Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Transition metal catalysed C−H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C−C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C−H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C−H/C−X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C−H/C−H cross-coupling protocols driven by the activation of monomers’ C(sp²)−H bonds. Furthermore, poly(annulation) via C−H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C−H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C−H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C−H activation polymerization to prepare conjugated polymers were discussed and commented.     

基于巯基点击反应与RAFT聚合的功能性聚合物合成

可逆加成-裂解链转移聚合(RAFT)由于单体适用面广、聚合条件温和、不受聚合方法的限制等特性, 已经成为活性合成聚合物的有效手段之一。点击化学(click chemistry)由于具有良好的选择性、模块性以及官能团耐受性等特点迅速成为许多研究领域,如药物、聚合物、功能材料等合成的有力工具,同时涌现出了多种基于巯基的点击反应。本文综述了近年来基于巯基的点击反应, 如巯基-烯、巯基-炔、巯基-异氰酸酯、巯基-环氧化物以及巯基-卤代烃等新型点击反应与RAFT聚合相结合在功能性聚合物的制备和修饰中的应用, 相信这两种手段的结合将在其中发挥积极的作用。     

Through-space conjugated polymers based on cyclophanes

Conjugated polymers display unique electronic and optical properties, which favor their use in applications as optoelectronic materials and molecular devices. Despite the recent remarkable progress in the chemistry of conjugated polymers, the synthesis of conjugated polymers containing cyclophane units in the main chain is limited to only a few examples. This Minireview presents recent developments in the synthesis, properties, and applications of through-space conjugated polymers based on cyclophanes.     

Green polymer chemistry: new methods of polymer synthesis using renewable starting materials

The present article reviews the recent results reported mainly from our group on “green polymer chemistry”. Characteristic important aspects of green polymer chemistry include herein, typically (1) using renewable resources as starting materials for polymer production, and (2) employing green method for the polymer synthesis. As renewable starting materials, the following materials were employed; lactic acid, itaconic anhydride, renewable plant oils, and cardanol. Polymer production using these materials contributes to mitigate the carbon dioxide emission because of their “carbon neutral” nature. As green method, lipase enzyme was mainly used for polymerization catalyst, since lipase is a natural benign catalyst, showing a specific catalysis as well as recyclable character. Polymer synthesis from these materials and the catalyst provided various value-added functional polymers, demonstrating good examples of green polymer chemistry.

     

高分子材料的微波辅助合成研究进展

微波加热以其省时、高效、清洁环保的显著优势而使微波辅助合成成为一种广受欢迎的合成技术。高分子材料的传统合成反应时间长、耗能大。将微波辐射应用于高分子材料的合成可缩短反应时间、降低反应能耗,已成为有机合成领域的研究热点。本文简要综述了微波辅助合成技术在工程材料高分子聚酰胺、聚酰亚胺、聚丙烯酸苄基酯以及在医用功能高分子、吸附功能高分子、导电功能高分子和光学功能高分子合成中的研究进展,并展望了微波辅助合成在高分子材料合成中的发展前景。     

“点击”反应在制备环状聚合物中的应用

环状聚合物具有不同于线性高分子的独特性质,是一类具有应用前景的新型聚合物材料,但复杂的结构导致其合成过程复杂繁琐.＂点击＂化学由于其高效、可靠、高选择性的特点已成为拓扑高分子合成的新方法,活性自由基聚合（ATRP、RAFT和NMP）具有聚合物结构可控等特点,二者联用为环状聚合物的合成拓宽了思路.本文就近几年＂点击＂反应、＂点击＂反应与活性自由基聚合联用以及其他方法联用在环状聚合物中的应用进行综述.＂点击＂反应与这些方法的结合将在功能性环状聚合物的设计与合成中发挥积极的作用.     

