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表面引发聚合新进展及应用 总被引:1,自引:0,他引:1
综述了近年来聚合物刷合成与应用方面的新进展.简要介绍了利用表面引发原子转移自由基聚合(SI-ATRP)制备聚合物刷的历程和重要进展.重点论述了通过电化学、光诱导以及牺牲阳极技术、仿生合成等发展了多种表面引发ATRP新方法,基于如何将聚合物从分子尺度过渡到微米尺度的思考,实现了多尺度聚合物刷结构的制备.简要综述了聚合物刷在以下3个方面的应用研究:(1)智能驱动,利用聚合物刷构象变化,实现微悬臂驱动、辅助放大的电驱动以及仿毛毛虫运动.(2)生物润滑,利用聚合物的环境响应行为实现了对摩擦系数的调控,并发展了球刷型润滑材料.(3)表面防污,表面接枝含离子液体官能团的聚合物刷,并与仿生技术相结合,利用化学组成和结构化协同效应,得到一系列高性能低毒海洋防污界面材料. 相似文献
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瓶刷聚合物(BBPs)具有独特的分子结构和富有前景的应用领域,因此受到学者们日益广泛的关注。通过共价键接枝策略来合成瓶刷聚合物费时、合成困难,难以功能化。而通过非共价键作用,则容易将侧链接枝到共聚物主链上,为构建超分子瓶刷共聚物提供有利条件。超分子作用的引入,不仅带来瓶刷聚合物制备方面的灵活性,同时使材料具备更多的响应性、可逆性等功能。本文介绍了氢键、主客体相互作用、金属配位作用、离子相互作用等多种超分子作用介导的瓶刷聚合物的构建及组装,分析讨论了其各自特点、构筑策略,阐明了超分子作用介导的瓶刷聚合物的巨大应用潜能和重要研究意义,最后对其目前仍面临的问题和未来发展进行了分析和展望。 相似文献
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《化学进展》2017,(10)
近年来,刺激响应聚合物因其独特的性质而受到广泛关注,这类聚合物能够感受外界环境刺激(包括光、电、热、力、氧化还原、pH、化学、环境和生物信号等刺激)而产生响应,从而引起体系物理或化学性质的改变。而梯度聚合物则是伴随着可控自由基聚合技术的诞生、发展而出现和形成的一类新型聚合物,区别于无规和嵌段聚合物,梯度聚合物表现出单体组成沿分子链渐变的性质,其中,由亲水性单元和憎水性单元组成的两亲性梯度聚合物在选择性溶剂中可自组装形成多种聚集体,因此具有多方面的潜在应用价值,比如超分子组装体、智能涂料、网络或这些可能应用的组合。本文调研了有关梯度聚合物方面的研究工作,综述了几种梯度聚合物的合成方法,如活性阴离子聚合法、可控自由基聚合法(包括氮氧稳定自由基聚合、原子转移自由基聚合及可逆加成断裂链转移自由基聚合)和开环聚合法等,同时阐述了梯度聚合物的自组装及刺激响应行为,尤其是其独特的热和pH敏感性。此外,还对由两亲性嵌段聚合物和两亲性梯度聚合物自组装形成的聚集体的刺激响应行为进行了详细地论述和比较,并指出了梯度聚合物的应用前景和发展方向。 相似文献
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Sergio Enrique Moya Jagoba Jon Iturri Ramos Irantzu Llarena 《Macromolecular rapid communications》2012,33(12):1022-1035
This feature article deals with the self assembly and physical chemistry of polyelectrolytes: multilayers and brushes. The article highlights the interesting behavior of polyelectrolytes in nanoscale assemblies, giving more insight into the complexity of the formation of the assemblies. The water content of multilayers and brushes is studied during the assembly and in different ionic strengths. Similarities are found in the behavior of the brushes and multilayers with ionic strength, with regard to changes in the thickness and the water content. An invariance of the zeta potential with ionic strength is also observed for both systems, which can be explained as a result of conformational changes of the polymer chains. Finally, the combination of brushes and multilayers for surface modification is presented. 相似文献
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Functionalized poly(ethylene oxide) (PEO) macromonomers (alpha -tertiary amino and omega -methacryloyl groups) were prepared by ring-opening polymerization of live PEO anions end-capped with styrene oxide using 2-[2-(N ,N -dimethylamino)-ethoxy]ethanol potassium alkoxides as an initiator with methacryloyl chloride. PEO brushes were synthesized by free-radical homopolymerization of such PEO macromonomers. These brushes were converted into peripherally charged brushes by quaternization. We studied the solution properties of both types of brushes from the viewpoint of charge effect. It was found from dynamic light scattering (DLS) that the polymer brushes formed a single macromolecule in solution due to crowding of side chains. It was speculated from angular dependence measurements that the polymer brushes with large aspect ratios took a geometrical anisotropic conformation such as a cylinder. In methanol with a low dielectric constant, radius of gyration (R(G)), and cross-sectional radius of gyration (R(G,C)) of the polymer brushes with charged side chains were smaller than those of the polymer brushes without charges. In a solvent with a low dielectric constant such as methanol, ionic groups do not dissociate and condense. On the other hand, these physical values in an aqueous solution were somewhat larger than those of the polymer brushes without charges. In water with a high dielectric constant, peripherally charged brushes were strongly stabilized by electric double layers. 相似文献
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Scott T. Milner 《Journal of Polymer Science.Polymer Physics》1994,32(16):2743-2755
