A perspective on polyoxometalates as versatile synthons for precisely hybridized polymer materials

We summarize the emerging advances of polyoxometalate (POM)–polymer hybrid materials in the last decade and chart the future possibilities in this field. The discussion is mainly focused on two critical roles of POMs: the structural synthon for fabricating well‐defined macromolecular architectures, and the functional synthon for advanced hybrid polymer materials in energy‐ and health‐related applications. The precise structures, modular synthesis and task‐directed functional design to overcome the current societal challenges are proposed to be a developing trend in POM–polymer hybrid materials. © 2019 Society of Chemical Industry     

Preparation and application of fluorocarbon polymer/SiO2 hybrid materials,part 1: Preparation and properties of hybrid materials

For this study, we first prepared a fluorocarbon polymer and its hybrid materials. We found that fluorocarbon copolymers can produce hydrogen bonds with SiO₂ to form hybrid materials. We also used thermogravimetric analyzer and tested the thermostabilities of the four products, which were ranked as follows: fluorocarbon copolymer/SiO₂ hybrid material > fluorocarbon polymer/SiO₂ hybrid material > fluorocarbon copolymer > fluorocarbon polymer. In addition, we found that, due to the inorganic SiO₂ used, the number of pores and the specific surface areas of the hybrid materials both increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1140–1145, 2007     

Preparation and application of fluorocarbon polymer/SiO2 hybrid materials,part 2: Water and oil repellent processing for cotton fabrics by sol–gel method

This research employed different procedures for out water and oil repellent finish on cotton fabrics with fluorocarbon copolymer or its hybrid materials. The experimental results indicated that fabrics processed with fluorocarbon copolymer have larger contact angle for water and oil repellent finish, and the fabric processed with simultaneous bathing of fluorocarbon copolymer/TEOS is the strongest but has poorer softness. Furthermore, when processing with chemical compounds, the processes or orders had little effect on the fabric's angle of contact and bleaching, but had more significant influence on strength. Regarding to washing fastness, after ten‐time water washing, the angle of contact of processed fabrics decreased by about 3%. Overall, the fabric pretreated with TEOS, followed by fluorocarbon polymer, had the best balance of physical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3019–3024, 2007     

Preparation of polymer/silica/polymer tri-layer hybrid materials and the corresponding hollow polymer microspheres with movable cores

Tri-layer poly(methacrylic acid-co-ethyleneglycol dimethacrylate)/silica/poly(ethyleneglycol dimethacrylate) (P(MAA-co-EGDMA)/SiO₂/PEGDMA) and P(MAA-co-EGDMA)/SiO₂/polydivinylbenzene hybrid microspheres were prepared by distillation precipitation polymerization of ethyleneglycol dimethacrylate (EGDMA) and divinylbenzene (DVB) in the presence of 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified P(MAA-co-EGDMA)/SiO₂ microspheres as the seeds. The polymerization of EGDMA and DVB was performed in neat acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as initiator to coat the MPS-modified P(MAA-co-EGDMA)/SiO₂ seeds through the capture of EGDMA and DVB oligomer radicals with the aid of vinyl groups on the surface of modified seeds in the absence of any stabilizer or surfactant. Monodisperse P(MAA-co-EGDMA)/SiO₂ core-shell microspheres were synthesized by coating of a layer of silica onto P(MAA-co-EGDMA) microspheres via a sol-gel process, which were further grafted by MPS incorporating the reactive vinyl groups onto the surface to be used as the seeds for the construction of hybrid microspheres with tri-layer structure. Hollow poly(ethyleneglycol dimethacrylate) (PEGDMA) and poly(divinylbenzene) (PDVB) microspheres with movable P(MAA-co-EGDMA) core were subsequently developed after the selective etching of the silica mid-layer from the tri-layer hybrid microspheres in hydrofluoric acid. The morphology and structure of the tri-layer polymer hybrids and the corresponding hollow polymer microspheres with movable P(MAA-co-EGDMA) core were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectra and X-ray photoelectron spectroscopy (XPS).     

