含二茂铁基聚合物的合成及应用研究进展

二茂铁基聚合物由于具有独特的结构特点,使其在电化学、催化、材料等方面受到了广泛的关注.二茂铁聚合物的种类较多且合成方法多种多样.本文综述了近年来含二茂铁基聚合物的合成及应用.从缩聚、开环聚合和接枝共聚等方面介绍了近年来二茂铁基聚合物的合成方法,讨论了二茂铁基聚合物在电化学、生物材料及其他方面的应用.最后,对二茂铁基聚合...     

二茂铁基聚合物超分子体系构建和性能的研究进展

二茂铁基聚合物具有独特的氧化还原、电、磁等性能，其构建成超分子体系后在传感器、催化、分子电子学、生物和医学等领域有着广泛的应用前景。本文综述二茂铁基线型聚合物和二茂铁基树枝状聚合物的超分子体系构建和性能方面的研究进展，并对今后的发展方面作一展望。     

主链或侧链含二茂铁的聚合物的合成和应用

由于二茂铁基聚合物独特的结构和性能,其在电化学、生物医学及光学等领域具有广阔应用前景。开发新型二茂铁基聚合物并探索其应用已经成为科研工作者的研究热点。本文主要综述主链或侧链含二茂铁的聚合物的合成及应用。其中合成主链含二茂铁的聚合物的方法主要有缩聚法和开环聚合法等。合成侧链含二茂铁的聚合物的方法主要有自由基聚合法、原子转移自由基聚合法和可逆加成断裂链转移聚合法等。最后,对二茂铁基聚合物的应用前景进行了展望。     

全共轭型二茂铁基聚合物

由于二茂铁独特的夹心结构使含二茂铁基聚合物具有独特的电、磁、催化以及氧化还原性能。全共轭型二茂铁基聚合物由于其特殊的π-π电子结构,使其在电学、光学等方面的表现出优越的性质。本文从3个方面（主链型、侧链型和超支化型）介绍了近年来含有二茂铁基团全共轭聚合物的合成及其性能方面的研究进展,讨论了聚合物的结构对溶解性、氧化还原性等方面的影响,并探讨了这一领域存在的问题及可能的发展方向。     

二茂铁基环氧衍生物

二茂铁基环氧的分子结构中同时含有环氧和二茂铁,是一类兼具化学活性和多功能性的特殊材料。这类材料具有单体结构多样性和聚合物的多功能性,近年来对其制备方法和应用的研究受到广泛关注。研究者们已利用二茂铁醛、酮、烯、氯醇、双醇、乙酰氯等为中间体,制备出二十多种小分子化合物。采用二茂铁接枝环氧聚合物或含烯单体自由基聚合,分别得到多种结构的聚合物。本文在综述二茂铁基环氧制备方法的基础上,进一步讨论了这类材料的结构稳定性。研究发现,当二茂铁处于环氧的邻位时,极易形成卡宾结构,使得环氧开环并重排成醛。通过列举典型研究实例,阐明其在功能材料、传感介质、燃速催化、催化剂配体以及药物合成等方面的应用,并就其在材料表界面的发展趋势进行了展望。     

基于环糊精的高度支化聚合物*

环糊精（CD）与高度支化聚合物都存在空腔结构,若将两者结合起来可构筑出含有两种不同疏水空腔且具有特异物理化学功能的高分子体系,并有望在分子包合与识别、药物控释、基因传输等领域得到新的应用。本文根据高度支化聚合物与环糊精结合方式的不同,从以环糊精为核的高度支化聚合物、外端悬挂环糊精的高度支化聚合物、高度支化聚合物的结构单元与环糊精包合、环糊精与客体分子包合后自组装成高度支化聚合物,以及用功能化的环糊精单体合成超支化聚合物等5个方面对其研究进展进行了总结和评述,并在此基础上展望了该类聚合物的研究方向和发展趋势。     

超支化聚合物制备方法的研究进展

超支化聚合物是一类可以通过一步法来合成的具有高度支化结构的体型大分子.经过二十年的研究,超支化聚合物由于其独特的结构和性能特点以及可实现规模化生产的特点, 已经迅速成为一类重要的和具有广阔应用潜力的高分子材料.本文从单体类型的角度介绍了超支化聚合物的主要制备方法及其发展历程,主要涉及ABx型,AB*型,A2 B3型以及潜在ABx型单体(包括开环聚合和偶合单体法)等,同时论述了各制备方法的优点和局限性 .     