Polymer “brushes” are formed when long-chain molecules are somehow attached by one end at an interface with a relatively small area per chain. Such adsorbed brushes in the presence of solvent may be used to modify surface properties, stabilize colloidal particles, etc. Strongly segregated block copolymer phases, or interfacial layers of such “polymeric surfactants” may also be modeled in terms of “melt brushes,” (i.e., brushes without solvent). In both cases, when chain attachments are crowded on the interface, the chains stretch out to avoid neighboring chains. The resulting physical state has properties markedly different from polymer solutions, gels, or weakly adsorbed polymer layers. When the chains are strongly stretched, their statistical mechanics become simpler, as fluctuations around the set of most probable conformations are suppressed. This makes possible many pencil-and-paper calculations of brush properties, including bending and compressional moduli, and detailed knowledge of the chain conformations. As a recent example, I will describe calculations of phase diagrams of strongly segregated block copolymers including bicontinuous double-diamond phases. © 1994 John Wiley & Sons, Inc. 相似文献
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Andruzzi L Senaratne W Hexemer A Sheets ED Ilic B Kramer EJ Baird B Ober CK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2495-2504
The nitroxide-mediated polymerization of styrenic monomers containing oligo(ethylene glycol) (OEGn) moieties was chosen for the preparation of biocompatible polymer brushes tethered to silicon oxide surfaces due to the broad range of monomer structures available and the use of a nonmetallic initiator. These surfaces were characterized by near-edge X-ray absorption fine structure and water contact angle measurements. The biocompatibility of these grown polymer brushes was studied and compared with deposited assemblies of surface-bound OEGn-terminated silanes with selected chain lengths. Grown polymer brushes with short OEGn side chains suppressed protein adsorption significantly more than the deposited assemblies of short OEGn chains, and this was attributed to higher surface coverage by the brushes. Cell adhesion studies confirmed that OEGn-containing polymer brushes are particularly effective in preventing nonspecific adhesion. Studies of protein adsorption and cell localization carried out with specific ligands on surfaces patterned demonstrated the potential of these surface-tethered polymer brushes for the formation of micro- and nanoscale devices. 相似文献
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Control of surface properties using fluorinated polymer brushes produced by surface-initiated controlled radical polymerization 总被引:1,自引:0,他引:1
Andruzzi L Hexemer A Li X Ober CK Kramer EJ Galli G Chiellini E Fischer DA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10498-10506
Surface-grafted styrene-based homopolymer and diblock copolymer brushes bearing semifluorinated alkyl side groups were synthesized by nitroxide-mediated controlled radical polymerization on planar silicon oxide surfaces. The polymer brushes were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and time-dependent water contact angle measurements. Angle-resolved XPS studies and water contact angle measurements showed that, in the case of the diblock copolymer brushes, the second block to be added was always exposed at the polymer-air interface regardless of its surface energy. Values of z*/Rg were estimated based on the radius of gyration, Rg, of the grafted homopolymer or block copolymer chains for the grafted brushes and thickness of the brush, z*. The fact that z*/Rg > 1 suggests that all these brushes are stretched. These results support the idea that after grafting the first block onto the surface the nitroxide-end capped polymer chains were able to polymerize the second block in a "living" fashion and the stretched brush so formed was dense enough that the outermost block in all cases completely covers the surface. NEXAFS analysis showed a relationship between the surface orientation of the fluorinated side chains and brush thickness with thicker brushes having more oriented side chains. Time-dependent water contact angle measurements revealed that the orientation of the side chains of the brush improved the surface stability toward reconstruction upon prolonged exposure to water. 相似文献
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Elena Vlasova Boris Volchek Irina Tarasenko Guennadii Vlasov 《Macromolecular Symposia》2011,305(1):116-121