Organic–inorganic hybrid materials. II. Preparation and properties of higher silica containing polycarbonate–silica hybrid materials

The sol–gel reaction of a polycarbonate (PC) oligomer having triethoxysilyl groups at both ends of the PC chain (PCS) with a tetraethoxysilane or tetramethoxysilane oligomer provided transparent or semitransparent films of higher silica containing organic–inorganic hybrid materials (HSPC‐HMs). The films were superior to those from PC and from PCS in terms of the morphological homogeneity, heat resistance, and surface hardness. The HSPC‐HM films had minimum oxygen permeability at a PCS/tetraethoxysilane ratio of 3/7. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4273–4279, 2006     

聚合物/无机杂化纳米复合材料制备方法的研究进展

聚合物/无机杂化纳米复合材料是纳米材料发展的一个重要方向。简述了纳米粒子对聚合物纳米复合材料的力学性能和功能特性的影响,介绍了聚合物/无机杂化纳米复合材料的制备方法及应用,并对其研究进行了展望。     

煤系高岭土表面改性及在高分子材料中的应用

介绍了煤系高岭土的特征、对其表面改性的目的及改性设备和工艺,浅析了硅烷偶联剂和钛酸酯偶联剂的构造与改性机理,综述了我国煤系高岭土在高分子材料中的应用情况。     

Preparation of ellipsoidal hematite/polymer hybrid materials and the corresponding hollow polymer ellipsoids

Ellipsoidal hematite/poly(ethyleneglycol dimethacrylate) core-shell hybrid materials were prepared by distillation precipitation polymerization of ethyleneglycol dimethacrylate (EGDMA) in the presence of 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified hematite (α-Fe₂O₃) particles as the seeds. The polymerization of EGDMA was performed in neat acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as initiator to coat MPS-modified hematite seeds through the capture of EGDMA oligomer radicals with the aid of vinyl groups on the surface of the MPS-modified hematite particles in absence of any stabilizer or surfactant. The shell-thickness of the core-shell hybrid particles was controlled by the feed of EGDMA monomer during the polymerization. Other hematite/polymer core-shell hybrid particles, such as hematite/polydivinylbenzene (α-Fe₂O₃/PDVB) and hematite/poly(divinylbenzene-co- methacrylic acid) (α-Fe₂O₃/P(DVB-co-MAA)) were also prepared by this procedure. Hematite/poly(N,N′-methylenebisacrylamide-co-methacrylic acid) (α-Fe₂O₃/P(MBAAm-co-MAA)) were synthesized with unmodified hematite particles as the seeds. Hollow polymer ellipsoids were subsequently developed after the selective removal of the hematite core with hydrochloric acid (HCl) from hematite/polymer core-shell hybrids. The resultant core-shell hybrid particles and hollow polymer ellipsoids were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR) and vibrating sample magnetometer (VSM).     

POSS/聚合物有机-无机杂化材料的研究进展

介绍了笼型倍半硅氧烷(POSS)的特点。综述了POSS/聚合物杂化材料近年来的研究进展(包括POSS/环氧树脂杂化材料、POSS/聚酰亚胺杂化材料、POSS/有机硅杂化材料、POSS/聚乙烯杂化材料、POSS/聚丙烯杂化材料和其他类型含POSS的杂化材料等),并对其应用前景进行了展望。     

无机/聚合物杂化纳米复合材料的研究综述

无机/聚合物杂化纳米复合材料是纳米材料发展的一个重要方面,本文介绍了纳米粒子效应,以及纳米复合材料的特殊性能,并详细介绍了无机/聚合物纳米复合材料的制备方法,最后对无机/聚合物纳米复合材料研究进行了展望.     

Novel composite polymer electrolyte comprising poly(ethylene oxide) and triblock copolymer/mesostructured silica hybrid used for lithium polymer battery

Ordered mesoporous materials, due to its potential applications in catalysis, separation technologies, and nano-science have attracted much attention in the past few years. In this work, a novel PEO-based composite polymer electrolyte by using organic-inorganic hybrid EO₂₀PO₇₀EO₂₀ @ mesoporous silica (P123 @ SBA-15) as the filler has been developed. The interactions between P123 @ SBA-15 hybrid and PEO chains are studied by X-ray diffraction (XRD), differential scanning calorimeter (DSC), and FT-IR techniques. The effects of P123 @ SBA-15 on the electrochemical properties of the PEO-based electrolyte, such as ionic conductivity, lithium ion transference number are studied by electrochemical ac impedance spectroscopy and steady-state current method. The experiment results show that P123 @ SBA-15 can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolyte, which are induced by the special topology structure of P123 in P123 @ SBA-15 hybrid, at the same time. The excellent lithium transport properties and broad electrochemical stability window suggesting that PEO-LiClO₄/P123 @ SBA-15 composite polymer electrolyte can be used as candidate electrolyte materials for lithium polymer batteries.     

