (195) [PDF 559KB](3)
Benzothiadiazole (BT) is an electron-deficient unit with fused aromatic core, which can be used to construct conjugated polymers for application in organic solar cells (OSCs). In the past twenty years, huge numbers of conjugated polymers based on BT unit have been developed, focusing on the backbone engineering (such as by using different copolymerized building blocks), side chain engineering (such as by using linear or branch side units), using heteroatoms (such as F, O and S atoms, and CN group), etc. These modifications enable BT-polymers to exhibit distinct absorption spectra (with onset varied from 600 nm to 1000 nm), different frontier energy levels and crystallinities. As a consequence, BT-polymers have gained much attention in recent years, and can be simultaneously used as electron donor and electron acceptor in OSCs, providing the power conversion efficiencies (PCEs) over 18% and 14% in non-fullerene and all-polymer OSCs. In this article, we provide an overview of BT-polymers for OSCs, from donor to acceptor, via selecting some typical BT-polymers in different periods. We hope that the summary in this article can invoke the interest to study the BT-polymers toward high performance OSCs, especially with thick active layers that can be potentially used in large-area devices.
A Conjugated Copolymer Bearing Imidazolium-based Ionic Liquid: Electrochemical Synthesis and Electrochromic Properties
Xiao-Jing Lv, Li-Bin Xu, Liang Qian, Yuan-Yuan Yang, Zhi-Yi Xu, Jin Li, Cheng Zhang
2021, 39(5): 537-544. doi: 10.1007/s10118-021-2525-z
[Abstract](539) [FullText HTML] (243) [PDF 1075KB](1)
An imidazolium-based ionic liquid (IL) modified triphenylamine derivative, namely 1-(4-((4-(diphenylamino)benzoyl) oxy)butyl)-3-methyl imidazole tetrafluoroborate (TPAC6IL-BF4), was designed and synthesized, and further applied with 3,4-ethylene dioxythiophene (EDOT) to prepare conjugated copolymer P(EDOT:TPAC6IL-BF4) via electrochemical polymerization. The cyclic voltammetry curves show that the copolymer P(EDOT:TPAC6IL-BF4) possesses two pairs of redox peaks, which should be ascribed to the redox behaviors of EDOT and triphenylamine. The ultraviolet-visible (UV-Vis) absorption spectrum of P(EDOT:TPAC6IL-BF4) exhibits one maximum absorption peak at 580 nm and a small shoulder characteristic peak at 385 nm under neutral state which are assigned to π-π* conjugated structure of EDOT and triphenylamine. After being applied at the positive voltage, the copolymer color changes from dark blue to light blue, which is close to the color of poly(3,4-ethylenedioxythiophene) (PEDOT). Surprisingly, the copolymer P(EDOT:TPAC6IL-BF4) shows shorter switching time of 0.37 s, 0.30 s at 580 nm and 0.38 s, 0.45 s at 1100 nm compared with PEDOT. It is more intriguing that the copolymer P(EDOT:TPAC6IL-BF4) exhibits electrochromism even in free supporting electrolyte. The results confirm that the existence of imidazolium-based ionic liquid has an improvement on the ion diffusion properties and the switching time of conjugated polymer, which may provide a potential direction for the preparation of high-performance electrochromic materials.
Reversible Mechanochemistry Enabled Autonomous Sustaining of Robustness of Polymers—An Example of Next Generation Self-healing Strategy
Ming-Xuan Li, Min-Zhi Rong, Ming-Qiu Zhang
2021, 39(5): 545-553. doi: 10.1007/s10118-021-2532-0
[Abstract](504) [FullText HTML] (273) [PDF 3116KB](4)
Even under low external force, a few macromolecules of a polymer have to be much more highly stressed and fractured first due to the inherent heterogeneous microstructure. When the materials keep on working under loading, as is often the case, the minor damages would add up, endangering the safety of use. Here we show an innovative solution based on mechanochemically initiated reversible cascading variation of metal-ligand complexations. Upon loading, crosslinking density of the proof-of-concept metallopolymer networks autonomously increases, and recovers after unloading. Meanwhile, the stress-induced tiny fracture precursors are blocked to grow and then restored. The entire processes reversibly proceed free of manual intervention and catalyst. The proposed molecular-level internal equilibrium prevention mechanisms fundamentally enhance durability of polymers in service.
