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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
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Summary: A novel hydroxyl‐functionalised initiator for atom transfer radical polymerisation (ATRP) was synthesised by esterification reaction of a non‐reducing sugar, meso‐inositol. Due to steric hindrance, one of the six hydroxyl groups present in the sugar was not derivatised to the corresponding 2‐bromoisobutyrate. The macroinitiator was used in ambient temperature ATRP of a hydrophobic monomer, methyl methacrylate (MMA) and a hydrophilic monomer, oligoethylene glycol methacrylate (OEGMA) using tri(ethylene glycol) monomethyl ether (TEGMME) as the polymerisation solvent and CuCl/CuCl2/PMDETA as the catalytic system. Under these conditions, polymerisation proceeded on to high conversion while maintaining low polydispersity giving well‐defined five‐arm star polymers. Hydrolysis under basic conditions was carried out to deduce the number of linear chains that were attached to the sugar.
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Gaohua Zhu Lifen Zhang Xiangqiang Pan Wei Zhang Zhenping Cheng Xiulin Zhu 《Macromolecular rapid communications》2012,33(24):2121-2126
A facile soap‐free miniemulsion polymerization of methyl methacrylate (MMA) was successfully carried out via a reverse ATRP technique, using a water‐soluble potassium persulfate (KPS) or 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (V‐50) both as the initiator and the stabilizer, and using an oil‐soluble N,N‐n‐butyldithiocarbamate copper (Cu(S2CN(C4H9)2)2) as the catalyst without adding any additional ligand. Polymerization results demonstrated the “living”/controlled characteristics of ATRP and the resultant latexes showed good colloidal stability with average particle size around 300–700 nm in diameter. The monomer droplet nucleation mechanism was proposed. NMR spectroscopy and chain‐extension experiments under UV light irradiation confirmed the attachment and livingness of UV light sensitive S C(S) N(C4H9)2 group in the chain end. 相似文献
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《Macromolecular rapid communications》2017,38(10)
It is well known that the recently developed photoinduced metal‐free atom transfer radical polymerization (ATRP) has been considered as a promising methodology to completely eliminate transition metal residue in polymers. However, a serious problem needs to be improved, namely, large amount of organic photocatalysts should be used to keep the controllability over molecular weights and molecular weight distributions. In this work, a novel photocatalyst 1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene (4CzIPN) with strong excited state reduction potential is successfully used to mediate a metal‐free ATRP of methyl methacrylate just with parts per million (ppm) level usage under irradiation of blue light emitting diode at room temperature, using ethyl α‐bromophenyl‐acetate as a typical initiator with high initiator efficiency. The polymerization kinetic study, multiple controlled “on–off” light switching cycle regulation, and chain extension experiment confirm the “living”/controlled features of this promising photoinduced metal‐free ATRP system with good molecular weight control in the presence of ppm level photocatalyst 4CzIPN.
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Summary: The living polymerization of N,N‐dimethylacrylamide was achieved by atom transfer radical polymerization catalyzed by copper chloride complexed with a new ligand, N,N′‐bis(pyridin‐2‐ylmethyl 3‐hexoxo‐3‐oxopropyl)ethane‐1,2‐diamine (BPED). With methyl 2‐chloropropionate as the initiator, the polymerization reached high conversions (> 90%) at 80 °C and 100 °C, producing polymers with very close to theoretical values and low polydispersity. The ligand, temperature, and copper halide strongly affected the activity and control of the polymerization.
