Journal of Polymer Science

ABSTRACT Utilizations of alkylboranes reagents in radical polymerization are summarized in this minireview. Alkylboranes act as conventional radical initiators or radical chain‐transfer agents in free‐radical polymerization and controlled radical polymerization. This review discusses various polymerizations operating through different alkylborane reagents with their accompanying mechanisms. The aim of this minireview is to present the state of art of alkylboranes in radical polymerization and to provide the future aspects of this direction. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 14–19

Chunna Lv

Yuxuan Du

Xiangcheng Pan

Alkylboranes in Conventional and Controlled Radical Polymerization

Abstract Poly (vinylidene fluoride‐ co ‐trifluoroethylene) [P(VDF‐TrFE)] has three crystal forms, including paraelectric α, ferroelectric β, and γ phases. In previous studies, the properties and performances of P(VDF‐TrFE) have been the focus of research. However, the formation mechanism and regulation mode of various crystal forms remain unclear. Therefore, it is an important topic for further research to elucidate, summarize, and prospect the polymorphism of P(VDF‐TrFE) and regulate the crystal forms. This review systematically summarizes the crystalline structure and phase transition between ferroelectric and paraelectric phase of P(VDF‐TrFE) crystals; discusses the influence of annealing, blending and electric field on the crystallinity, selection of polymorphic crystals, and phase transition behavior between them; reviews the effects of annealing, melt‐recrystallization, substrate and nanoconfinement on the crystal orientation. Finally, the effects of the crystal structure of P(VDF‐TrFE) on its properties are briefly summarized.

Xiao Bai

Haikuo Li

Xiao Chu

Mengling Liu

Huihui Li

Haijun Wang

Xiaoli Sun

Shouke Yan

The tuning of crystallization behavior of ferroelectric poly(vinylidene fluoride‐<i>co</i>‐trifluoroethylene)

Abstract Phosphonate, as an effective flame‐retardant group, has a dynamic phosphonate exchange behavior similar to the transesterification of carboxylate; and introducing it into the network of epoxy resin (EP) is beneficial for solving the fire risk and waste disposal problems of EP in the meantime. Herein, a reprocessable and flame‐retardant epoxy vitrimer (EV) with dual dynamic covalent reactions of phosphonate and carboxylate transesterifications is constructed by introducing a phosphonate‐containing diol named GHPP into an epoxy‐anhydride curing system. The presence of the phosphonate makes the EV intrinsically flame‐retardant; meanwhile, both of the dynamic phosphonate and carboxylate transesterifications are accelerated by the abundant primary hydroxyl groups, which show much higher activity than the as‐generated β‐hydroxyls during curing, leading to enhanced dynamic properties of the EV. As a result, on the one hand, the EV achieves the UL‐94 V‐0 rating with a high limiting oxygen index value of 37.3%; and it shows a 41% reduction for the peak heat release rate and a 39% reduction for the total heat release in the cone calorimetry test. On the other hand, such EV exhibits rapid stress relaxation and is reprocessed easily to maintain its mechanical properties, thermal properties and flame retardancy to the hilt.

Qing‐Ruo Ren

Song Gu

Yu‐Zhong Wang

Li Chen

A phosphonate‐derived epoxy vitrimer with intrinsic flame retardancy and catalyst‐free reprocessability

Abstract High‐performance polymers have been concomitant with advanced technology for half a century. With the advancement of synthetic chemistry, the recent development of high‐performance polymers has provided superior properties and enabled wide applications. This article reviews recent research progress in aromatic high‐performance polymers. Particularly, we focus on the synthesis and processing of polyimides, as well as the application in gas separation membranes. We begin with a brief introduction to highlight important history and physiochemical characteristics of polyimides. Then, we review the various synthesis methods, followed by recent advances for improving processability. Finally, we evaluate the use of high‐performance polymers in gas separation membranes with focus given to the key issues of plasticization and aging. Overall, the information presented herein provides an up‐to‐date overview of high‐performance polymers, polyimides particularly, and serves as a guide for further research involving the applications in membrane technologies.

Zhen Xu

Zacary L. Croft

Dong Guo

Ke Cao

Guoliang Liu

Recent development of polyimides: Synthesis, processing, and application in gas separation

Abstract In recent years, there has been a growing demand for UV‐curable hard coatings because they offer several advantages, for example, lower energy consumption and the absence of volatile organic compound emissions. Anionic UV curing with photobase generators (PBGs), such as epoxy–thiol cross‐linking, enables curing under ambient conditions. However, designing a room‐temperature photoanionic curing system for epoxy–thiols remains challenging due to the complex effects of resin combinations on the cured products, thus making it difficult to prepare films with high hardness. Herein, we present a controlled reaction design for an anionic UV‐curing system by combining the chemical structures of epoxy resins and multifunctional thiols. The anionic UV‐curing system using PBGs that generate organic superbases demonstrated UV‐delayed curability, as evidenced by FT‐IR and photorheological analyses. To achieve high hardness, it was necessary to create the thiols with ultrarigid structures; epoxy resins with a bisphenol F structure were optimal for reacting with thiols for ultrarigid structures. This combination afforded an indentation hardness of 262 MPa with an epoxy conversion rate of 77% even at room temperature.