Tough Double Metal-ion Cross-linked Elastomers with Temperature-adaptable Self-healing and Luminescence Properties
Qi-Yan Yin, Cheng-Hao Dai, Huan Chen, Kai Gou, Hong-Zhou Guan, Peng-Han Wang, Jing-Tao Jiang, Geng-Sheng Weng
2021, 39(5): 554-565. doi: 10.1007/s10118-021-2517-z
[Abstract](567) [FullText HTML] (257) [PDF 823KB](1)
Smart materials with a combination of tough solid-like properties, fast self-healing and optical responsiveness are of interests for the development of new soft machines and wearable electronics. In this work, tough physically cross-linked elastomers that show high mechanical strength, intriguing temperature-adaptable self-healing and fluorochromic response properties are designed using aluminum (Al) and fluorescent europium (Eu) ions as cross-linkers. The ionic Al-COOH binding is incorporated to construct the strong polymer network which mainly contributes to the mechanical robustness of the elastomer consisting of two interpenetrated networks. The Eu-iminodiacetate (IDA) coordination is mainly used to build the weaker but more dynamic network which dominate the elasticity, self-healing and luminescence of the elastomer. Moderate Eu3+ and Al3+ contents give these supramolecular elastomers high toughness. The temperature-sensitive Eu-IDA coordination enables tunable self-healing rate and efficiency along with fast Eu-centered “ON/OFF” switchable red emission. The mechanical, self-healing and luminescence properties of these elastomers can be adjusted by tuning the ratio of the two types of metal ions. This elastomer is potentially applicable for biosensors, wearable optoelectronics and anticounterfeiting materials.
Foam/Film Alternating Multilayer Structure with High Toughness and Low Thermal Conductivity Prepared via Microlayer Coextrusion
Qi Luo, Hong-Ting Pu, Zhi-Hua Zhang, Xiong Zhang, Cheng-Long Yu
2021, 39(5): 566-572. doi: 10.1007/s10118-021-2524-0
[Abstract](372) [FullText HTML] (226) [PDF 1094KB](0)
Multilayer membranes prepared via microlayer coextrusion have attracted wide attention due to their unique properties and broad applications. In present study, the foam/film alternating multilayer sheets based on ethylene-vinyl acetate copolymer (EVA) and high-density polyethylene are successfully prepared via microlayer coextrusion. The cells in the sheets are single-cell-array along the foamed EVA layers with uniform cell size. In addition, the effects of layer number and foam relative thickness on morphology, mechanical properties, damping and heat insulation properties are investigated. The cell size decreases significantly with increasing layer number due to the enhanced confine effects. The tensile strength, elongation at break, and heat insulation also increase significantly. However, the mechanical damping properties change little in the observed frequency. Meanwhile, with higher relative thickness of EVA foam, the sheets have lower tensile strength and lower thermal conductivity, while the damping properties are enhanced in a specific frequency scope. The elongation at break of the optimized sample comes to 800% and the thermal conductivity decreases to 61 mW·m−1·K−1, which shows high toughness and low thermal conductivity, indicating a possible method for preparing materials with high toughness and heat-insulating properties.
Facile Mechanochemical Preparation of Polyamide-derivatives via Solid-state Benzoxazine-isocyanide Chemistry
Xu Sun, Wei Shi, Xin-Yu Zhou, Sheng Ding
2021, 39(5): 573-584. doi: 10.1007/s10118-021-2510-6
[Abstract](520) [FullText HTML] (261) [PDF 1078KB](2)
With the exploration of novel sustainable protocol for functional polyamides’ (PAs) construction as the starting point, herein, the small molecular model compound (M1-ssBIC) was prepared firstly by manual grinding of monofunctional benzoxazine (1a) and isocyanide (1b) via solid-state benzoxazine-isocyanide chemistry (ssBIC) to evaluate the feasibility of ssBIC. Linear PAs (P1-series polymers) were subsequently synthesized from biunctional benzoxazine (2a) and isocyanide (2b), and the influence of the loading of catalyst (octylphosphonic acid) (OPA) on the polymerization was investigated. Afterwards, two kinds of cross-linked PAs were successfully constructed via ssBIC by using trifunctional benzoxazine (3a) and cross-linked polybenzoxazine (4a) as reaction substrates, respectively, thus verifying the adaptability of ssBIC. Structural characterization indicates that amide, phenolic hydroxyl and tertiary amine substructures, with metal-complexing capability, have been successfully integrated into the obtained PAs. A type of representative PA/silver composite (P3-AgNPs) was prepared subsequently via in situ reduction treatment, and its application as recyclable reduction catalyst for organic pollutant p-nitrophenol (4-NP) was preliminarily investigated here to provide the example for possible downstream application of ssBIC. We think that this current work could provide a new pathway for the construction of functional PAs through facile and sustainable ssBIC protocol.
