No abstract

Hydrosilylation of olefin groups at poly(ethylene glycol) chain ends catalyzed by Karstedt catalyst often results in undesired side reactions such as olefin isomerization, hydrogenation, and dehydrosilylation. Since unwanted polymers obtained by side reactions deteriorate the quality of end‐functional polymers, maximizing the hydrosilylation efficiency at polymer chain ends becomes crucial. After careful investigation of the factors that govern side reactions under various conditions, it was related that the short lifetime of the unstable Pt catalyst intermediate led to the formation of more side products under the inherently dilute conditions for polymers. Based on these results, two new chelating hydrosilylation reagents, tris(2‐methoxyethoxy)silane (5) and 2,10‐dimethyl‐3,6,9‐trioxa‐2,10‐disilaundecane (6), have been developed. It was demonstrated that the hydrosilylation efficiency at polymer chain ends was significantly increased by employing the internally coordinating hydrosilane 5. In addition, employment of the internally coordinating disilane species 6 in an addition polymerization with 1,5‐hexadiene by hydrosilylation reaction yielded a polymer with high molecular weight (Mn = 9300 g/mol), which was significantly higher than that (Mn = 2600 g/mol) of the corresponding polymer obtained with non‐chelating dihydrosilane, 1,1,3,3‐tetramethyldisiloxane. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 527–536