刚柔嵌段共轭聚合物自组装体系*

刚柔嵌段共轭聚合物的自组装是超分子化学研究的热点之一。本文综述了近年来刚柔嵌段共轭聚合物自组装体系研究进展。根据共轭刚性段的不同分类进行阐述,综述了聚芴,二（苯乙烯）-蒽,聚对苯撑,聚对苯乙烯撑,聚对苯撑乙炔,聚（2,5-苯甲酮）,聚噻吩,聚苯基喹啉等作为刚性链段的刚柔嵌段共轭聚合物自组装体系,介绍了刚柔嵌段共轭聚合物的合成和光物理性质;重点评述了刚柔嵌段共轭聚合物在不同溶剂、浓度、温度等条件下自组装形成一维、二维以及三维的周期性微结构,且具有方便的可控性。概括了刚柔嵌段共轭聚合物自组装体系广阔的应用前景,尤其在光电器件领域有着潜在的应用价值。最后展望了刚柔嵌段共轭聚合物自组装体系研究和发展的方向。     

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties

The graft‐through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self‐assembly of GBCPs resulted in ordered nanostructures with ultra‐small domain sizes down to 2.8 nm (half‐pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self‐assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.     

全共轭嵌段共聚物的合成组装与应用

全共轭嵌段共聚物体系将共轭聚合物的光电特性和嵌段聚合物的自组装优势相结合,是近几年发展起来的一类新型自组装光电功能材料,对其自组装机理、自组装结构与光电性能之间关系的研究,有利于共轭聚合物微观纳米结构的构筑以及未来光电器件的开发。本文主要介绍全共轭嵌段共聚物包括共轭聚电解质在内的合成发展过程,综述其在溶液中和薄膜状态下独特的自组装行为,介绍共轭聚合物在光电器件中的应用,并对其今后的研究方向做出展望。     

经两亲嵌段共聚物自组装制备纳米胶束

本文介绍两亲嵌段共聚物的合成,综述了经两亲嵌段共聚物自组装制备纳米胶束的研究进展,并对该领域的发展趋势进行了展望。     

两亲嵌段共聚物溶液自组装新进展

综述了两亲嵌段共聚物在溶液中自组装的新进展，重点介绍了两亲嵌段共聚物自组装聚集体中棒状、蠕虫状、囊泡、洋葱和实心洋葱等几种新形态的特点和形成机理；另外对两亲嵌段共聚物溶液自组装在光电、药物释放、靶向以及作为基因工程载体方面的应用前景及两亲嵌段共聚物聚集体的制备方法作了详细的评述。     

全亲水性嵌段共聚物及其超分子自组装

本文介绍了全亲水性嵌段共聚物(DHBCs)的定义与特点.根据不同的环境敏感自组装机理,分类详述了不同DHBCs的结构及其超分子自组装行为,并探讨了相应的应用现状与前景.     

Kinetics and Morphology of an Epoxy Resin Modified with PEO-PPO-PEO Block Copolymers

Block copolymers are a special class of polymers having the ability to self-assemble into nanoscale ordered structures which depend on molecular composition of the blocks. With the aim of studying the influence of copolymer composition, the kinetics of a 4,4′-diaminodiphenylmethane-cured diglycidyl ether of bisphenol-A (DGEBA) epoxy system modified with a PEO-PPO-PEO block copolymers has been investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), taking into account the relation between blocks in the copolymer as well as different copolymer contents. DSC results show that the rate of cure reaction decreases when the copolymer is added, which can be attributed to the interaction between the hidroxyl groups of the growing epoxy thermoset and the ether groups of the block copolymer observed by FTIR. The experimental results obtained have been related to the morphologies observed by atomic force microscopy (AFM).     

