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1.
原子转移自由基聚合(ATRP)是目前为止最具工业化应用前景的“活性”/可控自由基聚合之一。近年来对其广泛的研究使这一技术逐渐向着“提高可操作性”与“尽可能地减少金属催化剂用量”方面发展;与此同时,诞生了不同催化体系的ATRP衍生技术,如反向原子转移自由基聚合(RATRP)、正向反向同时引发的原子转移自由基聚合(SR&NI ATRP)、引发剂连续再生催化剂原子转移自由基聚合(ICAR ATRP)、电子转移生成催化剂的原子转移自由基聚合(AGET ATRP)和电子转移再生催化剂原子转移自由基聚合(ARGET ATRP)等多种基于ATRP的新方法。本文概述了这几种ATRP体系的发展历程与基本原理,并对其国内外的最新研究进展进行了综述。 相似文献
2.
铜体系催化原子转移自由基聚合机理研究的讨论 总被引：6，自引：0，他引：6
在综述现有文献的基础上,结合作者的研究结果,对ＡＴＲＰ的反应机理进行了讨论,同时,作者提出了ＡＴＲＰ中具有催化活性的络合物结构及自由基增长反应的可能历程。 相似文献
3.
含有热引发转移终止剂的引发体系在反向原子转移自由基聚合中的应用 总被引：6，自引：0，他引：6
原子转移自由基聚合 (ATRP)是实现活性聚合的一种颇为有效的途径 ,可以实现多种单体的活性自由基聚合 .反向原子转移自由基聚合 (ReverseATRP)的概念始提出于 1995年 ,是对传统ATRP的改进和拓展 .近年来关于此体系的引发剂的拓展、过渡金属及单体的适用性都得到了很大发展 .本文简要综述了我们研究组在反向原子转移自由基聚合方面的研究进展 相似文献
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原子转移自由基聚合的研究进展 总被引：7，自引：2，他引：7
综述了原子转移自由基“活性”聚合研究的进展,包括采用的各种引发体系、聚合反应机理、动力学研究以及所合成的各种模型聚合物。通过原子转移自由基聚合可以方便地合成各种结构的模型聚合物,包括窄分布的均聚物、交替、无规和渐变共聚物、特殊链端的聚合物、嵌段和接枝共聚物等。 相似文献
5.
甲基丙烯酸甲酯的原子转移自由基悬浮聚合 总被引：3，自引：0，他引：3
以1-苯基氯乙烷为引发剂 ,氯化亚铜为催化剂,2 ,2-联吡啶为配体 ,外加搅拌,氮气保护下进行了甲基丙烯酸甲酯 (MMA)在80℃下的原子转移悬浮聚合.结果表明 ,聚合反应符合对单体浓度为一级的动力学关系 .经计算聚合体系的增长自由基浓度为5.74×10-8mol/L.聚合物分子量随转化率呈线性增加 ,分子量分布较窄 ,Mw/Mn 在1.37～ 1.40之间 .还以AIBN为引发剂 ,在三氯化铁和三苯基膦存在下进行了MMA的反向原子转移本体和悬浮聚合研究 .结果证明本体聚合具有好的可控特征 ,分子量随转化率呈线性增长 ,分子量分布指数在 1.2 7～ 1.31之间 .聚合反应速率较快 ,聚合体系中的增长自由基浓度较高 ,为 1.6 4× 10-7mol/L .而在此催化体系下的悬浮聚合则完全失去了活性特征. 相似文献
6.
水分散体系中由BPO或KPS引发的苯乙烯反向原子转移自由基聚合 总被引：12，自引：0，他引：12
分别以过氧化二苯甲酰 (BPO)和过硫酸钾 (KPS)为引发剂、1 ,10-邻二氮菲为催化剂配体、十二烷基磺酸钠为乳化剂 ,在水分散体系中进行了苯乙烯的反向原子转移自由基聚合反应 .结果表明 ,对于BPO引发的苯乙烯乳液聚合反应 ,必须由CuBr和CuBr2 形成复合催化剂体系才能达到较好的控制效果 ,其中CuBr可以是直接加入到催化剂体系中 ,也可以是由CuBr2 与Cu0 就地快速反应生成 .CuBr迅速地与BPO反应而实现活性聚合中所谓的“快引发” ,从而有效地控制苯乙烯的聚合反应 .对于KPS引发的苯乙烯乳液聚合体系 ,反应介质的pH值对聚合有很大的影响 ,反应速度随着反应介质pH值的升高而加快 .实验结果表明 ,由两种不同引发剂引发的苯乙烯的乳液的粒径及粒径分布也有很大的差异. 相似文献
7.
