Ortmann Patrick, Wimmer Florian P, Mecking Stefan
Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, D-78457 Konstanz, Germany.
ACS Macro Lett. 2015 Jul 21;4(7):704-707. doi: 10.1021/acsmacrolett.5b00324. Epub 2015 Jun 19.
Long-spaced polyketones containing 0-52.6 ketone groups per 1000 methylene units were prepared by ADMET copolymerization of docosa-1,21-dien-11-one () with undeca-1,10-diene (), followed by exhaustive hydrogenation. Melting point differences of 5-10 °C were found between these polyketones and their reported congeners from ethylene/CO copolymerizations with comparable CO contents, which were related to additional methyl branching occurring in insertion copolymerization. Consequently, ADMET-derived polyketones can act as defect-free model polyketones. Comparison with polymers containing the same degrees of other carbonyl functionalities (esters, carbonates) shows that the partial compensation of the disturbance of polyethylene crystallization goes along with the groups' polarity.
通过二十二碳-1,21-二烯-11-酮（）与十一碳-1,10-二烯（）的ADMET共聚反应，随后进行彻底氢化反应，制备了每1000个亚甲基单元含有0 - 52.6个酮基的长间隔聚酮。发现这些聚酮与其报道的来自具有可比CO含量的乙烯/CO共聚反应的同系物之间的熔点差异为5 - 10℃，这与插入共聚反应中发生的额外甲基支化有关。因此，ADMET衍生的聚酮可以作为无缺陷的模型聚酮。与含有相同程度其他羰基官能团（酯、碳酸酯）的聚合物的比较表明，聚乙烯结晶干扰的部分补偿与基团的极性有关。