Tunable Lower Critical Solution Temperature of Poly(butyl acrylate) in Ionic Liquid Blends
Lie Chen, Jin Huang, Cong Zhao, Jia-Jia Zhou, Ming-Jie Liu
2021, 39(5): 585-591. doi: 10.1007/s10118-021-2522-2
[Abstract](531) [FullText HTML] (229) [PDF 338KB](1)
We describe the lower critical solution temperature (LCST)-type phase behavior of poly(butyl acrylate) (PBA) dissolved in hydrophobic 1-alkyl-3-methylimidazolium bis{(trifluoromethyl) sulfonyl}amide ionic liquids (ILs). The temperature-composition phase diagrams of these PBA/ILs systems are strongly asymmetric with the critical composition shifted to low concentrations of PBA. As the molecular weight increases from 5.0×103 to 2.0×104, the critical temperature decreases by about 67 °C, and the critical composition shifts to a lower concentration. Furthermore, the LCST of PBA/ILs system increases as increasing the alkyl side chain length in the imidazolium cation. Using IL blends as solvents, the LCST of PBA can be tuned almost linearly over a wide range by varying the mixing ratio of two ionic liquids without modifying the chemical structure of the polymers.
Scalable Reaction-spinning of Rigid-rod Upilex-S® Type Polyimide Fiber with an Ultrahigh Tg
Sen-Sen Zheng, Han Dong, Shi-Hua Wang, Jie Dong, Tao Guo, Xin Zhao, Qing-Hua Zhang
2021, 39(5): 592-600. doi: 10.1007/s10118-021-2508-0
[Abstract](470) [FullText HTML] (391) [PDF 776KB](1)
In the family of polyimide (PI) materials, Upilex-S® film has been a shining star through the research PI materials due to its appealing merits. Unfortunately, the wholly rigid-rod backbone and easily formed skin-core micromorphology and microvoids of Upilex-S® type PI lead to the high difficulty in melt- and wet-spinning fabrication. Herein, we propose a facile and scalable method, reaction-spinning, to fabricate the Upilex-S® type PI fiber, in which the rapid solidification of spinning dope and partial imidization take place simultaneously. Thus, the stability and mechanical strength of as-spun fibers can be improved, and the microvoids in fibers can be greatly reduced in relative to the wet-spun fibers. The resultant Upilex-S® type PI fiber shows higher tensile strength and modulus than most commercial thermal-oxidative polymeric fibers with an ultrahigh glass transition temperature Tg of 478 °C. Moreover, the WAXS and SAXS results indicate that orthorhombic crystals are formed for Upilex-S® type PI fiber in the post hot-drawing process. Increasing the hot-drawing temperature results in a continuous crystallization and high orientation of PI chains in amorphous phase and perfects the existing lamellar structure, which make a great contribution to the improved mechanical property.
Structural Changes and Electrodynamic Effects in Polymers under Fast Uniaxial Compression
Aleksey. I. Aleksandrov, Ivan A. Aleksandrov, Vitaliy G. Shevchenko, Aleksandr N. Ozerin
2021, 39(5): 601-609. doi: 10.1007/s10118-021-2511-5
[Abstract](456) [FullText HTML] (264) [PDF 729KB](1)
Rheological explosion in polymers under uniaxial compression in an open volume occurs at the end of continuous rapid plastic deformation after several stages of creep. Two types of polymers were chosen for this study: brittle glassy amorphous polystyrene and thermoplastic semi-crystalline polypropylene. Electric pulses were detected during explosion, and their spectra were analyzed with two models. X-ray diffraction methods were used to investigate changes in the structure and morphology of polymers during deformation and rheological explosion. The pores appear in polymer in this process, and their shape and size distribution were derived from X-ray experiments. The main reason for the formation of pores in polymer samples in rheological explosion experiments is the intense microshifts in the polymer volume under the action of high applied pressure.