综述了铁系催化剂在原子转移自由基聚合（atom transfer radical polymerization,ATRP）中的应用,其中着重介绍了在常规ATRP 和AGET ATRP 聚合中铁类催化体系的研究进展,并且对其它体系如反向 ATRP（R-ATRP）中的铁类催化剂的研究也作了简要介绍,同时概括了铁类催化剂的配体以及产物中残留的该类催化剂的脱除;众多的研究表明铁系催化剂在ATRP 中不仅有良好的催化作用而且易于脱除,该类催化剂在设计新型高分子材料方面也有很好的应用价值;最后总结了铁系催化剂的无毒、易脱除等优点,并对其前景进行了展望。 相似文献
8.
原子转移自由基聚合(ATRP)作为一种有效的\"活性\"/可控聚合可对聚合物进行分子设计,制备结构和相对分子质量可控的各类聚合物,具有潜在而广泛的研究价值。本文综述了ATRP的研究进展,特别是对传统ATRP催化引发体系、RATRP催化引发体系、AGET ATRP催化引发体系、SR&NI ATRP催化引发体系、ICAR ATRP催化引发体系、ARGET ATRP催化引发体系、杂化或双金属催化体系等的催化引发机理进行了详细的介绍。并综述了ATRP聚合中各种实施方法如本体聚合法、溶液聚合法、悬浮聚合法、乳液聚合法等的研究现状。 相似文献
9.
异丙醇铝改进的原子转移自由基聚合催化体系 总被引：4，自引：1，他引：4
以α 溴代异丁酸乙酯［２ （ＥｉＢ） Ｂｒ］ 为引发剂,溴化亚铜（ＣｕＢｒ）／ 联二吡啶（ｂｐｙ）／ 异丙醇铝［Ａｌ（ＯｉＰｒ）３］ 为复合催化剂,在环己酮溶液中进行了甲基丙烯酸正丁酯（ＢＭＡ） 的原子转移自由基聚合（ＡＴＲＰ） ．研究了异丙醇铝对聚合速率及产物分子量分布的影响．异丙醇铝可与引发剂和聚合物中的羰基配位,使相邻的Ｃ—Ｂｒ 键活化,ＡＴＲＰ 反应可以在较低温度下进行．适量溴化铜的加入,可调节ＡＴＲＰ 活性,可得到分子量可控且分子量分布窄的ＰＢＭＡ（ ＭＷＤ＝ １－３ ～１－５） ． 相似文献
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In situ ATRPs of MMA, St in the presence of TD catalyzed by FeCl3/PPh3 and CuBr2/bpy have been studied, respectively. The results showed that the initiator Et2NCS2X (X = Cl or Br) and catalyst FeCl2 or CuBr were formed in situ from the initiating components and the polymerization exhibited living radical polymerization characteristics. In the case of St polymerization with TD/CuBr/bpy initiating system, an inverse ATRP was observed. 相似文献
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Hanying Zhao S. Dayana Argoti Brendan P. Farrell Devon A. Shipp 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):916-924
Polymer–silicate nanocomposites were synthesized with atom transfer radical polymerization (ATRP). An ATRP initiator, consisting of a quaternary ammonium salt moiety and a 2‐bromo‐2‐methyl propionate moiety, was intercalated into the interlayer spacings of the layered silicate. Subsequent ATRP of styrene, methyl methacrylate, or n‐butyl acrylate with Cu(I)X/N,N‐bis(2‐pyridiylmethyl) octadecylamine, Cu(I)X/N,N,N′,N′,N″‐pentamethyldiethylenetriamine, or Cu(I)X/1,1,4,7,10,10‐hexamethyltriethylenetetramine (X = Br or Cl) catalysts with the initiator‐modified silicate afforded homopolymers with predictable molecular weights and low polydispersities, both characteristics of living radical polymerization. The polystyrene nanocomposites contained both intercalated and exfoliated silicate structures, whereas the poly(methyl methacrylate) nanocomposites were significantly exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 916–924, 2004 相似文献
14.
Dave J. Adams Iain Young 《Journal of polymer science. Part A, Polymer chemistry》2008,46(18):6082-6090
Polymer–peptide conjugates are receiving significant interest. Here, we show that, under the appropriate conditions, a small family of oligopeptide‐based initiators can be used successfully to initiate the polymerization of methacrylic monomers by atom transfer radical polymerization (ATRP), generating new examples of such materials. However, the use of the peptidic amide‐based initiators results in polymers which have a higher molecular weight than expected and a significantly higher polydispersity than those prepared from ester‐based initiators. In many cases significant initiator remains, suggesting that either not all peptides successfully initiate polymerization or that significant termination reactions occur early in the reaction. This low initiator efficiency agrees with other reports for amino acid‐based initiators. It therefore appears that such amide‐based initiators can be used successfully, but have a significantly lower applicability than the more commonly used ester‐based initiators. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6082–6090, 2008 相似文献
15.