Bioinspired catecholic chemistry for surface modification

The attachment strategy based on catecholic chemistry has been arousing renewed interest since the work on polymerized catecholic amine (polydopamine) (Messersmith et al., Science, 2007, 318, 426) was published. Catechols and their derived compounds can self-assemble on various inorganic and organic materials, including noble metals, metals, metal oxides, mica, silica, ceramics and even polymers. It opens a new route to the modification of various substrates and the preparation of functional composite materials by simple chemistry. However, there is still not a full review so far about the attachment chemistry despite the dramatically increasing number of publications. This critical review describes the state-of-the-art research in the area: the design and synthesis of catecholic molecules, their adsorption mechanisms and the stability of assemblies in solution, and their applications etc. Some perspectives on future development are raised (195 references).     

Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring-Opening Polymerization to Give Polymers with Low Molecular Weight Distribution

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (Đ) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low Đ are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3–3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low Đ and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.     

Metal-free synthesis of pyridyl conjugated microporous polymers with tunable bandgaps for efficient visible-light-driven hydrogen evolution

Conjugated microporous polymers (CMPs) with tunable bandgaps have attracted increasing attention for photocatalytic hydrogen evolution. However, the synthesis of CMPs usually needs expensive metal-based catalysts. Herein, we report a metal-free synthetic route to fabricate pyridyl conjugated microporous polymers (PCMPs) via a condensed polymerization between aldehyde and aryl ketone monomers. The PCMPs show widely tunable specific surface areas (347–418 m²/g), which were controlled via changing the used monomers. The PCMPs synthesized using monomers of dialdehyde and diacetylbenzene (diacetylpyridine) in the presence of pyridine exhibited the highest visible-light driven hydrogen evolution rate (9.56 µmol/h). These novel designed PCMPs provide wide adaptability to current materials designed for high-performance photocatalysts in different applications.     

Alkynylation of Bio‐Based 5‐Hydroxymethylfurfural to Connect Biomass Processing with Conjugated Polymers and Furanic Pharmaceuticals

Acetylene‐functionalized platform chemicals were synthesized from biomass‐derived 5‐hydrohymethylfurfural (HMF). Demanding mono‐ and bis‐ethynylfurans were obtained in high yields (89–99 %). Applications of these products in the synthesis of smart organic conjugated materials and pharmaceuticals were examined in a series of transformations. Conjugated polyacetylenic polymers with morphology control have been prepared by incorporation of the HMF core.     

Advanced Polymeric Materials for High-tech Innovations

High technology is advancing our society and modernizing our life and advanced materials play an important role in the technological innovations. My research group has been working on the development of advanced polymeric materials and in this talk I will report our recent work on the creation of new conjugated polymers with novel molecular structures and unique materials properties.1-18 Our work include the design of molecular structures of monomeric building blocks, development of stable, effective and environmentally benign "green” polymerization catalysts, discovery of new polymerization reactions, synthesis of functional macromolecules, fabrication of nanodimensional composites, assembly and control of hierarchical structures, and construction of electrooptical devices. We have revealed the liquid crystallinity, light emission, photoconductivity, optical limiting, nano-hybridization, solvatochromism, optical activity, self-organization, and biological activity of the linear polyacetylenes and hyperbranched polyarylenes. The utilization of the advanced polymers and their interesting materials properties for high-tech innovations will be discussed.     

Design and synthesis of self-healing polymers

Self-healing polymers represent a class of materials with built-in capability of rehabilitating damages. The topic has attracted increasingly more attention in the past few years. The on-going research activities clearly indicate that self-healing polymeric materials turn out to be a typical multi-disciplinary area concerning polymer chemistry, organic synthesis, polymer physics, theoretical and experimental mechanics, processing, composites manufacturing, interfacial engineering, etc. The present article briefly reviews the achievements of the groups worldwide, and particularly the work carried out in our own laboratory towards strength recovery for structural applications. To ensure sufficient coverage, thermoplastics and thermosetting polymers, extrinsic and intrinsic self-healing, autonomic and non-autonomic healing approaches are included. Innovative routes that correlate materials chemistry to full capacity restoration are discussed for further development from bioinspired toward biomimetic repair.     

