原子转移自由基聚合(ATRP)的研究进展

介绍了可以实现活性聚合的ATRP、RATRP、AGET ATRP和ARGET ATRP 4种原子转移自由基聚合的机理,综述了原子转移自由基聚合技术在合成两亲性嵌段共聚物、接枝聚合物和星型共聚物等中的研究进展。     

偏氯乙烯活性自由基聚合及其嵌段共聚物合成研究进展

偏氯乙烯(VDC)是重要含氯单体之一,通过活性自由基聚合可以制备分子量可控、分子量分布窄的VDC聚合物,并可进一步制备VDC嵌段共聚物,提高VDC聚合物的性能、拓展其应用。本文对VDC活性自由基聚合(主要是可逆加成-断裂链转移聚合)及其嵌段共聚物合成研究进行了综述。     

原子转移自由基聚合在聚合物分子设计中的应用

原子转移自由基聚合反应 ( ATRP)是一种新的活性自由基聚合方法 ,自 1995年提出后 ,引起高分子合成化学及工业界的关注。本文详细介绍了 ATRP在端功能基聚合物、大分子单体、嵌段共聚物、接枝共聚物、星形聚合物、梯度共聚物、超支化聚合物等聚合物分子设计中的应用     

原子转移自由基聚合在树形聚合物合成中的应用

原子转移自由基聚合(ATRP)技术是一种新型的可控/活性聚合技术,可有效地对聚合物的分子结构进行设计,制备出各种不同性能、不同组成、不同功能化的结构确定的聚合物。综述了利用ATRP技术合成树枝状-线性嵌段共聚物、类树枝状聚合物(dendrimer-like polymer)、具有刺激-响应性末端基团的树枝状聚合物、树枝状-星型嵌段共聚物和基于树枝状聚合物的聚合物刷的研究进展。     

原子转移自由基聚合在合成接枝共聚物中的应用

本文综述了采用原子转移自由基聚合（ATRP）法合成接枝共聚物的研究进展。主要从大分子引发剂法和大分子单体法两方面介绍了原子转移自由基聚合在合成接枝聚合物中的应用。     

原子转移自由基聚合研究进展及其在聚合物制备中的应用

概述了原子转移自由基聚合(ATRP)的机理及其在引发体系、单体等方面的进展。论述了ATRP反应在进行聚合物分子设计,制备具有特定结构的聚合物,如梯度共聚物,嵌段共聚物,末端官能团聚合物,接枝聚合物,星型超支化聚合物,响应型聚合物等方面的应用。     

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进展及其在新型聚合物制备中的应用

概述了原子转移自由基聚合(ATRP)的机理及其在引发体系、单体、反应温度和介质等方面的进展;着重论述了ATRP在进行聚合物分子设计,制备具有特定结构的聚合物,如无规、梯度和交替共聚物,嵌段共聚物,末端官能团聚合物,接枝和梳状聚合物,星型高支化聚合物等方面的应用。     

结构可控含氟共聚物的合成及其应用研究新进展

近年来,含氟聚合物以其优异的耐热性、耐氧化性、耐候性、耐腐蚀性以及低介电常数、低表面能等特点,在疏水材料、抗污材料、表面活性剂、造影剂等领域具有广泛的应用前景,受到研究者的密切关注,各种拓扑结构的含氟共聚物被设计合成出来并在相关领域得到应用。本文首先简要介绍了含氟聚合物的性质和研究现状,然后详细叙述了可逆加成-断裂链转移聚合（RAFT）、原子转移自由基聚合（ATRP）、碘转移自由基聚合（ITP）、单电子转移活性聚合（SET-LRP）、氮氧稳定自由基聚合（NMP）以及活性阴离子聚合（LAP）等聚合方法在结构可控含氟共聚物合成中的研究新进展,并对其聚合机理、优缺点以及所得共聚物的性质和应用进行了总结,最后对结构可控含氟共聚物的设计、合成及实际应用前景进行了展望,提出发展绿色环保功能性含氟聚合物将是未来的主要研究热点。     

苯乙烯和甲基丙烯酸甲酯梯度共聚物的合成

以2－溴异丁酸乙酯为引发剂,溴化亚酮／联二吡啶／铜为催化剂,通过原子转移自由基聚合（ATRP）以及连续补加第二单体的方法制备苯乙烯（St)－甲基丙烯酸甲酯（MMA）梯度共聚物。共聚物相对分子质量的可控性和窄分布证明这是一种活性聚合过程,反应过程中聚合物链的组成变化情况说明形成了梯度结构;聚合温度和MMA加料速度影响聚合速率和共聚物梯度结构,聚合温度升高和加料速度增大使聚合速率加快;改变单体与引发剂的配比,可以得到相应的相对分子质量聚合物。     

Block copolymer grafted-silica particles: a core/double shell hybrid inorganic/organic material

Hybrid inorganic/organic materials consisting of a poly(n-butyl acrylate)-b-poly(styrene) diblock copolymer anchored to silica particles were synthesized via ‘grafting from’ technique using a controlled/living free radical polymerization named stable free radical polymerization. XPS and FTIR analysis were used to control the effectiveness of the chemical modification of the silica particles. Thermal characterizations were performed by thermal gravimetric analysis (TGA) and by differential scattering calorimetry (DSC). The TGA permitted the determination of the quantity of grafted polymer and thus the grafting density; DSC was used to study the influence of the silica and blocks of the copolymer on their thermal behaviors. The glass transition temperature of the grafted copolymers was compared to these of free polymers or copolymers homologues.     