Yuya Tanaka

Nanae Tanaka

Daisuke Aoki

Koji Arimitsu

Rational design of a room‐temperature curing method, based on the epoxy–thiol click reaction, for <scp>UV</scp>‐curable hard coatings with ultrahigh strength and adhesion

基于环氧-硫醇点击反应的室温固化方法的合理设计，用于制备具有超高强度和附着力的<scp>UV</scp>固化硬涂层

ABSTRACT The excessive accumulation of reactive oxygen species (ROS) on wound surfaces poses considerable challenges to the wound healing process, as it exacerbates inflammation and heightens the risk of skin infections. Consequently, the development of multifunctional dressings that possess both ROS‐scavenging and antimicrobial properties is of clinical significance for enhancing wound healing. To address these challenges, we synthesized a dual‐scavenging hydrogel utilizing dual‐dynamic crosslinking techniques. This hydrogel is composed of poly‐lysine‐grafted D‐glucono‐1,5‐lactone, dithiodipropionic acid/lipoic acid, and dopamine (PLGDTD), in conjunction with borax. The multifunctional attributes of the hydrogel can be attributed to the incorporation of borate esters, dopamine, and disulfide bonds. Experimental results demonstrate that this hydrogel exhibits a robust antioxidant capacity and a pronounced inhibitory effect against Staphylococcus aureus and Escherichia coli . The results of cellular studies indicate that the hydrogel is capable of effectively scavenging ROS and mitigating oxidative stress, attributable to its dual‐scavenging mechanism involving borate and disulfide bonds. This multifunctional hydrogel demonstrates significant potential as a candidate for enhancing wound healing associated with ROS.

Xing Wang

Haohao Cui

Qingyun Ning

Huayang Feng

Xue Sun

Boyuan An

Zhanrong Li

Jianliang Shen

Jingguo Li

Borate and Disulfide Dual‐Dynamic Hydrogel for <scp>ROS</scp> Dual‐Scavenging

硼酸盐和二硫化物双重动态水凝胶用于ROS双重清除

ABSTRACT To mitigate the strong aggregation and limited solubility observed in the previously reported vinylene‐bridged alkoxyfluorobenzothiadiazole (FOBTzE)‐based polymer, PFOE4T, we designed and synthesized PBFOE‐1. This novel semiconducting polymer, based on the FOBTzE framework, incorporates an alkylthienyl‐substituted benzodithiophene (BDT) as the donor unit. PBFOE‐1 demonstrated broad and intense absorption between 300 and 700 nm with a relatively wide bandgap of 1.7 eV. Additionally, PBFOE‐1 features a low HOMO energy level (−5.43 eV) compared to PFOE4T (−5.23 eV), likely due to the incorporation of weakly electron‐donating BDT into the polymer backbone. While the PFOE4T/Y12‐based solar cell yielded a modest power conversion efficiency (PCE) of 4.37%, characterized by a short‐circuit current density ( J sc ) of 13.5 mA cm −2 , an open‐circuit voltage ( V oc ) of 0.69 V, and a fill factor (FF) of 0.47, the PBFOE‐1/Y12 cell exhibited a substantially higher PCE of 10.96%. This improvement is reflected in the enhanced J sc (23.23 mA cm −2 ), V oc (0.84 V), and FF (0.56). The superior performance of PBFOE‐1 is primarily attributed to its improved solubility and aggregation behavior, promoting a more ordered face‐on orientation and optimal blend morphology.

Yi Yan

Hiroki Mori

Ryuchi Hosogi

Hiroki Yamane

Tomoki Yoshino

Yasushi Nishihara

Vinylene‐Bridged Alkoxyfluorobenzothiadiazole (<scp>FOBTzE</scp>)‐Based Semiconducting Polymers for Enhanced Performance in Non‐Fullerene Organic Photovoltaic Cells

基于乙烯桥联烷氧基氟苯并噻二唑（<scp>FOBTzE</scp>）的半导体聚合物用于提高非富勒烯有机光伏电池性能

ABSTRACT Among the classes of synthetic polymers, disulfide‐containing structures offer unique opportunities due to their accessibility to redox chemistry that allows for degradation or reversible disulfide formation and exchange under mild conditions. Here, we examine the role of disulfides in olefin metathesis polymerization, specifically alternating diene metathesis (ALTMET) polymerization, for synthesizing unsaturated polyolefins with embedded disulfides. Our synthetic strategy hinged on the use of α,ω‐diacrylate monomers, including those connected by a disulfide unit, via copolymerization by the ALTMET mechanism to yield copolymers containing a range of disulfide content. In addition, the potential impacts of sulfur‐ruthenium interactions on the ALTMET process were investigated spectroscopically, while the degradation of the resultant polymers was affected by mild reducing agents. Overall, this study contributes to the development of degradable synthetic polymers using olefin metathesis methods, with an increased understanding of the potential for further use of disulfide groups in such metathesis reactions.

