Ren, YixinMiller, Justin T.Polderman, Stefanie T.Vo, Trinh D.Wallace, Adele C. M.Cue, John Michael O.Tran, Sarah T.Biewer, Michael C.Stefan, Mihaela C.2020-10-292020-10-292019-01-242046-2069https://dx.doi.org/10.1039/c8ra10050khttps://hdl.handle.net/10735.1/9058Supplementary material is available on publisher's website. Use the DOI link below.Neodymium-based Ziegler-Natta type catalytic systems are known to produce polydienes with high cis-1,4 content. It is generally believed that in Ziegler-Natta catalytic systems, a halide or pseudohalide, whether in the catalyst itself or a separate source, is required for the success of the polymerization. In this work, we have synthesized an unusual halide-free neodymium diethyl phosphate catalyst for diene polymerization. This neodymium complex combined with triisobutylaluminum (TIBA), formed a binary catalytic system and was used to polymerize β-myrcene. The catalytic system displays high stereospecificity and produces poly(β-myrcene) with 96% cis-1,4 content and a relatively narrow molecular weight distribution (Mᵥᵥ/Mₙ = 1.80). Also, kinetic studies indicated the catalytic system gives a pseudo-living polymerization. The block copolymer poly(β-myrcene)-b-poly(isoprene) was successfully synthesized by sequential monomer addition, further demonstrating the pseudo-living nature of polymerization with the neodymium diethyl phosphate catalyst.enCC BY-NC 4.0 (Attribution-NonCommercial)©2019 The Royal Society of Chemistryhttp://creativecommons.org/licenses/by-nc/4.0/MethylaluminoxaneCrystals--StructurePolymerizationButadieneNeodymiumChemistryarticleRen, Yixin, Justin T. Miller, Stefanie T. Polderman, Trinh D. Vo, et al. 2019. "Halide-free neodymium phosphate based catalyst for highly cis-1,4 selective polymerization of dienes." RSC Advances 9(6): 3345-3350, 10.1039/c8ra10050k96