两步转化法合成聚苯乙烯亚磺酸钠树脂

聚合物载体的合成一直是固相有机合成和组合化学领域研究的重要课题之一。聚苯乙烯亚磺酸盐树脂具有离子交换性能和一定的亲核性能，可以通过亲核反应制得一系列带砜基侧链基团的聚合物。由于砜基具有独特的化学性质,它既是一种强极性基团，又有     

有机硅改性有机合成树脂的研究状况

有机硅聚合物具有优异的耐候性、耐玷污性和耐高低温性,高度的疏水性,良好的透气性等被广泛应用.各种有机合成树脂有各自的优点和缺点,它们的缺点正好是有机硅聚合物的优点.将有机硅引入有机合成树脂,利用有机硅优点改进有机合成树脂的不足,使有机硅和有机合成树脂的性能更加完善,这对有机硅和有机合成树脂工业发展具有重大的意义.因此有机硅改性有机树脂是近年来研究的热点.本文简单综述了几种有机硅化学改性有机合成树脂的性能特点、制备方法及研究发展状况.     

微波辅助固相有机反应

固相有机合成是组合化学中构建化合物库的主要工具之一［１,２］,但是,由于它是连接在固相载体（如树脂等）上的试剂与溶解在有机溶剂中的试剂之间的反应,因此反应比较缓慢．考虑到微波技术对有机反应的协助作用,我们将微波技术应用到固相有机反应中,对比研究了微波...     

功能基化聚合物作为高分子试剂在固相有机合成中的应用研究

本文讨论了作者近年在制备功能基化聚合物方面的新方法,所制得的功能基化聚合物和工业离子交换树脂作为高分子载体,试剂和相转移催化剂在固相有机合成中的应用性能,以及功能基结构,反应介质,温度对固相合成反应的影响。     

固相载体上的环加成反应及其应用

固相有机合成和组合化学是近年来发展起来的快速合成数种有机化合物的新方法。本文介绍了在固相载体上进行的环加成反应, 及其在有机合成及反应机理研究中的应用。     

利用离子液体负载反应底物的有机合成

综述了固相、液相组合化学中以可溶性离子液体为载体的有机合成新概念及最新研究进展,并主要介绍了离子液体作为载体负载反应底物在有机合成中的一些应用,如有关的重要有机反应、组合化学、小分子库合成等。该方法具有上载率高、适用反应范围宽、分离纯化简便、结构检测容易和可回收重复使用等诸多优越性,这对于传统的固相、液相合成方法是一个重大的进步。     

聚合物假冠醚研究(Ⅴ)多胺型类氮杂冠醚聚合物的合成与性能及在化学实验室的应用

以聚乙二醇(PEG400,PEG200)为起始剂,以多乙烯多胺为交联剂,合成了4种新型多胺交联型类氮杂冠醚聚合物,研究了聚合物的溶胀性能和对金属离子的静态吸附性能.结果表明,聚合物在极性溶剂中具有良好的溶胀性能,在水中的溶胀系数达12.67,吸水容量达12.14g/g(20℃);在25℃下,对Cu2+,Ni2+,Hg2+,Pb2+的吸附量分别达1.793mmol/g,1.675mmol/g,1.849mmol/g和1.048mmol/g.测试了反应物摩尔比、溶剂温度及其pH值对溶胀性能的影响,试研究了聚合物在化学实验室的应用.     

新型阻溶促溶酚树脂用于热敏CTP版的性能研究

使酚树脂与乙烯基醚发生反应,合成出一种新型醚化物,作为新型阻溶促溶剂.将它与产酸剂、背景染料、红外染料、成膜树脂、其它助剂及有机溶剂作为热敏CTP组合物.研究了该热敏CTP组合物的化学性能和热敏成像性能,发现在热敏CTP组合物中适量的新型阻溶促溶剂能够使热敏CTP版的热敏性、显影性、抗碱性及耐异丙醇性都得到了较大的改善.     

