Organic Lewis Pairs Based on Phosphine and Electrophilic Silane for the Direct and Controlled Polymerization of Methyl Methacrylate: Experimental and Theoretical Investigations

Abstract

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Linear not cyclic – unravelling an anionic initiation pathway for Lewis pair polymerization of lactones

“…It should be noted that LP catalyzed polymerization rates can be favored both by an excess of Lewis base to Lewis acid, 4,7,15 or an excess Lewis acid to Lewis base. 6,16,17,25 It is likely that the ability of the LP to form adducts dictates whether excess Lewis acid is beneficial or not.…”

“…[3][4][5][6][7][8][9][10][11] Due to the differences in interacting nature between a LP and the monomer, LPs exhibit large variations in activity, where some LPs show high activity for some monomers, but at the same time are unable to achieve any conversion of others. [12][13][14][15][16][17][18] An example of a monomer considered 'challenging to polymerize' is the macrolactone ω-pentadecalactone (PDL), as it has low ring strain and the polymerization thermodynamics are entropy driven. [19][20][21] Yet, PDL is of high commercial and scientific interest, since the properties of poly (ω-pentadecalactone) PPDL resemble those of low density polyethylene (LDPE).…”

Advances, Challenges, and Opportunities of Poly(γ-butyrolactone)-Based Recyclable Polymers

“…(Thio)­urea exhibited a buffering effect between the anion and [ t Bu-P 4 H] + , which weakened the nucleophilicity of the anion and prevented the backbiting reaction, leading to a linear product ( M n GPC = 4.30 kg/mol, Đ = 1.51) . Meanwhile, Lewis pair polymerization (LPP) has been demonstrated to be efficient for polymer synthesis. − An N-heterocyclic olefin (NHO)/LiCl system was used for the ROP of GBL . A linear ( M n = 5.8 kg/mol, Đ = 1.60) or cyclic polymer (conv.% < 6%) could be selectively prepared through different NHO/LiCl catalysts with varied nucleophilicity and steric hindrance (Figure b).…”

Synthetic and mechanistic aspects of anionic polymerization of methyl methacrylate using tetrabutyl ammonium thioimidate

“…Very recently, Lewis pairs polymerization have been described by Lu, 36 Chen and Zhang 36,37 as well as Rieger, 38 which prove to be a powerful tool and enable well‐controlled polymerization at room temperature, relying on the matching of Lewis acidity/basicity and the interplay of Lewis acid/base. Meanwhile, Taton reported a silane/phosphine organic Lewis pair for MMA polymerization 39 . We first time reported a bimetallic Lewis acid and its catalytic behavior in MMA and n ‐butyl acrylate (nBA) polymerization 40 …”