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Novel photosensitive azopolymer brushes were synthesized via surface initiated atom transfer radical polymerization using initiator self‐assembled on Au surface. The chemical structures of azobenzene derivatives were confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The surface morphology of azopolymers via atom transfer radical polymerization (ATRP) for different time was investigated by atomic force microscopy (AFM). Additionally, the photoisomerization of azopolymer was measured by ultraviolet‐visible spectroscopy (UV‐Vis). The results indicate that such azopolymers can undergo trans‐cis‐trans photoisomerization efficiently by photo‐irradiation with UV light. Furthermore, this photoisomerization property could also induce the reversible adsorption of bovine serum albumin (BSA) adsorption on azopolymer brush surfaces. This adsorption kinetics of the reversible process can be measured by surface plasmon resonance (SPR) spectroscopy in situ. It suggests that the protein biochips could be regenerated safely by UV irradiation rather than by being rinsed with chemical reagents. 相似文献
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原子转移自由基细乳液聚合* 总被引:2,自引:0,他引:2
本文从正向、反向、同时正向/反向、电子转移活化剂等不同原子转移自由基聚合(ATRP)细乳液引发体系的角度,综述了近年来国内外关于ATRP细乳液聚合的研究进展。在细乳液体系中进行正向ATRP,聚合可控性不理想,反向ATRP相对适合于细乳液体系,其缺点是表面活性剂用量较大。同时正向/反向引发体系的ATRP中催化剂用量大为减少,并且聚合具有良好的可控性;电子转移活化剂(AGET)ATRP是通过电子转移反应来还原过渡金属的氧化态,克服了同时正向/反向ATRP中需要引入自由基引发剂的缺点。 相似文献
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Joanna Pietrasik Chin Ming Hui Wojciech Chaladaj Hongchen Dong Jihoon Choi Janusz Jurczak Michael R. Bockstaller Krzysztof Matyjaszewski 《Macromolecular rapid communications》2011,32(3):295-301
Hybrid nanoparticles with a silica core and grafted poly(methyl methacrylate) (PMMA) or poly(n‐butyl methacrylate) (PBMA) chains were prepared via activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) at room temperature under high pressure. Due to enhanced propagation rate constant and reduced termination rate constant for polymerizations conducted under high pressure, the rate of polymerization was increased, while preserving good control over polymerization when compared to ATRP under ambient pressure. Molecular weights of greater than 1 million were obtained. The PMMA and PBMA brushes exhibited “semi‐diluted” or “diluted” brush architecture with the highest grafting densities ≈0.3 chain·nm−2.
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Giancarlo Masci Laura Giacomelli Vittorio Crescenzi 《Macromolecular rapid communications》2004,25(4):559-564
Summary: Controlled polymerization of N‐isopropylacrylamide (NIPAAM) was achieved by atom transfer radical polymerization (ATRP) using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/tris(2‐dimethylaminoethyl)amine (Me6TREN) as a catalytic system. The polymerization was carried out in DMF:water 50:50 (v/v) mixed solvent at 20 °C. The first order kinetic plot was linear up to 92% conversion. Controlled molecular weights up to 2.2 × 104 and low polydispersities (1.19) were obtained. The living character of the polymerization was also demonstrated by self‐blocking experiments. Block copolymers with N,N‐dimethylacrylamide (DMAAM) and 3‐sulfopropyl methacrylate (SPMA) were successfully prepared.
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Maria Valentina Dinu Mariana Spulber Kasper Renggli Dalin Wu Christophe A. Monnier Alke Petri‐Fink Nico Bruns 《Macromolecular rapid communications》2015,36(6):507-514
Polymersomes that encapsulate a hydrophilic polymer are prepared by conducting biocatalytic atom transfer radical polymerization (ATRP) in these hollow nanostructures. To this end, ATRPase horseradish peroxidase (HRP) is encapsulated into vesicles self‐assembled from poly(dimethylsiloxane)‐block‐poly(2‐methyl‐2‐oxazoline) (PDMS‐b‐PMOXA) diblock copolymers. The vesicles are turned into nanoreactors by UV‐induced permeabilization with a hydroxyalkyl phenone and used to polymerize poly(ethylene glycol) methyl ether acrylate (PEGA) by enzyme‐catalyzed ATRP. As the membrane of the polymersomes is only permeable for the reagents of ATRP but not for macromolecules, the polymerization occurs inside of the vesicles and fills the polymersomes with poly(PEGA), as evidenced by 1H NMR. Dynamic and static light scattering show that the vesicles transform from hollow spheres to filled spheres during polymerization. Transmission electron microscopy (TEM) and cryo‐TEM imaging reveal that the polymersomes are stable under the reaction conditions. The polymer‐filled nanoreactors mimic the membrane and cytosol of cells and can be useful tools to study enzymatic behavior in crowded macromolecular environments.
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Summary: A supported and highly recyclable catalyst complex, CuBr/HMTETA physically adsorbed to silica gel, was used for the ATRP of MMA to elucidate the nature of the catalytic site. In some polymerizations, the reaction solutions were filtered and compared with their unfiltered references for catalytic activity. The filtered systems had high catalyst activity indicating the presence of active catalyst sites in solution. These sites are the primary catalytic contributors.