聚合物支载氧化剂研究新进展

随着高分化学研究的深入,聚合物的应用范围越来越广。聚合物已用作催化剂、氧化剂、功能试剂等。本文综述自1989年以来聚合物支载氧化剂研究的新进展及在有机合成中的应用。     

有机合成中聚合物试剂的应用

聚合物作为材料早就应用在工业中,至于其化学反应直到五十年代还研究得比较少,而最近十年来聚合物试剂作为新方法应用于有机合成中颇有发展。“聚合物试剂”是以聚合物作为较低分子量试剂的载体,在合适的溶剂中使聚合物试剂与溶解的作用物反应。根据不同的情况反应产物或是溶解在溶液中,或是与聚合物相结合。如为后一种情况,则需将产物从聚合物上断裂下来。     

PEG-related polymer resins as synthetic supports

Combinatorial chemistry has become a significant part of the discovery and optimization process for novel drugs, affinity ligands, and catalysts. The polymeric supports play a key role in combinatory chemistry. Therefore, various kinds of functional polymer resins have been exploited as supports, reagents, and catalysts in organic synthesis. In comparison to the conventional Merrifield resins, the poly(ethylene glycol) (PEG)-related polymer resins have advantages including good compatibilities with polar solvents, good solvent absorbency and swelling properties. This review focuses primarily on the more recent work in the field of developing PEG-related polymer resins as supports for organic synthesis.     

Synthesis, characterization and evaluation of sulfonic resins as catalysts

Ion-exchange resins have been often used as catalysts especially those based on styrene-divinylbenzene copolymers with sulfonic acid groups in the aromatic rings of polymer chains. That is due to the advantages of heterogenous catalysis over the homogeneous acid catalysis. Moreover, resin catalysts can often lead to high selectivity in organic reactions due to the matrix effects. Therefore, the study of copolymers synthesis conditions to determine the type of polymer structure produced as well as the characterization of sulfonic resins obtained thereof are of great interest. The current paper describes the synthesis, characterization and evaluation as catalysts of sulfonic resins derived from polymer supports synthesized by aqueous suspension polymerization of styrene and divinylbenzene. The reaction conditions were varied and polymer supports with different physical properties and morphological characteristics were obtained. The polymer supports were chemically modified by sulfonation. The resultant sulfonic resins had their catalyst activity evaluated in the esterification of acetic acid with n-butanol.     

Dendrimers and hyperbranched polymers as high-loading supports for organic synthesis

Polymeric supports have become a big necessity for automated synthesis and combinatorial chemistry, yet, the loading capacities of most polystyrene resins are very limited (typically < 1.5 mmol x g(-1)). Dendrimers and hyperbranched polymers have been discussed for this application and now became readily available. These soluble polymers can either be used directly as high-loading supports for substrates, reagents, and catalysts or alternatively in hybrid polymers linked to conventional polystyrene resins.     

Synthesis and evaluation of poly(oxyethylene glycol) polymer (POP) supports

Mono- and alpha,omega-bis-styryl-oligo(oxyethylene glycol) ethers have been constructed in an efficient two-step synthesis. From these precursors, poly(oxyethylene glycol) polymer (POP) supports of varying monomer and cross-linker composition have been produced. The swelling properties and mass-solvent uptake of these novel materials have been evaluated in a variety of solvents, demonstrating that POP supports exhibit enhanced solvent compatibilities over the commercial resins TENTA-GEL, ARGO-GEL, and Merrifield's resin. The utility of POP supports in solid-phase organic chemistry has also been demonstrated successfully. It is anticipated that these high-loading polymeric supports will have generic application in the solid-phase synthesis of combinatorial libraries and the in situ screening of these libraries in the aqueous environment of a bioassay.     

固相合成及组合化学用的高聚物载体

综述了用于固相合成及组合化学的高聚物载体的制备方法、特征、应用和最新进展,重点介绍了目前广泛用作固相载体的交联聚苯乙烯树脂、聚酰胺树脂和TentaGel树脂,并对几类新型载体如聚乙二醇、聚四氢呋喃衍生物交联剂改性的聚苯乙烯树脂、非芳环体系的POEPOP,树脂和SPOCC树脂作了简要的概述。     

Polymer‐supported reagents,catalysts, and sorbents: Evolution and exploitation—A personalized view