Wear and mechanical properties of reactive thermotropic liquid crystalline polymer/unsaturated polyester/glass fiber hybrid composites

To improve the performance of unsaturated polyester (UP) under cold‐heat alternate temperature, self‐synthesized reactive thermotropic liquid crystalline polymer (TLCP)‐methacryloyl copolymer (LCMC), UP, and glass fiber (GF) hybrid composites was prepared by molding technology. The apparent activation energy and crystal behavior analysis of LCMC/UP blends were investigated by Differential scanning calorimetry and X‐ray diffraction (XRD), respectively, the results showed that the addition of LCMC can reduce apparent activation energy and accelerate the curing reaction of UP, the XRD analysis indicated that the crystal phase of LCMC still exist in the blends after blending with UP. The effect of LCMC content on the properties of LCMC/UP/GF hybrid composites such as impact strength, bending strength, and ring‐on‐block wear were also investigated through static mechanical tests and wear tests. The mechanical properties of hybrid composites increased significantly because of the addition of LCMC. The wear tests showed that LCMC can improve the wear resistance of the UP/GF/LCMC hybrid composites even though the content of LCMC was at a relatively low level (5–7.5 wt %). This makes it possible to develop novel kind of UP‐based materials with good wear resistance for various applications. The Worn surface was observed by scanning electron microscopy (SEM) and the mechanism for the improvement is discussed in this paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3899–3906, 2007     

铁氧体／高分子纳米复合材料的制备方法及展望

纳米吸波材料是解决电磁污染和雷达隐身的关键因素之一,能提高电子系统的电磁兼容性和隐身装备的突防能力。综述铁氧体／高分子纳米复合吸波材料的制备技术以及国内外研究进展,展望制备强、宽、轻、薄的纳米复合吸波剂。     

Polyoxometalate-Incorporated Supramolecular Self-Assemblies: Structures and Functional Properties

As a family of functional inorganic clusters, polyoxometalates (POMs) were introduced into hybrid self-assemblies with the assistance of the supramolecular interaction with diverse organic cationic molecules, which reinforced both the processibility and functionality of the POMs. This method not only improved the surface properties of the POMs, but also provided excellent amphiphilic building blocks for the construction of advanced self-assembled nanostructures. In this review, we summarize the fundamental aspects of surfactant-encapsulated POMs (SEPs) and the most recent progress in potential applications of SEPs and the related POM-containing systems (hybrids composed of POMs and polymers and other cationic molecules beyond surfactants). The functionalization of such organic/inorganic hybrids in self-assembled systems is also described. Furthermore, perspectives regarding self-assemblies and possible applications of POM complexes with synergetic interactions between organic and inorganic components are outlined.     

纳米材料/十四酸混合相变蓄热材料的制备与特性

选用纳米金属Cu和碳素材料石墨烯纳米片（GnPs）为改性剂分别添加至十四酸（MA）中,制备出Cu质量分数为1%、2%、3%和4%的Cu/MA混合相变蓄热材料及GnPs质量分数为1%、2%和3%的GnPs/MA混合相变蓄热材料,并对混合相变材料性能进行表征。结果表明：Cu/MA固态和液态热导率随Cu质量分数增加呈线性提高,1%（质量）GnPs/MA固态热导率较纯MA显著提高101.51%,随GnPs质量分数增加,热导率增幅减缓;FT-IR谱图表明Cu与MA及GnPs与MA间的混合均为物理作用;DSC结果显示添加Cu或GnPs可降低MA的过冷度和相变潜热,且随质量分数增加,相变潜热逐渐降低;4%（质量）Cu/MA和3%（质量）GnPs/MA放热时间相比于纯MA分别减少了23.4%和38.7%;4%（质量）Cu/MA和3%（质量）GnPs/MA在经历300次快速热循环试验后,晶体结构和相变温度基本保持不变,相变潜热分别降至168 J·g^-1和181 J·g^-1左右,仍满足蓄放热要求,两种材料均具有良好的热循环稳定性。     

有机-无机杂化材料制备质子交换膜的研究进展

综述了近年来采用有机-无机杂化材料制备质子交换膜的研究进展，重点介绍了由掺入了质子导电单元或经过磺化的有机-无机杂化材料制得的质子交换膜及由带磺酸基的有机硅通过溶胶-凝胶工艺制备的有机-无机杂化质子材料制得的交换膜，并从制备方法出发分析了每种质子交换膜的性能。     

Preparation and properties of organosoluble montmorillonite/polyimide hybrid materials