超支化/星形聚合物电解质的研究进展

与液体电解质相比较,聚合物电解质以其易加工、设计灵活、质量轻、安全无毒的特点而受到人们的广泛关注,具有取代液态电解质的潜在应用价值,而超支化/星形聚合物以其无定形、低玻璃化转变温度、支化结构等特点可被用于固态电解质。本文综述了超支化/星形聚合物电解质材料的研究进展,重点介绍了超支化/星形聚合物基电解质和超支化/星形聚合物共混基电解质,并对超支化/星形聚合物单一离子导体在锂离子电池方面的应用前景作了概述。     

爆炸物检测用荧光聚合物材料

作为荧光传感材料,荧光聚合物不仅具有传感单元多、荧光亮度高、光稳定性好等特点,而且方便制备荧光传感薄膜,易于实现器件化,在爆炸物荧光检测中得到了广泛的研究与应用。近年来,随着荧光聚合物从传统的线型结构向支化和多孔网络结构的拓展,以及各种功能单元的引入,大量的新型荧光聚合物有效地提升了爆炸物检测的灵敏度、选择性和响应速度等性能。本综述从线型聚合物、支化聚合物、多孔聚合物三类体系出发,总结和评述了用于爆炸物荧光检测的线型共轭与非共轭聚合物、树枝状分子与超支化聚合物、无定形与结晶型多孔聚合物等典型体系的分子结构设计策略、功能特点以及传感性能,并展望了荧光聚合物未来在爆炸物检测应用中所面临的机遇和挑战。     

原子转移自由基法合成4-(4′-甲氧基苯基甲亚胺)苯酚功能化的六臂星型聚苯乙烯

星型聚合物由于其独特的构型及其粘弹性能使其可能在交联剂,离子交换聚合物,表面活性剂,增容剂,热塑性弹性体等方面得到广泛的应用.星型聚合物按其链结构可以分为,星型(嵌段)聚合物[1],星型-支化聚合物[2],星型-梳状聚合物[3].星型聚合物的合成始于20世纪50年代活性负离子聚合[     

含二茂铁基树枝状化合物研究进展

综述了近年来含二茂铁基树枝状化合物的合成进展, 并讨论了其结构对二茂铁基电化学性质的影响, 展望了此类化合物良好的应用前景.     

Modeling highly branched structures: Description of the solution structures of dendrimers,polyglycerol, and glycogen

We show that Random Branching Theory (RBT) accurately describes the structures of various synthetic and natural highly branched polymers in solution. We test the theory against data taken from the literature, including radii of gyration of glycogen, hyperbranched polyglycerols, and polyamidoamine dendrimers and the small‐angle X‐ray scattering profiles of these same dendrimers. In particular, all these polymers can be described adequately by sequentially branching units, packed together in a random close packing arrangement. Combined with previous tests against experiments and computer simulations, the evidence presented here shows that RBT is a simple, but surprisingly useful, theory of highly branched polymers' solution structure. We suggest that it is sufficiently powerful to be useful in the design of new polymers. Our most surprising conclusion is that random attachment of component parts produces a good model of regularly branched polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1525–1538, 2011     

