Reiter M, Vagin S, Kronast A, Jandl C, Rieger B
WACKER-Lehrstuhl für Makromolekulare Chemie , Technische Universität München , Lichtenbergstraße 4 , 85748 Garching b. München , Germany . Email:
Zentralinstitut für Katalyseforschung , Technische Universität München , Ernst-Otto-Fischer Straße 1 , 85747 Garching b. München , Germany.
Chem Sci. 2017 Mar 1;8(3):1876-1882. doi: 10.1039/c6sc04477h. Epub 2016 Nov 17.
A β-diiminato-zinc-N(SiMe) complex () was synthesised and fully characterised, including an X-ray diffraction study. The activity of catalyst towards the coupling reaction of CO and various epoxides, including propylene oxide (PO), cyclohexene oxide (CHO), styrene oxide (SO), limonene oxide (LO), octene oxide (OO) and epichlorohydrin (ECH), was investigated. Terpolymerisation of CO, PO and LO, as well as CO, CHO and PO, was successfully realised, resulting in polymers with adjustable glass transition temperatures and transparencies. Reaction conditions such as temperature, pressure and catalyst concentration were varied to find the optimal reaction values, especially regarding LO/CO. IR experiments hinted that at 60 °C and a critical LO concentration, polymerisation and depolymerisation are in an equilibrium (ceiling effect). Pressurising catalyst with carbon dioxide resulted in a dimeric catalyst () with a OSiMe group as a new initiator. Homopolymerisation of different epoxides was carried out in order to explain the reactivity concerning copolymerisation reaction of CO and epoxides.
合成并全面表征了一种β-二亚胺基锌-N(SiMe)配合物(),包括进行了X射线衍射研究。研究了催化剂对CO与各种环氧化物(包括环氧丙烷(PO)、氧化环己烯(CHO)、氧化苯乙烯(SO)、氧化柠檬烯(LO)、氧化辛烯(OO)和环氧氯丙烷(ECH))偶联反应的活性。成功实现了CO、PO和LO以及CO、CHO和PO的三元共聚,得到了玻璃化转变温度和透明度可调的聚合物。改变温度、压力和催化剂浓度等反应条件以找到最佳反应值,特别是关于LO/CO的。红外实验表明,在60℃和临界LO浓度下,聚合和解聚处于平衡状态(上限效应)。用二氧化碳对催化剂进行加压得到了一种以OSiMe基团为新引发剂的二聚催化剂()。进行了不同环氧化物的均聚反应,以解释其在CO与环氧化物共聚反应中的反应活性。