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

聚二茂铁基硅烷二嵌段共聚物的制备、组装及应用研究

二茂铁分子由于含有独特的芳香结构和过渡金属元素铁,具有特殊的光、电、磁特性,一直以来是科学研究和技术应用的热点之一,在功能高分子材料的制备方面具有广泛的应用前景。聚二茂铁硅烷嵌段共聚物是一类新型的主链含有二茂铁和有机硅单元的聚合物,以其可控的分子量和丰富的自组装形貌,不断得到科研人员的关注。本文主要从聚合、自组装和应用三个方面系统介绍了聚二茂铁硅烷二嵌段共聚物。其中重点介绍了应用广泛的活性阴离子聚合和进一步发展起来的阴离子两步法聚合,解释了活性聚合机理,归纳了目前成功合成的不同种类的二嵌段共聚物;论述了在选择性溶剂中,聚二茂铁硅烷二嵌段共聚物可以自组装形成柱状、管状、球状等常规胶束和片层、刷形等复杂胶束,胶束的形成同聚合一样具有活性特征,并且在一定的刺激条件下,不同类型的胶束可完成相互转变过程,另外可以对胶束局部进行功能化以赋予其特殊的性能;最后介绍了聚二茂铁硅烷二嵌段共聚物在药物缓释、纳米材料、特种催化方面的具体实例,并对其应用前景加以展望。     

Quasi‐Block Copolymers Based on a General Polymeric Chain Stopper

Quasi‐block copolymers (q‐BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end‐terminated by a functionality that interacts with the supramolecular monomer (a “chain stopper” functionality). A new design of q‐BCPs based on a general polymeric chain stopper, which consists of polystyrene end‐terminated with a sulfonate group (PS‐SO₃Li), is described. Through viscosity measurements and a detailed diffusion‐ordered NMR spectroscopy study, it is shown that PS‐SO₃Li can effectively cap two types of model supramolecular monomers to form q‐BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q‐BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q‐BCPs as smart, nanostructured materials.     

柱状相聚苯乙烯-b-聚乳酸的合成及引导组装

设计并合成了2种柱状相结构的聚苯乙烯-b-聚乳酸(PS-b-PLA)两嵌段共聚物,并表征了它们在化学图案上的引导自组装行为。在辛酸亚锡(Sn(Oct)_2)催化下,采用羟基官能化的聚苯乙烯(PS-OH)大分子引发剂分别引发外消旋丙交酯(rac-LA)和左旋丙交酯(L-LA)开环聚合,制备了两个相对分子质量相近但构型不同的PS-b-PLA:PS-b-PDLLA和PS-b-PLLA。通过核磁共振波谱仪(NMR)、凝胶渗透色谱仪(GPC)、示差扫描量热仪(DSC)、热重分析仪(TGA)、小角X射线衍射仪(SAXS)等测试手段对两个嵌段共聚物的性质进行了表征。然后,将PS-b-PDLLA和PS-b-PLLA薄膜在六方点阵化学图案模板上加热引导自组装,得到长程有序排列的六方柱状相结构。相对于柱状相的PS-b-PLLA,柱状相的PS-b-PDLLA具有较大的拉伸比例,可以在更大的周期范围内组装出规整的六方结构。这一结果与层状相PS-b-PDLLA和PS-b-PLLA薄膜在线性化学图案上组装的结果相似。     

嵌段共聚物薄膜快速自组装方法

嵌段共聚物 (BCP) 薄膜可通过不同的退火方法诱导其微相分离,从而获得大面积圆柱状、层状和球状等纳米图案。这些长程有序的纳米结构形态,已经广泛应用在纳米光刻和电子器件等多个领域中。目前,有效且快速的退火方法仍然是BCP薄膜自组装技术中的研究热点。本文首先介绍了制备BCP薄膜纳米结构图案常用的退火技术,然后综述了三种新型快速退火技术,最后分析总结了这些退火技术的优缺点。     

Modular Synthesis of Functional Block Copolymers

Summary: The free‐radical addition of ω‐functional mercaptans to the vinyl double bonds of 1,2‐polybutadiene‐block‐poly(ethylene oxide) copolymers was used for modular synthesis of well‐defined functional block copolymers. The modification reaction proceeds smoothly and yields quantitatively functionalized block copolymers (¹H NMR and FT‐IR spectroscopy) without disturbing the molecular‐weight distribution of the parent copolymer (PDI < 1.09, size exclusion chromatography).

