原子转移自由基聚合研究进展

原子转移自由基聚合(ATRP)反应是实现活性聚合的一种颇为有效的途径,可以合成分子量可控、分子量分布窄的各种聚合物.介绍了ATRP的研究进展,包括ATRP反应的特点、聚合反应机理、应用、研究现状及前景展望.     

原子转移自由基聚合进展

综述了原子转移自由基聚合(ATRP)的发展：引发剂、过渡金属络合物的发展,低温下的反应可节省能源,水分散体系的ATRP也是发展的方向ATRP可合成结构清晰的嵌段、接枝、星型、超支化高聚物,大大拓宽了高聚物的应用范围。     

原子转移自由基聚合的近期研究进展

对原子转移自由基聚合(ATRP)的引发体系、催化体系及反应介质进行了全面的综述。介绍了四种不同催化剂脱除技术;结合最新的研究成果,介绍了ATRP在进行聚合物分子设计尤其是在制备嵌段共聚物方面的进展。     

原子转移自由基聚合体系中催化剂的脱除

采用甲苯为溶剂,酸性三氧化二铝为吸附剂脱除原子转移自由基聚合体系中的含铜催化剂,ICP AES表征铜的含量可降至10-6级。研究了两种催化剂CuCl/bpy和CuCl/dNbpy对苯乙烯和甲基丙烯酸丁酯的原子转移自由基本体和乳液聚合的催化及脱除, 结果表明:虽然CuCl/dNbpy对聚合反应具有较好的催化活性,但由于与聚合物具有较好的相溶性,使得催化剂较难从体系中脱除,脱除效果次于 CuCl/bpy。而乳液聚合,由于体系的复杂性,使其在吸附剂脱除之后聚合物中的铜含量高于本体聚合。     

苯乙烯-丙烯腈原子转移自由基聚合

采用四氯化碳为引发剂,三氯化铁与丁二酸复合物为催化剂,在N,N-二甲基甲酰胺溶剂中对苯乙烯、丙烯腈进行原子转移自由基共聚合。研究了苯乙烯和丙烯腈物质的量比、引发剂用量、反应时间、温度等工艺条件对共聚物收率的影响。得到最佳反应条件：原料配比n（苯乙烯）：n（丙烯腈）为3：1;引发剂用量为12．5mL,三氯化铁与丁二酸复合催发剂的量分别为0．2865g,0．1180g;反应温度为90％,反应时间48h。     

原子转移自由基聚合研究进展

综述了原子转移自由基聚合的研究进展。     

原子转移自由基聚合最新研究进展

活性聚合具有无终止、无转移、引发速率远远大于链增长速率等特点,是实现分子设计、合成具有特定结构和性能聚合物的重要手段。但常用的活性聚合方法如阴离子聚合、阳离子聚合、基团转移聚合等反应条件比较苛刻、适用单体较少,从而限制了它们的广泛应用。与之相对,自由基聚合具有反应条件温和、适用单体广泛、合成工艺多样、操作简便、工业化成本低等优点。     

活性自由基聚合的分类及原子转移自由基聚合的研究进展

阐述了活性自由基聚合的产生背景和基本概念,介绍了活性自由基聚合的分类,描述了原子转移自由基聚合的研究进展。     

原子转移自由基聚合反应机理及其应用

概述了有关原子转移自由基聚合(ATRP)的反应机理.研究成果表明,应用ATRP法进行聚合反应可以制备窄分子量分布的聚合物、嵌段共聚物、接技聚合物、无规共聚物、星型聚合物等.ATRP在聚合反应领域具有非常广阔的应用前景.     

原子转移自由基聚合法（ATRP）制备聚丙烯酰胺

以苄基氯为引发剂,氯化亚铁为催化剂,三苯基膦为配体研究了丙烯酰胺在N,N-二甲基甲酰胺中的原子转移自由基聚合,考察了聚合时间、催化剂与配体的摩尔配比、温度等因素对单体转化率、分子量的影响。结果表明：80℃下,[AM]/[C6H5CH2Cl]/[FeCl2]/[PPh3]=100/1/0.5/1时,聚丙烯酰胺分子量随单体转化率增加线性增大,ln[[MM]]0与聚合时间呈线性关系,温度对聚合特征有较大影响。     

Preparation of Carborane-Containing Polymers by Atom Transfer Radical Polymerization

A para-carborane functionalized acrylate monomer was prepared and utilized in atom transfer radical polymerizations to produce carborane-loaded linear polymers. Copolymerization with a poly(ethylene glycol) monomethyl ether methacrylate (MPEGMA) allowed for the preparation of a water-soluble random copolymer having a boron content of 7.4%. In addition, a homopolymer of the carborane acrylate monomer was utilized as a macroinitiator to produce a block copolymer where the second block consisted of MPEGMA units. Each of the resulting polymer structures was irradiated with thermal neutrons to observe boron neutron capture events occurring within the boron-loaded polymers. The characteristic gamma radiation that signifies neutron capture events was observed at ∼480 keV.     

Copper Removal in Atom Transfer Radical Polymerization through Electrodeposition

Summary: We describe the removal of copper from atom transfer radical polymerization (ATRP) through electrochemistry. tert‐Butyl methacrylate ATRP initiated by a PEO macroinitiator was run with CuBr complexed by N‐alkyl‐2‐pyridylmethanimine (Schiff base) or 2,2′‐bipyridyl (bpy) as catalyst. Voltammetry experiments using a CuBr/(Schiff base N‐morpholine‐2‐pyridylmethanimine)₂ complex on a Pt electrode shows an oxidation peak of the ligand at 1.2 V permitting the oxidative destruction of the complex and so the elimination of copper. Using a Hg electrode, it is possible to directly reduce these complexes (at ?2.1 V for the morpholine‐2‐pyridylmethanimine, ?2.19 V for the butyl‐2‐pyridylmethanimine, and ?2.25 V for the bpy). This complex reduction, followed by the formation of a copper amalgam, leads to the quantitative removal of copper and proceeds without polymer degradation.