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A new synthetic approach for the preparation of block copolymers by mechanistic transformation from atom transfer radical polymerization (ATRP) to visible light‐induced free radical promoted cationic polymerization is described. A series of halide end‐functionalized polystyrenes with different molecular weights synthesized by ATRP were utilized as macro‐coinitiators in dimanganese decacarbonyl [Mn2(CO)10] mediated free radical promoted cationic photopolymerization of cyclohexene oxide or isobutyl vinyl ether. Precursor polymers and corresponding block copolymers were characterized by spectral, chromatographic, and thermal analyses. 相似文献
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原子转移自由基聚合(ATRP)应用于乳液聚合体系的主要挑战在于如何同时保证乳液的稳定性和聚合反应的可控性。本文主要对乳液ATRP体系中影响聚合反应可控性和乳液稳定性的各种因素、乳液ATRP的机理和乳液ATRP的应用等方面进行了综述。表面活性剂亲水亲油性及其亲水亲油基团的化学性质、催化剂/配体在油/水两相之间的分配行为、引发剂的溶解性、反应温度以及各组分的浓度是影响反应可控性和乳液稳定性的主要因素。各组分在油/水两相中的分配行为使得乳液ATRP的机理比传统乳液聚合更加复杂。乳液原子转移自由基聚合结合了活性自由基聚合和乳液聚合的优点,在理论研究和工业生产上具有很大的应用前景。 相似文献
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Selvaraj Munirasu Ashwini Deshpande Durairaj Baskaran 《Macromolecular rapid communications》2008,29(18):1538-1543
A simple method has been described to remove catalyst from the copper mediated atom transfer radical polymerization (ATRP) of benzyl methacrylate and methyl methacrylate in anisole at 25 °C using hydrated natural clay (sodium montmorillonite, Na‐clay). The method consists of (1) addition of hydrated clay (CuI/clay ≈ 5 wt.‐%) either during or after the polymerization, (2) oxidation of catalyst complex by exposing the terminated reaction mixture in air, and (3) filtration to obtain catalyst free polymer solution. A strong coordination of CuBr‐ligand complex onto hydrated clay (10 wt.‐% < H2O/clay < 30 wt.‐%) upon oxidation resulted in polymers with no or insignificant residual catalyst (<1.74 ppm), as determined by UV‐vis and atomic absorption spectroscopy. The recovered clay exhibited expanded intercalary layers and absence of polymer within it.
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Jean‐Franois Lutz Hans G. Brner Katja Weichenhan 《Macromolecular rapid communications》2005,26(7):514-518
Summary: The bromine chain ends of well‐defined polystyrene ( = 2 700 g · mol−1, = 1.11) prepared using ATRP were successfully transformed into various functional end groups (ω‐hydroxy, ω‐carboxyl and ω‐methyl‐vinyl) by a two‐step pathway: (1) substitution of the bromine terminal atom by an azide function and (2) 1,3‐dipolar cycloaddition of the terminal azide and functional alkynes (propargyl alcohol, propiolic acid and 2‐methyl‐1‐buten‐3‐yne). The “click” cycloaddition was catalyzed efficiently by the system copper bromide/4,4′‐di‐(5‐nonyl)‐2,2′‐bipyridine. In all cases, 1H NMR spectra indicated quantitative transformation of the chain ends of polystyrene into the desired function.
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基于原子转移自由基聚合技术的偶氮苯星形液晶聚合物的合成与表征 总被引:1,自引:0,他引:1
利用原子转移自由基聚合(ATRP)技术合成了含不同端基取代基的偶氮苯三臂星形侧链液晶聚合物. 均苯三酚与2-溴异丁酰溴通过酯化反应制备三官能团引发剂, 引发偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)或6-[4-(4-乙氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(EMAzo)的ATRP反应. 利用核磁共振氢谱(1H NMR)、凝胶色谱(GPC)、差示扫描量热法(DSC)和偏光显微镜(POM)等手段对星形聚合物进行表征. 星形聚合物的液晶性与相应均聚物相似, 但偶氮苯端基取代基的不同导致星形聚合物的液晶性差别显著. 在紫外/可见光照射下星形聚合物呈现明显的异构化转变. 相似文献
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原子转移自由基聚合(ATRP)是“活性”/可控自由基聚合方法中研究最为广泛的一种,它不仅适用单体广泛、反应条件温和,而且可以方便地对聚合物进行结构设计.为了能够更深入地了解和控制聚合过程,通过ATRP动力学模型化并耦合不同操作方式下的反应器模型已成为必然,它可以更精确地控制大分子链结构,如分子量及其分布、共聚组成及组成分布,同时还能优化聚合条件.从传统自由基聚合理论入手并结合ATRP与传统 自由基聚合的异同,本文首先论述了ATRP动力学模型化过程;其次系统综述了已有的ATRP动力学模型研究,着重对三类不同的数学模型处理方法(矩方法,蒙特卡罗法、商业软件包-PREDICI,GEPASI等)进行了总结. 相似文献