Ring Opening Metathesis Polymerization (ROMP) of Five-to Eight-Membered Cyclic Olefins: Computational, Thermodynamic, and Experimental Approach
Ring Opening Metathesis Polymerization (ROMP) of Five-to Eight-Membered Cyclic Olefins: Computational, Thermodynamic, and Experimental Approach
复制标题
DOI：
10.1002/pola.28695
复制
发表时间：
2017-09-15
影响因子：
--
通讯作者：
Bazzi, Hassan S.
中科院分区：
文献类型：
--
作者：
Hlil, Antsar R.;Balogh, Janos;Bazzi, Hassan S.
采用第二代Hoveyda-Grubbs催化剂，研究了一系列低应变环烯烃及其羟基衍生物的开环易位聚合反应。此外，进行密度泛函理论（DFT）计算，以评估环烯烃及其羟基衍生物的环应变能，再加上ROMP反应的动力学研究。结果发现，在不同环尺寸的单体中，与其他环烯烃相比，Cy 8具有相对适中的环应变能，表现出最高的单体转化率。研究了环烯烃Cy 5和Cy 7的温度（0、10、15和25 ℃）和单体浓度（1 M; Cy 5为2.5M和5 M; Cy 7为1 M和5 M）的影响。在一般情况下，使用复杂的HG 2获得的动力学ROMP研究的实验结果与DFT计算确定的环烯烃的环应变能非常好地相关。为了比较，DFT计算预测了环应变能Cy 8> Cy 5> Cy 7> Cy 6的以下趋势，并且实验进行的聚合在单体转化率方面遵循相同的趋势，除了在较低浓度下的Cy 5和Cy 7之外，其遵循该趋势Cy 8> Cy 7> Cy 5> Cy 6。2017年《威利期刊》杂志
Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda-Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 8C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6. VC 2017 Wiley Periodicals, Inc.