烯烃易位聚合制备遥爪聚合物及嵌段共聚物

遥爪聚合物因其聚合物链的两端带有反应性官能团,可用于制备嵌段、接枝、星形、超支化等具有特殊结构的聚合物,其制备方法主要包括传统自由基聚合与可控/“活性”自由基聚合、阴离子聚合、阳离子聚合、易位聚合和缩合聚合等。相比于其他的传统聚合方法,烯烃易位聚合是一种较为温和的、产物分子量及结构可控的聚合方法。本文主要概述在各种链转移剂的存在下,采用环烯烃的开环易位聚合(ring-opening metathesis polymerization, ROMP)和非环二烯易位(acyclic diene metathesis, ADMET)聚合制备带有各种官能团的遥爪聚合物以及与其他活性聚合方法(NMRP、ATRP、RAFT、ROP等)相结合制备嵌段共聚物的研究进展。     

烯烃易位聚合研究新进展 在合成嵌段共聚物及功能高分子上的应用

本文详述了利用环烯烃开环易位聚合合成，ＡＢ，ＡＢＡ和星形嵌段共聚物，接枝共聚物，氧化还原性聚合物，侧链液晶高分子，导电高分子及含金属纳米聚合物材料，并对其具体合成线路作了概述。     

开环易位聚合聚双环戊二烯的合成及结构与性能的研究进展

开环易位聚合环烯烃已成为高分子工程领域的一个研究热点。其中,由于双环戊二烯（DCPD）价格低廉、来源充分、聚合后形成的聚双环戊二烯（PDCPD）具有优异的力学性能等优点,使得DCPD的开环易位聚合得到广泛关注。本文综述了DCPD开环易位聚合反应机理、催化体系、PDCPD的结构、PDCPD的表面改性、纳米共聚物以及PDC...     

开环易位聚合合成瓶刷聚合物

瓶刷聚合物是一类具有独特侧链结构的梳形聚合物。功能性瓶刷聚合物在光子晶体、表面活性剂、医药载体、防污涂层以及智能材料等领域具有良好的应用价值。通过开环易位聚合合成瓶刷聚合物的方法具有合成步骤简单、聚合物接枝密度高和侧链组成均一等优点,在控制聚合物组成、分子量和分散性等方面具有显著优势。本文基于开环易位聚合,简述了合成瓶刷均聚物以及嵌段型、混合型和核-壳型三种类型的瓶刷共聚物的方法,并介绍了合成精确结构的瓶刷聚合物的新进展。     

含咪唑离子盐的环辛烯在离子液体中开环易位聚合微观研究

用核磁共振方法研究了带电荷的环辛烯单体在离子液体和CDCl3中开环易位聚合反应的微观特征,根据单体在化学位移δ=5.66~5.58处双键氢积分峰面积的减少和聚合物主链上不饱和双键氢移至高场δ=5.38~5.39处峰面积积分的增加来表征聚合反应的情况.检测和记录了单体在有离子液体参与的条件下均相聚合反应和在CDCl3中的异相聚合反应过程,根据在不同反应体系中Grubbs第二代崔化剂中与Ru相连的苯亚甲基上氢在核磁图谱上δ=19.2处的峰型变化,探讨在两种介质中的不同聚合行为.研究表明,该单体在离子液体介质中的均相聚合有可控聚合的微观特点,并通过ln[M]0/[M]与反应时间的关系曲线,证实了反应的活性特征.     

环硅氧烷开环聚合研究进展

聚硅氧烷(如硅油、硅橡胶、硅树脂等)具有很多优异的性能,如耐高低温、耐紫外线辐射、耐候、低表面张力、电气绝缘、生理惰性等,已被广泛应用于航空航天、电子电器、化工、机械、建筑、交通、医疗卫生、农业等领域。聚硅氧烷制备方法主要有环硅氧烷开环聚合和硅氧烷缩聚。本文从环硅氧烷阴离子开环聚合、阳离子开环聚合和其它聚合方法等出发,较详细介绍了环硅氧烷开环聚合近年来的研究进展,并指出环硅氧烷开环聚合制备有机硅高分子材料所面临的问题。     

无环二烯烃易位聚合的研究进展

无环二烯烃易位聚合(ADMET)是烯烃复分解反应(OM)细分后的重要类别之一。ADMET基于Chauvin反应机理，利用金属卡宾络合物对碳碳双健进行重排。ADMET反应中能量驱动力不同于其他复分解反应，ADMET聚合可通过除去反应生成的乙烯控制，且多被用于生成有明确的主结构和主干取代物在精确位置的聚合物。本文综述了ADMET聚合的研究进展，包括Chauvin反应机理、钼基和钌基催化剂发展历程以及ADMET聚合演化、反应条件和应用。     

面向本科生教学的开环聚合内容拓展

开环聚合作为与缩聚、加聚并列的第三大类聚合反应,具有如下特点：基于环状单体的特殊性,开环聚合反应无副产物生成;聚合物组成与单体的元素组成相同,即具有100%的原子利用率;大部分开环聚合反应具有连锁反应特征,链增长速度快;形成的聚合物链中含有杂原子,所得材料具有降解可控性。本文总结了近年来在开环聚合研究上的一些进展,如γ-丁内酯的成功开环聚合、活性开环聚合、易位开环聚合等,为本科生《高分子化学》课程中的“开环聚合”一章内容的有益补充。通过提供额外的一些参考文献来拓展本科生对前沿知识的了解,开阔优秀本科生的国际学术视野。     