Organosoluble montmorillonite/polyimide hybrids were prepared using a monomer solution intercalation polymerization method. Montmorillonite was organo-treated with p-aminobenzoic acid and the organosoluble polyimide was based on pyromellitic dianhydride and 4,4′-diamino-3,3′-dimethyldiphenylmethane. The particle size of montmorillonite in the hybrid containing 1 wt % of montmorillonite is about 400 nm. The strength and the toughness of montmorillonite/polyimide hybrids are improved simultaneously when the montmorillonite content is below 5 wt %. The thermal stabilities of montmorillonite/polyimide hybrids are obviously improved and their thermal expansion coefficients are reduced. When the montmorillonite content is below 5 wt %, the montmorillonite/polyimide hybrids are soluble in strong aprotonic polar organic solvents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2063–2068, 1999     

Preparation of solid-state composite electrolytes based on organic/inorganic hybrid star-shaped polymer and PEG-functionalized POSS for all-solid-state lithium battery applications

A series of composite electrolytes (CEs) consisting of organic/inorganic hybrid star-shaped polymer (SPP13), plasticizer (PEG-functionalized POSS derivatives), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared to investigate the effects of the composite compositions and PEG chain length of PEs on the properties of CEs. SPP13 was prepared via ATRP from poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryl-cyclohexyl-POSS (MA-POSS) using an octafunctional initiator, and the PEG-functionalized POSS derivatives were synthesized by the hydrosilylation reaction of octakis(dimethylsilyloxy)silsesquioxane (OHPS) and allyl-PEG. The CEs were found to be dimensionally-stable enough to separate the electrodes in batteries, but they still possessed high mobility of ion-conducting P(PEGMA) segments, as estimated by the low glass transition temperatures (T_g). The CEs having solid-state show quite high ionic conductivity (4.5 × 10⁻⁵ S cm⁻¹ at 30 °C) which is about three times of magnitude larger than that of the matrix polymer (SPP13) electrolyte (1.5 × 10⁻⁵ S cm⁻¹ at 30 °C). The CEs were electrochemically stable up to +4.2 V without the decomposition of electrolytes. An all-solid-state lithium battery prepared from the CEs exhibited larger discharge capacity than that prepared from the SPP13 electrolyte at 60 °C.     

壳聚糖/纳米SiO_2杂化材料的研究

在甲醇和乙酸介质中,通过酸酐与壳聚糖反应,合成了水溶性的N-酰化壳聚糖,并将纳米二氧化硅颗粒与N-酰化壳聚糖水溶液经溶胶-凝胶过程,制备了壳聚糖/纳米S iO2杂化材料。通过傅立叶变换红外光谱、元素分析、扫描电镜等方法对杂化材料进行了表征,采用热重分析对杂化材料的热性能进行研究。扫描电镜分析结果表明,杂化材料为纳米尺度的无机S iO2加强化的片状材料,S iO2颗粒分散在材料中,形成均匀的表面;热重分析结果表明,杂化材料的热性能有较大提高。     

Preparation and properties of poly(siloxane‐ether‐urethane)‐acrylic hybrid emulsions

Poly(siloxane‐ether‐urethane)‐acrylic (PU‐AC) hybrid emulsions were prepared by introducing different hydroxyethoxypropyl‐terminated polydimethylsiloxane (PDMS) content into the acrylic‐terminated poly(ether‐urethane) backbone and then in situ copolymerizing with methyl methacrylate and butyl acrylate via emulsion process. The effects of PDMS on the particle size and viscoelastic behavior of the hybrid emulsions were investigated. Meanwhile, the hydrogen bonding, mechanical and thermal mechanical properties, water resistance, the surface gloss, and wettability of the resultant hybrid films were also studied. The results showed that all the hybrid emulsions showed shear‐thinning behaviors, and the introduction of PDMS resulted in the formation of the hybrid emulsions with increased average particle size and decreased viscosity. The chemical bonds built between PU and AC yielded higher than 73% crosslinking fraction in all the hybrid materials, but this value decreased with increasing PDMS content because PDMS reduced the hydrogen bonding interactions and enhanced the phase separation. As a result, an increase in the PDMS content led to an increase in the elongation, water resistance, surface roughness, and water hydrophobic of the films, but the tensile strength, hardness, storage modulus, and glass transitions temperature decreased. It is suggested that introduction of PDMS can provide the hybrid materials with the improved flexibility, water resistance, and surface hydrophobicity, which has potential application value in the fouling‐release coatings, biomaterials, and surface fishing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44927.