Organic/inorganic hybrid composites prepared by polymerization compounding and controlled free radical polymerization

A new method to produce highly filled and well dispersed polymer solid composites using controlled free radical polymerization has been developed. Grafting of polymers onto ultrafine silica was done in bulk polymerization at 120 °C in presence of N-tert-butyl-1-diethylphosphono2,2-dimethyl propyl nitroxide (DEPN) as a nitroxide stable free radical. Optimum conditions for tert-butyl hydroperoxide grafting onto fumed silica were first determined. The percentage of grafting, the architecture of grafted polymers, the length of chains, and the polydispersity index can be controlled at will using this approach. The effect of the number of grafted polymer chains combined with its molecular weight on the processing of these materials was investigated. The syntheses performed in this work gave grafting percentages of polymers and copolymers ranging from 12 to 88 wt%. All ‘synthesized’ composites gave stable suspensions in toluene and tetrahydrofuran.     

Synthesis of liquid crystalline–amorphous block copolymers by combination of CFRP and ATRP mechanisms

Block copolymers of liquid crystalline 6‐(4‐cyanobiphenyl‐4′‐oxy) hexyl acrylate (LC6) and styrene (St) were obtained by the combination of two different free‐radical polymerization mechanisms namely conventional free‐radical polymerization (CFRP) and atom transfer radical polymerization (ATRP). In the first part, thermosensitive azo alkyl halide, difunctional initiator (AI), was prepared and then used for CFRP of LC6 monomer. The obtained bromine‐ended difunctional liquid crystalline polymers (PLC6) were used as initiators in ATRP of St, in bulk in conjunction with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst. In the second part, AI was firstly polymerized by CFRP in the presence of St and then the obtained difunctional bromine ended polystyrenes (PSt) were used as initiators in ATRP of LC6 in diphenyl ether solvent in conjuction with CuBr/PMDETA. The spectral, thermal, and optical measurements confirmed a fully controlled living polymerization, which results in formation of ABA‐type block copolymers with very narrow polydispersities. In both cases, blocks of the different chemical composition were segregated in the solid and melt phases. The mesophase transition temperatures of the liquid crystalline block were found to be very similar to those of the corresponding homopolymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

丙烯腈与衣康酸在1-丁基-3-甲基咪唑氯化物中的共聚反应

以离子液体1-丁基-3-甲基咪唑氯化物为溶剂,研究了丙烯腈（AN）与衣康酸（IA）的二元共聚反应。利用红外光谱和元素分析法对聚合物进行了化学结构和组成分析,结果表明在离子液体中制备的AN与IA的共聚物与在常规溶剂中的产物有相同的结构并且组成相近。对共聚反应动力学进行了详细探讨,确定了AN与IA在离子液体中较适宜的反应条...     

原子转移自由基聚合最新研究进展

概述了原子转移自由基聚合（ATRP）在引发体系、反应温度、反应介质、实施方法等方面的进展；介绍了3种不同催化剂脱除技术；结合最新的研究成果，着重论述了ATRP在进行聚合物分子设计，制备窄分子量分布聚合物、无规、梯度和交替共聚物，嵌段共聚物，末端官能团聚合物，接枝和梳状聚合物，星型及高支化聚合物等方面的应用。     

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.     

A novel approach for synthesis of poly(norbornene)‐co‐poly(styrene) block copolymers via metathesis polymerization and free‐radical polymerization

It is successfully realized that block copolymers are synthesized via metathesis polymerization followed by free‐radical polymerization. This method is performed using styrene (St) and norbornene, one block is synthesized using the Grubbs second generation catalyst in the presence of chain transfer agents, and the subsequent polymerization of St is initiated by azo compounds to complete the additional blocks in the copolymers. The use of free‐radical polymerization instead of controlled radical polymerization or ionic polymerization can be potentially superior for industrialization. As a result, the molecular weights of the block copolymers ranging from 10.4 to 54.3 kDa and polydispersity indices ranging from 1.30 to 1.91 are obtained. In principle, this new method can be potentially useful to prepare a broad range of block copolymers with cyclic olefin groups in the main chains, which may be used in some particular applications.     

水性苯乙烯-丙烯酸-马来酸酐共聚物的合成及表征

以过氧化苯甲酰为引发剂、二丙二醇二甲醚为溶剂,采用自由基聚合方法,合成苯乙烯-丙烯酸-马来酸酐三元共聚物。考察单体配比、引发剂用量、反应温度对聚合物性能的影响,并用红外光谱、凝胶色谱、差示扫描量热法等对共聚物进行表征。结果表明,最佳工艺条件是:n(ST):n(AA):n(MA)=6:3:1,反应温度为85℃,引发剂为单体质量的12%;得到数均分子量为4678、分子量多分散指数为1.45的三元共聚物。     

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.