The electrochemical removal of copper from the ATRP reaction.     

Thermosensitive Nanocables Prepared by Surface-Initiated Atom Transfer Radical Polymerization

Thermosensitive nanocables consisting of Au nanowire cores and poly(N-isopropylacrylamide) sheaths (denoted as Au/PNIPAAm) were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP). The formation of PNIPAAm sheath was verified by Fourier transform infrared (FTIR) and hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy. Transmission electron microscope (TEM) results confirmed the core/shell structure of nanohybrids. The thickness and density of PNIPAAm sheaths can be adjusted by controlling the amount of cross-linker during the polymerization. Signature temperature response was observed from Au/cross-linked-PNIPAAm nanocables. Such smart nanocables show immense potentials as building blocks for novel thermosensitive nanodevices in future.     

Atom Transfer Radical Polymerization: From Mechanisms to Applications

Atom transfer radical polymerization (ATRP) is currently one of the most often used synthetic polymerization methods to prepare well-defined polymers with complex architecture. This review covers some fundamentals of copper-based ATRP, presents basic structure–reactivity correlation for initiators and catalyst complexes and discusses the radical nature of reactive intermediates. New ATRP initiating processes with ppm amounts of copper catalysts and various reducing agents are described together with recent electrochemically controlled ATRP and polymerization in aqueous homogeneous and dispersed media. Examples of polymers with precisely controlled architecture are presented together with the effect of variable amounts of catalysts on molecular weight distribution and morphology of nanostructured block copolymers. Some current and forthcoming applications of polymers made by ATRP are presented.     

水分散体系中原子转移自由基聚合研究进展

水分散体系中原子转移自由基聚合(ATRP)具有自由基聚合、乳液聚合和活性/可控聚合的优点,因此近年来关于水分散体系中ATRP的研究日益增多。本文综述了近年来水分散体系(包括乳液体系、细乳液体系、微乳液体系)中原子转移自由基聚合的研究进展,对应用在水分散体系中的几种ATRP反应机理做了简要介绍,包括正向AT-RP、反向ATRP(RATRP)、正向/反向同时进行的(SR&NI)ATRP、电子转移活化剂(AGET)ATRP,并对RATRP、SR&NI、ATRPAGET ATRP的优缺点进行了总结。     

借助ATRP法合成星型多臂氯甲基苯乙烯甲基丙烯酸甲酯共聚物

以对氯甲基苯乙烯(CMS)作为活性单体,CuCl/2,2’-联吡啶(bpy)为催化体系,用原子转移自由基聚合(ATRP)法,在120℃下,通过改变n(CuCl):n(CMS)配比,合成具有不同支化度的超支化聚对氯甲基苯乙烯(h-PC MS),分别考察了催化剂与单体的配比、溶剂极性、用量等因素对所合成的h-PCMS的组成结构、相对分子质量分布指数和转化率的影响.再分别以具有不同支化度的h-PCMS作为大分子引发剂,引发第二单体甲基丙烯酸甲酯(MMA)聚合,制得以超支化大分子h-PCMS为核,以聚甲基丙烯酸甲酯(PMMA)为臂的星型多臂共聚物h-PCMS-b-PMMA.借助红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)等技术对所制得的聚合物进行表征.本研究的特点是运用先核后臂的方法来合成具有精确分子结构参数的星型多臂共聚物,为进一步深入研究其结构与性能的关系提供了物质依据,更重要的是提供了合成具有复杂但结构可控的多元共聚物的新思路.     

Reverse Atom Transfer Radical Polymerization of MMA Initiated by Triphenylmethane

Summary Triphenylmethane (TPM) was successfully employed for the reverse atom transfer radical polymerization (RATRP) of methyl methacrylate (MMA) in the presence of CuCl₂/pentamethyldiethylenetriamine (PMDETA). The conventional free radical polymerization (CFRP) of MMA was firstly carried out in the presence of TPM, proving that TPM can initiate the polymerization. The RARTP of MMA in cyclohexanone (CHO) exhibited the living/controlled characteristics: the first-order kinetics with respect to monomer, linear increase of number-average molecular weight (M_n) with conversion, narrow polydispersity index (PDI) (<1.4) and successful chain extension. The possible mechanism was also proposed.     

原子转移自由基聚合在纳米粒子改性方面的研究进展

介绍了原子转移自由基聚合(ATRP)在纳米粒子改性方面的研究进展,综述了基于 ATRP 的多种不同催化体系的衍生技术在纳米粒子表面改性方面的应用,其中主要包括反向原子转移自由基聚合（RATRP）和电子转移活化再生催化剂原子转移自由基聚合(AGET ATRP),并对其特点进行了概述,对纳米粒子表面引发ATRP的发展进行了展望。     

离子液体在原子转移自由基聚合反应中的研究进展

作为一种新型环境友好的"绿色溶剂",室温离子液体已逐步被人们认识和接受。近年来人们将之应用在聚合反应中的研究越来越多,特别是近年发展起来的原子转移自由基活性聚合反应中,使用离子液体不仅可以增大聚合速率和分子量,而且有助于催化剂与聚合物的分离。本文根据近几年的文献资料,阐述了原子转移自由基聚合机理以及离子液体在其中的应用。