The modular synthetic pathway towards the functional block copolymers reported here.     

Random Block Copolymers via Segment Interchange Olefin Metathesis

Polycarbonate/polyethylene random block copolymers (RBCs) have been produced using olefin metathesis catalysis in a process termed segment interchange metathesis. An olefin metathesis catalyst tolerant of polar functionality was added to reagent polycarbonate and polyethylene polymers which contained internal unsaturated carbon–carbon bonds. Subsequent metathesis occurred, segmenting the reagent polymers, resulting in RBCs. The block copolymers self-assembled into microphase structures which persisted into the melt state as determined by small angle X-ray scattering (SAXS).

     

Structure of Styrene and Acrylate Block Copolymers

Abstract

Using UV light as the energy source and polystyrene- (PS-) or polymethyl methacrylate- (PMMA-) macroinitiators with active aromatic or aliphatic thiyl end groups, PS-PMMA and PMMA-PEA (poly-ethyl acrylate) block copolymers were synthesized. The molecular weights of both block copolymers increased with increasing reaction time. The reactivity of macroinitiators depended on the type of thiyl groups and monomer and not on the length of the polymer chain. The most reactive were macroinitiators containing resonance stabilized non-substituted or substituted aromatic end groups. The decomposition of the macroinitiators took place over the formation of the thiyl radical and macroradical. The bond length, the bond dissociation energy, and the bond order of macroradical end groups were calculated. The most reactive monomer was ethyl acrylate; the less reactive was styrene. The structure, the molecular weight, and the T _g of the styrene-acrylate block copolymers were determined. The PMMA/PEA block copolymer had two of block's T _g s, the first at 105°C, the second at ?24°C, and a third at 16°C which probably represents contacting segments.     

两嵌段聚合物自组装微观形貌中的网状结构

嵌段聚合物由于不同嵌段热力学不相容而形成微观相分离,进而发生自组装排列成规则有序的微观结构,其中网状结构是自组装微观结构中的复杂结构,具有令人瞩目的特性,在纳米科技领域应用价值极高,备受各国研究者的青睐。本文介绍了嵌段聚合物自组装原理和网状结构的特点,重点综述了两嵌段聚合物自组装结构中常见的三种网状结构的发展、制备方法以及在纳米科技中的应用,并指出当今网状结构的研究热点,预测该领域的发展趋势。     

Tunable Self-Assembly of Diblock Copolymers into Colloidal Particles with Triply Periodic Minimal Surfaces

We herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse or mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.     

Fluorinated Amphiphilic Block Copolymers: Combining Anionic Polymerization and Selective Polymer Modification

We report the preparation of novel fluorinated block copolymers using a two-step modification sequence. We first prepared model polyisoprene-poly-tert-butylmethacrylate block copolymers by anionic polymerization. Exposing these materials to difluorocarbene (generated by the thermolysis of hexafluoropropylene oxide) resulted in modification of the polyisoprene block to the corresponding difluorocyclopropane repeating unit without compromising the integrity of the poly-tert-butylmethacrylate block. Hydrolysis of the difluorocarbene-modified materials gave the corresponding difluorocarbene-modified polyisoprene-polymethacrylic acid diblock copolymers. These amphiphilic materials are expected to exhibit interesting self-assembly behavior in aqueous solution.     

An Improved Rapid Synthesis of Oligo(p‐benzamide) Block Copolymers

We describe a new synthesis that allows the preparation of oligo(p‐benzamide)s up to the heptamer on solid support without the need of semi‐temporary amide N‐protective groups. With increase in length, the solubility of oligo(p‐benzamide)s reduces dramatically. Even the tetra(p‐benzamide) is not soluble in common organic solvents. Therefore, solution syntheses of oligomers beyond the tetramer are not feasible. As will be shown in this paper, solid supported synthesis allows the preparation of even longer oligomers (up to the heptamer) in good yields. The high dilution on the solid support is most likely responsible for their pseudo‐solution‐like reactivity and the prevention of aggregation. This procedure is a significant improvement of previous syntheses and an important tool for the rapid exploration of supramolecular rod–coil copolymers based on oligoaramides.