Joseph V. Nguyen Christopher W. Jones 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1367-1383
Silica‐supported CuBr/pyridylmethanimine (PMI) complexes that facilitate the atom transfer radical polymerization of methyl methacrylate have been prepared and characterized. Four different synthetic routes, including multistep‐grafting (M1), two‐step‐grafting (M2), one‐pot (M3), and preassembled‐complex (M4) methods, have been evaluated on three different silica supports (mesoporous SBA15 with 48‐ and 100‐Å pores and nonporous Cab‐O‐Sil EH5). The resulting solids have been characterized by a battery of techniques, including thermogravimetric analysis/differential scanning calorimetry, FT‐Raman spectroscopy, 13C and 29Si magic‐angle‐spinning and cross‐polarity/magic‐angle‐spinning spectroscopy, low‐temperature nitrogen physisorption, and elemental analysis. The combination of elemental analysis and spectroscopic results has indicated that a variety of different surface species likely exist for most catalysts, including copper species that are both monocoordinated and biscoordinated by PMI ligands, and PMI‐free copper bromide species interacting with the silica surface. M4 appears to give a material that has the smallest amount of the uncomplexed ligand (by FT‐Raman spectroscopy) and is, therefore, the most homogeneous. After M4, the metallation efficiency decreases in the order M2 ≥ M3 > M1, with M1 giving a material with a highly heterogeneous surface composition. The ligand loading on all the catalysts has been determined to be approximately 1 mmol/g of SiO2, with Cab‐O‐Sil‐supported materials giving much higher ligand densities because of its lower surface area. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1367–1383, 2004 相似文献
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Synthesis and decoloration capacity of well-defined and PMMA-grafted palygorskite nanocomposites 总被引：1，自引：0，他引：1
Structurally well-defined PMMA-grafted palygorskite nanoparticles were prepared by modifying the surface of palygorskite nanoparticles with initiators for reverse atom transfer radical polymerization (reverse ATRP) and by using these initiator-modified nanoparticles as macroinitiators. Reverse ATRP from palygorskite nanoparticles was then performed to attach well-defined polymer on to an inorganic core. It has been found that the dispersibility of palygorskite particles in organic solvents is significantly improved by grafting polymers onto the surface of palygorskite particles. The polymer-grafted palygorskite nanoparticles possess excellent decoloration capacity in organic solvents. 相似文献
17.
Joseph V. Nguyen Christopher W. Jones 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1384-1399
A systematic study of the effect of the synthesis method and catalyst structure on the atom transfer radical polymerization (ATRP) performance of copper(I) bromide/pyridylmethanimine complexes supported on silica is described. Four different synthetic routes, including multistep‐grafting (M1), two‐step‐grafting (M2), one‐pot (M3), and preassembled‐complex (M4) methods, have been evaluated on three different silica supports (mesoporous SBA15 with 48‐ and 100‐Å pores and nonporous Cab‐O‐Sil EH5). The resulting solids have been used for ATRP of methyl methacrylate. The catalysts allow for moderate to poor control of the polymerization, with polydispersity indices (PDIs) ranging from 1.46 to greater than 2. The materials made with the preassembled‐complex (M4) and one‐pot (M3) approaches are generally more effective than those prepared with a grafting method (M1 and M2) on porous silica, whereas all the methods provide similarly performing catalysts on the nonporous support. Nonporous Cab‐O‐Sil EH5 is the most effective support because of its small particle size, lack of porosity, and relative compatibility in the reaction media. All the catalysts leach copper into solutions in small amounts. In addition, the catalysts can be effectively recycled, with improved controlled character in recycle runs (PDI ～ 1.2). Control experiments have shown that this improved performance of the used catalysts is likely due to the presence of a soluble Cu(II) complex in the materials that effectively deactivates the growing polymer chain, leading to narrow PDIs and controlled molecular weights. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1384–1399, 2004 相似文献
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Nicolay V. Tsarevsky Jinyu Huang Krzysztof Matyjaszewski 《Journal of polymer science. Part A, Polymer chemistry》2009,47(24):6839-6851
Degradable hyperbranched polymers with multiple alkyl halide chain ends were synthesized by the atom transfer radical polymerization of inimers containing ester (2‐(2′‐bromopropionyloxy)ethyl acrylate) or disulfide (2‐(2′‐bromoisobutyryloxy)ethyl 2′′‐methacryloyloxyethyl disulfide) groups. Both the homo‐ and copolymerizations (with styrene in the former case and methyl methacrylate in the latter) were studied. The hyperbranched polymers derived from the ester‐type inimer were hydrolytically degradable under basic conditions, whereas those derived from the disulfide‐containing inimer could be efficiently degraded in the presence of reducing agents such as tributylphosphine. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009 相似文献