Detailed Kinetic and Mechanistic Insight into Radical Polymerization by Spectroscopic Techniques
Detailed Kinetic and Mechanistic Insight into Radical Polymerization by Spectroscopic Techniques
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DOI：
10.1021/acs.macromol.5b02660
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发表时间：
2016-05-10
期刊：
影响因子：
5.5
通讯作者：
Kattner, Hendrik
中科院分区：
文献类型：
--
作者：
Buback, Michael;Schroeder, Hendrik;Kattner, Hendrik
深入理解传统和可逆失活自由基聚合（RDRP）策略的动力学和机理，需要有效的技术来获得准确的速率系数的各个反应步骤。在最近开发的SP-PLP-EPR技术中，由激光单脉冲（SP）诱导的脉冲激光聚合（PLP）与自由基的类型和浓度的高时间分辨EPR检测结合进行。该方法提供了一个无与伦比的直接访问链长度相关的终止和传播速率的测量。即使对于由于转移反应而出现具有明显不同性质的不同类型的自由基物质的系统，也可以进行完整的动力学分析。SP-PLP-EPR技术也适用于可逆加成-断裂转移（RAFT）聚合、原子转移自由基聚合（ATRP）和有机金属介导的自由基聚合（OMRP）的RDRP相关速率系数的测量。对后两种聚合策略的调查受益于另外应用UV/维斯/NIR结合穆斯堡尔光谱来监测金属催化剂的反应。
The in-depth understanding of the kinetics and mechanism of conventional and reversible deactivation radical polymerization (RDRP) strategies requires efficient techniques to attain accurate rate coefficients of the individual reaction steps. Within the recently developed SP-PLP-EPR technique, pulsed-laser polymerization (PLP) induced by a laser single pulse (SP) is carried out in conjunction with highly time resolved EPR detection of the type and the concentration of radicals. The method provides an unrivaled direct access to the measurement of chain-length-dependent termination and also of propagation rate. Even for systems where as a consequence of transfer reactions different types of radical species with distinctly different properties occur, a full kinetic analysis is within reach. The SP-PLP-EPR technique is also applicable toward the measurement of RDRP-related rate coefficients for reversible addition-fragmentation transfer (RAFT) polymerization, atom transfer radical polymerization (ATRP), and organometallic-mediated radical polymerization (OMRP). Investigations into the latter two polymerization strategies benefit from additionally applying UV/vis/NIR in conjunction with Mossbauer spectroscopy to monitor reactions of the metal catalyst.