The solid‐phase method for oligopeptide synthesis was introduced by Professor Bruce Merrifield in 1963, but in practice the origins of polymer‐supported reagents, catalysts, and so forth trace back to the early development of ion exchange and catalysis by sulfonic acid resins. This highlight summarizes how the evolution of solid‐phase organic synthesis occurred in parallel with the development of supported reactive species and indicates the interchange between these areas in the last 30 years or so. The treatment is essentially a personalized one as seen from the author's own laboratory in the United Kingdom and is not intended to review the whole field. The emergence of the international series of conferences on polymer‐supported organic chemistry is emphasized as a key development that stimulated and maintained the area before its importance was recognized more widely by both academic and industrial chemists. The requirement of robotic technologies, as the basis for high‐throughput combinatorial and parallel synthesis in the pharmaceutical industry, has brought the relevance of supported chemistry to the attention of all synthetic chemists. At the same time, the recognition that all industrial chemical processes need to meet appropriate environmental standards has focused attention on the use of heterogenized reactive species as a potentially important technology for achieving the greening of chemistry. These two factors have brought polymer‐supported reactive chemistry to center stage, so to speak, and the early principles laid down over 2 decades ago are now being developed and exploited at an amazing rate. From a rather slow start, through a number of ups and downs in its development, the area of polymer‐supported chemistry now seems poised to join the more routine world of synthesis and to become a methodology used by all as and when appropriate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2364–2377, 2001     

高分子支载手性催化剂在Michael反应中的研究进展

高分子手性催化剂用于不对称有机合成,它易与产物分离、可通过适当的处理后回收重复使用;具有毒性或气味的手性催化剂支载在高分子上后,使用更加安全和方便;而且,适当结构的高分子聚合物可以为不对称反应提供更有利的微环境,提高立体选择性.正是这些优点,高分子手性催化剂的研究越来越受到人们的关注.不对称Michael反应是形成手性碳-碳、碳-杂键的重要反应,在有机合成和药物合成中起着重要的作用.本文综述了近年来的高分子手性催化剂在Michael反应中的应用及最新进展.     

Using polymers to control substrate,ligand, or catalyst solubility

The attributes and design of soluble polymer supports for catalysis and synthesis are discussed. By manipulating polymer structure, polymer supports can be prepared so that the solubility of an attached reagent, substrate, or ligand is affected by heating, cooling, pH, or solvent identity. Supports with such engineered solubility are useful both in organic synthesis and catalysis. They can be used as purification handles in organic synthesis as a way to recover catalysts, as a way to turn reactions on or off, and more generally, as a handle for separations. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2351–2363, 2001     

Crown Ethers and Phase Transfer Catalysis in Polymer Chemistry

Abstract

This paper is the first half of a two part review on the applications of crown ethers, cryptands, glymes and various onium ion salts to polymer chemistry. Part 1 surveys the use of these phase transfer catalysts (PTC's) in the synthesis and modification of macromolecules. Applications to ring-opening and vinyl polymerizations generally have involved solubilization and activation by PTC's of organic and inorganic salts which serve as anionic initiators. Change in the polymerization rates, polymer yields and product microstructure often resulted from association of the PTC with the active chain end.

Polymer modification and functionalization reactions have been enhanced by the use of PTC's. Macromolecular substrates have included both soluble and insoluble polymers, although the most popular have been the readily-available Merrifield resins. Generally these two-phase reactions have involved polymer solutions interacting with insoluble reagents or insoluble polymers reacting with the reagent solution. Some of the groups incorporated have been thiols, nitriles, carboxylic acids, esters, and crown ether analogs themselves. Most of this work has aimed at synthesis of polymer derivatives which can serve as chelating agents, catalysts and reagents in subsequent reactions. In almost all cases described, phase transfer catalysis offers definate advantages in selectivity and yield over conventional methods. The outline below gives the general subject areas of both Part 1 and Part 2; the latter will be published shortly.     

Synthesis and reactions of N-heterocyclic carbene boranes

Boranes are widely used Lewis acids and N-heterocyclic carbenes (NHCs) are popular Lewis bases, so it is remarkable how little was known about their derived complexes until recently. NHC-boranes are typically readily accessible and many are so stable that they can be treated like organic compounds rather than complexes. They do not exhibit "borane chemistry", but instead are proving to have a rich chemistry of their own as reactants, as reagents, as initiators, and as catalysts. They have significant potential for use in organic synthesis and in polymer chemistry. They can be used to easily make unusual complexes with a broad spectrum of functional groups not usually seen in organoboron chemistry. Many of their reactions occur through new classes of reactive intermediates including borenium cations, boryl radicals, and even boryl anions. This Review provides comprehensive coverage of the synthesis, characterization, and reactions of NHC-boranes.