Tailoring Morphology of PVDF-HFP Membrane via One-step Reactive Vapor Induced Phase Separation for Efficient Oil-Water Separation
Peng Huo, Cheng-Tang Zhong, Xiao-Peng Xiong
2021, 39(5): 610-619. doi: 10.1007/s10118-021-2527-x
[Abstract](446) [FullText HTML] (223) [PDF 1105KB](2)
Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) receives increasing attention in membrane separation field based on its advantages such as high mechanical strength, thermal and chemical stability. However, controlling the microporous structure is still challenging. In this work, we attempted to tailor the morphology of PVDF-HFP membrane via a one-step reactive vapor induced phase separation method. Namely, PVDF-HFP was dissolved in a volatile solvent and then was cast in an ammonia water vapor atmosphere. After complete evaporation of solvent, membranes with adjustable porous structure were prepared, and the microstructures of the membranes were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction characterizations. Based on the results, a mechanism of dehydrofluorination induced cross-linking of PVDF-HFP has been suggested to understand the morphology tailoring. To our knowledge, this is the first report of one-step reactive vapor induced phase separation strategy to tailor morphology of PVDF-HFP membrane. In addition, the membranes prepared in the ammonia water vapor exhibited enhanced mechanical strength and achieved satisfactory separation efficiency for water-in-oil emulsions, suggesting promising potential.
Comparison of the Structural Evolution of β Polypropylene during the Sequential and Simultaneous Biaxial Stretching Process
Dao-Xin Zhang, Lei Ding, Feng Yang, Fang Lan, Ya Cao, Ming Xiang
2021, 39(5): 620-631. doi: 10.1007/s10118-021-2534-y
[Abstract](430) [FullText HTML] (206) [PDF 6086KB](0)
In this work, the lamellar structural evolution and microvoids variations of β polypropylene (β-PP) during the processing of two different stretching methods, sequential biaxial stretching and simultaneous biaxial stretching, were investigated in detail. It was found that different stretching methods led to significantly different lamellae deformation modes, and the microporous membranes obtained from the simultaneous biaxial stretching exhibited better mechanical properties. For the sequential biaxial stretching, abundant coarse fibers originated from the tight accumulation of the lamellae parallel to the longitudinal stretching direction, whereas the lamellae perpendicular to the stretching direction were easily deformed and separated. Those coarse fibers were difficult to be separated to form micropores during the subsequent transverse stretching process, resulting in a poor micropores distribution. However, for the simultaneous biaxial stretching, the β crystal had the same deformation mode, that is, the lamellae distributed in different directions were all destroyed, forming abundant microvoids and little coarse fibers.
Stereocomplex Crystallization in Asymmetric Diblock Copolymers Studied by Dynamic Monte Carlo Simulations
Ying Xu, Jun Yang, Zong-Fa Liu, Zhi-Ping Zhou, Zhao-Peng Liang, Tong-Fan Hao, Yi-Jing Nie
2021, 39(5): 632-639. doi: 10.1007/s10118-021-2512-4
[Abstract](534) [FullText HTML] (285) [PDF 662KB](0)
Stereocomplex crystallization in asymmetric diblock copolymers was studied using dynamic Monte Carlo simulations, and the key factor dominating the formation of stereocomplex crystallites (SCs) was uncovered. The asymmetric diblock copolymers with higher degree of asymmetry exhibit larger difference between volume fractions of beads of different blocks, and local miscibility between different kinds of beads is lower, leading to lower SC content. To minimize the interference from volume fraction of beads, the SC formation in blends of asymmetric diblock copolymers was also studied. For the cases where the volume fractions of beads of different blocks are the same, similar local miscibility between beads of different blocks and similar SC content was observed. These findings indicate that the volume fraction of beads of different blocks is a key factor controlling the SC formation in the asymmetric diblock copolymers. The SC content can be regulated by adjusting the difference between the contents of beads of different blocks in asymmetric diblock copolymers.
Conformational and Dynamical Evolution of Block Copolymers in Shear Flow
Xiang-Xin Kong, Wen-Duo Chen, Feng-Chao Cui, Yun-Qi Li
2021, 39(5): 640-650. doi: 10.1007/s10118-021-2523-1
[Abstract](421) [FullText HTML] (218) [PDF 1625KB](0)
Conformation and dynamical evolution of block copolymers in shear flow is an important topic in polymer physics that underscores the forming process of various materials. We explored deformation and dynamics of copolymers composed of rigid or flexible blocks in simple shear flow by employing multiparticle collision dynamics integrated with molecular dynamics simulations. We found that compared with the proportion between rigid and flexible blocks, the type of the central blocks plays more important role in the conformational and dynamical evolution of copolymers. That is, if the central block is a coil, the copolymer chain takes end-over-end tumbling motion, while if the central block is a rod, the copolymer chain undergoes U-shape or S-shape deformation at mid shear rate. As the shear strength increases, all copolymers behave similar to flexible polymers at high shear rate. This can be attributed to the fact that shear flow is strong enough to overcome the buckling force of the rigid blocks. These results provide a deeper understanding of the roles played by rod and coil blocks in copolymers for phase interface during forming processing.