环烯烃聚合物的合成和应用研究进展

综述了近年来环烯烃均聚物及其与A2烯烃共聚物的合成和应用的研究情况, 讨论了不同聚合体系(包括开环易位聚合和加成聚合) 的研究发展, 对各种催化剂的结构、催化聚合的机理, 以及所得聚合物、共聚物性能进行了详尽的描述, 同时报道了有关聚合产物应用的现况与前景。     

环醚聚合化学与进展

本文综述了三元、四元及五元环醚单体的开环聚合机理(包括正、负离子及配位聚合)以及聚醚与共聚醚的制备与应用。     

活性开环歧化嵌段共聚合法合成聚合物的研究进展

综述了近年来利用活性开环歧化嵌段共聚合法合成聚合物的研究工作进展。     

活性开环歧化聚合合成梳形聚合物

综述了近年来利用活性开环歧化聚合反应合成规整结构梳形聚合物的研究工作进展。     

Latent Olefin Metathesis Catalysts for Polymerization of DCPD

Summary: Advances in design of latent ruthenium phenylindenylidene catalysts bearing salicylaldimine ligands for ring-opening metathesis polymerization are described. The presence of the substituents in ortho position in N-aryl ring of salicylaldimine ligand has been found to be the main factor determining the catalyst stability. The best of the studied catalysts after acid activation offers activity comparable to that of the dichloride systems in ring-opening metathesis polymerization of DCPD, while maintaining very high stability in the monomer solution.     

降冰片烯开环易位聚合反应的分子量及分子量分布控制

使用Grubbs催化剂催化降冰片烯单体进行开环易位聚合反应, 研究了催化剂搅拌溶解时间、聚合反应的溶剂极性和三苯基膦的加入等反应条件对降冰片烯单体ROMP反应分子量及分子量分布的影响, 从而得到降冰片烯ROMP反应的最佳条件.     

Ring‐Opening Metathesis Polymerization in Aqueous Media Using a Macroinitiator Approach

Water‐soluble and amphiphilic polymers are of great interest to industry and academia, as they can be used in applications such as biomaterials and drug delivery. Whilst ring‐opening metathesis polymerization (ROMP) is a fast and functional group tolerant methodology for the synthesis of a wide range of polymers, its full potential for the synthesis of water‐soluble polymers has yet to be realized. To address this, we report a general strategy for the synthesis of block copolymers in aqueous milieu using a commercially available ROMP catalyst and a macroinitiator approach. This allows for excellent control in the preparation of block copolymers in water. If the second monomer is chosen such that it forms a water‐insoluble polymer, polymerization‐induced self‐assembly (PISA) occurs and a variety of self‐assembled nano‐object morphologies can be accessed.     

Photoinduced Strain-Assisted Synthesis of a Stiff-Stilbene Polymer by Ring-Opening Metathesis Polymerization

Developing a novel strategy to synthesize photoresponsive polymers is of significance owing to their potential applications. We report a photoinduced strain-assisted synthesis of main-chain stiff-stilbene polymers by using ring-opening metathesis polymerization (ROMP), activating a macrocyclic π-bond connected to a stiff-stilbene photoswitch through a linker. Since the linker acts as an external constraint, the photoisomerization to the E-form leads to the stiff-stilbene being strained and thus reactive to ROMP. The photoisomerization of Z-form to E-form was investigated using time-dependent NMR studies and UV/Vis spectroscopy. The DFT calculation showed that the E-form was less stable due to a lack of planarity. By the internal strain developed due to the linker constraint through photoisomerization, the E-form underwent ROMP by a second generation Grubbs catalyst. In contrast, Z-form did not undergo polymerization under similar conditions. The MALDI-TOF spectrum of E-form after polymerization showed the presence of oligomers of >5.2 kDa.     

ADMET: Metathesis polycondensation

Although it is well known that Acyclic Diene METathesis (ADMET) describes an olefin metathesis polymerization mode that relies on double‐bond substituent interchange of a diolefin, the story behind its discovery is not. The story is divulged here. Olefin metathesis has a rich history dating to the 1950s, but the one particular metathesis mode mentioned, ADMET, has more recent historical roots. ADMET polymerization is easy to do and highlighted here are the particular reaction details for success. Additionally, the most recent advances from the past 5 years are detailed, exemplifying this reaction's wide utility from fundamental structure–property studies to multiple advanced applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

端炔丙基化合物的聚合反应研究进展

端炔丙基化合物的聚合产物以其优异电导性,非线性光学特性等性能而引起人们的广泛兴趣,本文了近年来端炔丙基化合物的氧化聚合、易位聚合、自由基聚合、缩聚等聚合的研究进展。     

Bulk Metathesis Polymerization of Cyclooctene

The bulk ring-opening metathesis polymerization (ROMP) of cyclooctene initiated with the WCI₆/Sn(CH₃)₄ catalytic system was investigated at 40, 100, and 160°C using high vacuum techniques. The polymerizations were followed over a period of several days. Detailed analyses of the polymerization products by gel permeation chromatography (GPC) and ¹H and ¹³C NMR were carried out. Along with unsaturated high molecular weight (HMW) polymer (polyoctenamer), low molecular weight (LMW) polymer was found, the proportion of the latter increasing with time. The LMW fraction contains saturated LMW polymer together with ring polymer. The results are explained in terms of kinetic and thermody-namic arguments.