结构规整支化聚合物的制备方法

结构规整支化聚合物可以通过主链引发法，大分子单体聚合法和主链－支链偶联法来合成，对结构较为规整的支化聚合物的制备进行总结和评述。     

双烯化合物类单体合成支化聚合物的支化结构的研究

分别以二乙烯基苯(DVB)、双甲基丙烯酸二缩三乙二醇酯(tri-EGDMA)和1,6-双马来酰亚胺基正己烷(BMIH)为支化单体,采用原子转移自由基聚合合成支化聚苯乙烯;以先核后臂法合成的星状支化聚苯乙烯为参照对合成的支化聚合物的支化形态进行研究.采用气相色谱(GC)、核磁共振氢谱(1H-NMR)和三检测凝胶渗透色谱(TD-SEC)测定了苯乙烯的转化率,聚合物分子量及其分布,特性黏数和均方回转半径.实验结果表明3个支化聚合反应体系内悬垂双键是逐步消耗的,不存在明显的成核过程.反应前期,以形成带有悬垂双键的初级链和轻度支化聚合物为主,聚合物分子量随单体转化率逐步上升;反应后期,悬垂双键聚合导致的分子之间的偶合更加明显,使得聚合物分子量快速上升,合成得到的都是无规支化聚合物.     

Radical alternating copolymerization: A strategy for hyperbranched materials

Novel hyperbranched polymers were synthesized in a high yield without gelation through the free‐radical alternating copolymerization of an AB/B′ (allyloxy maleic acid/maleic anhydride) system, in which group B and monomer B′ both could only alternately polymerize with group A. The arm number of the produced highly branched polymers was equal to the product of the linear chain length and the probability of pendent B groups being growing centers. The molecular weight of these novel hyperbranched polymers increased with increasing initiator concentration and prolonged polymerization times. The AB/B′ system, used as described, provides a new general methodology for highly branched and functional polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3074–3085, 2000     

A personal journey on using polymerization in aqueous dispersed media to synthesize polymers with branched structures

This short review is dedicated to celebrate Prof.Shoukuan Fu's 80 th birthday by discussing several of my accomplished projects over the past twenty years,which all applied radical polymerization in aqueous dispersed media for producing polymers with branched structures.These projects include the use of microemulsion polymerization for syntheses of fluorescent nanoparticles,hairy nanoparticles and hyperbranched polymers;the use of miniemulsion polymerization for synthesis of star polymers and light-emitting nanoparticles;the use of seeded emulsion polymerization for synthesis of hairy nanoparticles and hyperstar polymers;and the use of precipitation polymerization for synthesis of hollow polymer nanocapsules.Discussion of these projects demonstrates intriguing features of polymerization in biphasic dispersed media via either conventional radical polymerization or controlled radical polymerization to effectively regulate the branched structure of functional polymers.     

A personal journey on using polymerization in aqueous dispersed media to synthesize polymers with branched structures

Several projects were discussed to demonstrate the intriguing power of radical polymerization in aqueous dispersed media to regulate the branched structures in functional polymeric nanomaterials.     

Combining Living Anionic Polymerization with Branching Reactions in an Iterative Fashion to Design Branched Polymers

This paper reviews the precise synthesis of many‐armed and multi‐compositional star‐branched polymers, exact graft (co)polymers, and structurally well‐defined dendrimer‐like star‐branched polymers, which are synthetically difficult, by a commonly‐featured iterative methodology combining living anionic polymerization with branched reactions to design branched polymers. The methodology basically involves only two synthetic steps; (a) preparation of a polymeric building block corresponding to each branched polymer and (b) connection of the resulting building unit to another unit. The synthetic steps were repeated in a stepwise fashion several times to successively synthesize a series of well‐defined target branched polymers.

     

Precise synthesis of well‐defined dendrimer‐like star‐branched polymers by iterative methodology based on living anionic polymerization

Dendrimer‐like star‐branched polymers recently developed as a new class of hyperbranched polymers, which resemble well‐known dendrimers in branched architecture, but comprise polymer chains between junctions, are reviewed in this highlight article. In particular, we focus on the precise synthesis of various dendrimer‐like star‐branched polymers and block copolymers by the recently developed methodology based on iterative divergent approach using living anionic polymers and 1,1‐bis(3‐tert‐butyldimethylsilyloxymethylphenyl)ethylene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6659–6687, 2006     

Nanoscale structure–property relationships in conjugated polymers: Implications for present and future device applications

The most prevalent molecular level structures and structure–property relationships for three basic classes of conjugated polymers are summarized. This discussion encompasses linear unsubstituted conducting polymers and those containing linear side‐chain and branched side‐chain substituents. The impact of these structural attributes on charge transport and photophysics is emphasized. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2630–2648, 2003