Fourier transform infrared spectroscopy (FTIR) was used for determination of orientational and conformational characteristics of plane polypeptide brushes with different density of polypeptide chains grafted to modified silicon surface. The determination of grafting density of polypeptide chains in brushes, which depends on chemical structure of spacer groups, was carried out using ultraviolet (UV) spectroscopy. The influence of chemical structure of modifying spacer groups and outer conditions on the characteristics of plane polypeptide brushes was established. The peculiarities of α-helical structure (random coil transfer of polymer chains in brushes under the action of denaturants) were investigated. 相似文献
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We directly monitor the absolute separation profiles that function as film thickness between a single glass disk and the charged polyelectrolyte brushes decorated steel slider in water using a home-made slider-on-disk apparatus, which reflects the structural conformation variations and interactions of polymer brushes under externally applied pressure, in addition to probing the relative variation of friction forces under different applied loads and sliding velocities. We find that the polyelectrolyte brushes modified surfaces can sustain high pressure and have extremely low friction coefficients(around 0.006 at pressures of 0.13 MPa; 0.5-0.6 without brushes). The water-lubrication characteristics are correlated to the structural conformation changes of the polyelectrolyte brushes that are mainly governed by electrostatic interactions and the osmotic pressure of counterions inside the polymer chains, which can be used to support and distribute the normal pressure. The apparent thickness of the brush decreases with the increase of loading forces, an increase in the ionic strength causes the polymer chains collapse, and the friction forces increase. This fundamental research is of great importance to understand the mechanical and structural properties of polyelectrolyte brushes and their influences on the tribological behaviors, and helps to design friction/lubrication-controlled surface/interface by taking advantage of polyelectrolyte brushes. 相似文献
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建立了用于模拟双峰聚合物分子刷相结构的自洽场理论. 模拟结果表明, 良溶剂条件能够促使双峰聚合物分子刷裂分为内外两个亚分子层, 其中短链居于内分子层, 而长链伸展到外分子层. 体系溶解性的加强不仅使聚合物的密度分布逐渐趋近强分凝理论的解析结果, 而且加大了分子链的伸展和链段的局部取向程度. 分子链接枝密度的增加能够促使分子刷的层化, 并且在良溶剂区域, 不同接枝密度的分子链密度分布可以回归到同一条主线. 在良溶剂条件下, 长链的聚合度对短链的密度分布影响不大, 但能够导致长链向外分子层扩展. 相似文献
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Jian Zhang Yongfang Yang Chuanzhuang Zhao Hanying Zhao 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5329-5338
Polystyrene (PS) and poly(methyl methacrylate) (PMMA) mixed polymer brushes on the surface of clay layers were prepared by using in situ free radical polymerization. Free radical initiator molecules with two quaternary ammonium groups at both ends were intercalated into the interlayer spacing of clay layers. The amount of polymer brushes grafted on the surface of clay layers can be controlled by controlling the polymerization time. Thermogravimetric analysis, X‐ray diffraction, and high‐resolution transmission electron microscope results indicated successful preparation of the mixed polymer brushes on the surface of clay layers. The kinetics of the grafting of the monomers was also studied. The mixed polymer brushes on the surface of clay layers were used as compatibilizers in blends of PS and PMMA. In the blends, the intercalated clay particles tend to locate at the interface of two phases reducing the interfacial tension. In the meanwhile, PMMA homopolymer chains tend to intercalate into clay layers. The driving force for the intercalation is the compatibility between homo‐PMMA chains and PMMA brushes on the surface of clay layers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5329–5338, 2007 相似文献
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Valueva S. V. Vylegzhanina M. E. Meleshko T. K. Ivanov I. V. Gasilova E. R. Gel’fond M. L. Yakimansky A. V. Sukhanova T. E. 《Russian Journal of Applied Chemistry》2020,93(1):89-98
The optical and morphological characteristics of polymer molecular brushes with the polyimide backbone and polymethacrylic acid side chains, and also of binary nanosystems based on the molecular brushes and Radachlorine®, a photosensitizer of second generation, were studied. The brushes had the same backbone and approximately equal molecular mass of side chains, but strongly differed in the side chain grafting density. The side chain grafting density influences the molecular-conformation and morphological parameters of free molecular brushes and of the corresponding binary nanosystems.
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