Kyoungwon Lee

Thomas P. Russell

Todd Emrick

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

含二硫化物单体在交替二烯易位聚合中的影响

ABSTRACT In electrohydrodynamics, the regulation of the morphology and structures of electrospun nanofibers is crucial for tuning the properties of the final product. In the electrospinning process, the uniform and smooth morphology of polyvinylidene fluoride (PVDF) nanofibers can be obtained by controlling experimental parameters, environmental parameter, and system parameters. However, there is inadequate research on the effect of polymer addition on the morphology enhancement of PVDF nanofibers and the underlying mechanisms. In this study, the effects of the polyvinylpyrrolidone (PVP) molecular weight and content on various process parameters (i.e., Taylor cone length, straight fluid jet length, and spray angle) are evaluated. The obtained electrospun PVDF/PVP nanofibers were further characterized by SEM, EDS, FTIR, and XRD. The results indicate that the solution viscosity, which was controlled by varying the molecular weight and content of PVP, was linearly correlated with the process parameters. As the PVP molecular weight and content increased, the nanofiber diameter increased and the nanofiber morphology became smoother. The EDS results revealed that the nanofibers consisted of PVDF encapsulated by PVP. The FTIR and XRD results indicated that hydrogen bonding between PVP and PVDF weakened the crystallization of PVDF, leading to the formation of smooth PVDF/PVP nanofibers.

Junli Guo

Bingying Chen

Yueling Shen

Chen Chen

Yaoyao Yang

Dengguang Yu

Morphological Modulation of Electrospun <scp>PVDF</scp>/<scp>PVP</scp> Nanofibers

电纺<scp>PVDF</scp>/<scp>PVP</scp>纳米纤维的形态调制

ABSTRACT The radical (co)polymerization of 2‐acryloylfluorene ( 1a ) and 2‐acryloyl‐9,9‐dimethylflureoene ( 1b ) with methyl methacrylate and the thermal and optical properties of the resulting (co)polymers are investigated. Because the two methyl groups at the 9‐position prevent the interaction of aromatic rings, the solubility is drastically improved for the homopolymer of 1b . The incorporation of 1b ‐units increases both the glass transition temperature (118°C–170°C) and 5% weight‐loss temperature (289°C–354°C). In addition, the refractive index of the polymers at 589 nm increases from 1.49 to 1.65 with higher mole fractions of 1b ‐units, whereas the negative birefringence significantly increases. These features are attributed to the restricted bond rotation of the rigid aromatic pendant groups bound to the backbone via an sp 2 carbon atom (carbonyl group).

Masatoshi Ohyama

Rie Yasuda

Hirotsugu Kuratani

Shinsuke Miyauchi

Yasuhiro Kohsaka

Vinyl Ketones Containing Fluorene Skeletons for Acrylic Resins with High Refractive Index and Negative Birefringence

含芴骨架的乙烯基酮用于制备高折射率及负双折射的丙烯酸树脂

短名	J. Polym. Sci.
Journal Impact	3.76
国际分区	POLYMER SCIENCE(Q2)
期刊索引	SCI Q2中科院 3 区

ISSN	2642-4150, 2642-4169
h-index	164
国内分区	化学(3区)化学高分子科学(3区)

涉及主题	化学物理材料科学有机化学复合材料工程类核磁共振聚合物高分子化学量子力学生物化学工程生物化学共聚物计算机科学纳米技术聚合单体热力学机械工程
出版信息	出版商: John Wiley & Sons Inc.，出版周期: ，期刊类型: journal，开源期刊: 否
基本数据	创刊年份: 2020，原创研究文献占比: 84.55%，自引率:2.60%， Gold OA占比: 18.25%

Journal of Polymer Science

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Alkylboranes in Conventional and Controlled Radical Polymerization

The tuning of crystallization behavior of ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene)

A phosphonate‐derived epoxy vitrimer with intrinsic flame retardancy and catalyst‐free reprocessability

Recent development of polyimides: Synthesis, processing, and application in gas separation

Rational design of a room‐temperature curing method, based on the epoxy–thiol click reaction, for UV‐curable hard coatings with ultrahigh strength and adhesion

Borate and Disulfide Dual‐Dynamic Hydrogel for ROS Dual‐Scavenging

Vinylene‐Bridged Alkoxyfluorobenzothiadiazole (FOBTzE)‐Based Semiconducting Polymers for Enhanced Performance in Non‐Fullerene Organic Photovoltaic Cells

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

Morphological Modulation of Electrospun PVDF/PVP Nanofibers

Vinyl Ketones Containing Fluorene Skeletons for Acrylic Resins with High Refractive Index and Negative Birefringence