聚合物电致发光材料及其发光颜色调节的研究进展

聚合物电致发光材料已成为功能材料研究领域的一个热点.与无机材料和有机小分子材料相比,聚合物发光材料具有来源广泛、易加工成型、通过分子结构设计可调节发光颜色等优点,成为制备大面积、低成本、全色柔性显示器件的首选材料.本文介绍了聚合物发光材料的发光机理及调节发光颜色的常用方法,综述了聚对苯乙炔类、聚对苯类、聚芴类等多种共轭聚合物发光材料的合成及发光颜色调节的研究现状,并对聚合物发光材料的发展趋势以及聚合物电致发光器件的制备进行了评述和展望.     

Nanoporous thermosetting polymers

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.     

Plasma polymerization in the design of new materials: looking through the lens of maleic anhydride plasma polymers

Plasma polymerization is a well-established process for the deposition of thin polymeric films on various types of substrates. The potential of this technique for promoting changes of substrate’s wettability constitutes one of the most basic and often reported applications. However, as novel technological demands emerge, and with it the range of available characterizations, plasma polymers are having their niche of applications and properties expanded. The properties of these materials are commonly tailored through the variation of polymer chemistry, postfunctionalization, or other post-treatment processes. That chemical versatility allows the use of plasma polymers in adhesives, water treatment, biomedicine, and many other fields. The creation of nanostructures via lithography or during the deposition process itself constitutes other dynamic fields for new plasma polymer materials. In the current review, the design of materials through plasma polymerization is addressed with the direction given by our expertise in maleic anhydride plasma polymers (MAPP). A non-exhaustive number of applications of plasma polymers is provided to non-specialists as an overview of the materials coming out from the field of this chemical-vapor deposition process. A complete analysis of the literature on maleic anhydride plasma polymers is also performed.     

Novel chemistry of β-lactones anionic polymerization

Some examples of novel chemistry of lactones polymerization are presented. New evidences on β-lactones polymerization by akali metal alkoxides and, also unusual in organic chemistry, C-C bond scission in β-lactones polymerization induced by alkali metal supramolecular complexes are discussed. Preparation of functional polyesters and various block polymers exhibiting “tailored” properties are also described.     

Rational Design of Biomolecules/Polymer Hybrids by Reversible Deactivation Radical Polymerization (RDRP) for Biomedical Applications

Hybrids, produced by hybridization of proteins, peptides, DNA, and other new biomolecules with polymers, often have unique functional properties. These properties, such as biocompatibility, stability and specificity, lead to various smart biomaterials. This review mainly introduces biomolecule-polymer hybrid materials by reversible deactivation radical polymerization(RDRP), emphasizing reverse addition-fragmentation chain transfer(RAFT) polymerization, and nitroxide mediated polymerization(NMP)....     

Universal cyclic polymer templates

Two unique molecular templates for generating polymeric materials with a cyclic molecular architecture were developed by combining ring-expansion metathesis polymerization and click chemistry. These two universal cyclic polymers were used in three examples to demonstrate the wide range of potential materials enabled. They include functional cyclic polymers, cyclic polymer brushes, and cyclic gels.     

Narrowly-Distributed Conjugated Polymers Synthesized through Suzuki Polymerization with Palladium(II) N-Heterocyclic Carbene Complex Confined in Dendritic Mesoporous Silica Nanoparticles

A catalytic heterogenous Suzuki polymerization method was developed by confining the Pd(II)-catalyzed cross coupling reactions to take place exclusively in the nanochannels of dendritic mesoporous silica nanoparticles. Conjugated polymers with various monomer combinations, including donor-acceptor structures, were obtained in high yields. The molecular weights of the obtained polymers were well controlled with narrow molecular weight distributions (PDI value down to 1.13). All the polymeric products were highly soluble in common organic solvents, granting them with high processability. All the features of this confined Suzuki polymerization method endow the conjugated polymers great potential in optoelectronic applications.     

Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed.