Synthesis of Laterally Linked Poly(tetrahydrofuran)−Poly(methyl methacrylate) Block Copolymers via Use of a “Jekyll and Hyde” Comonomer

Abstract

Glycidyl methacrylate (GMA) is an example of a heterobifunctional monomer, a so-called "Jekyll and Hyde" monomer, in that one functional group can be polymerized via conventional free radical polymerization and the other via cationic ring-opening polymerization. Laterally linked diblock copolymers differ from conventional linear diblock copolymers in that the blocks are not linked via their termini but at a point some way along each chain. This architecture has therefore some of the characteristics of a graft copolymer. Free radical copolymerization of a low level of GMA with methyl methacrylate (MMA) yields MMA/GMA copolymers with a few pendent epoxide groups. Likewise cationic ring-opening copolymerization of low levels of GMA with tetrahydrofuran (THF) yields THF/GMA copolymers with a few pendent methacrylate groups. Subsequent cationic polymerization of the first copolymer type with THF, and subsequent free radical polymerization of the second copolymer type with MMA, yields laterally linked block copolymers of MMA and THF. The two strategies are complementary but the polymerization of the THF block first followed by the MMA block is more efficient and leads to good incorporation of both of these monomer segments. Typically mole ratios of THF/MMA segments approaching 1/1 are achievable with copolymer recoveries up to ∼60% and overall M w values up to 125 kDa. While the products are significantly more heterogeneous in terms of the molar mass distributions of the blocks and the backbone architecture than are conventionally produced diblock copolymers, we believe that they are complementary to, rather than competitive with, conventional diblocks and that this new synthetic strategy and ease of synthesis offers potential for the exploitation of these materials.

A Modular Approach for the Synthesis of Nanostructured Hybrid Materials with Tailored Properties: The Simultaneous Twin Polymerization

“…It is thus guaranteed that the growth of the two different polymer chains can become coupled in a reaction volume, which is limited both in terms of space, and mechanistically. TP is therefore clearly differentiated from the polymerization of hetero‐bifunctional monomers in which the two polymerizable groups polymerize independently of each other or in which one of the groups initially remains completely intact during the polymerization 2–4…”

Influences of weather, cultivar and fertiliser rate on grain protein polymer accumulation in field‐grown winter wheat, and relations to grain water content and falling number

“…Damit ist gewährleistet, dass das zeitlich nahe Wachstum der beiden unterschiedlichen Polymerketten in einem eingegrenzten Reaktionsvolumen räumlich und mechanistisch gekoppelt abläuft. Dadurch grenzt sich die ZP klar von der Polymerisation heterobifunktioneller Monomere ab, bei denen die beiden polymerisationsfähigen Gruppen unabhängig voneinander polymerisieren oder vorerst eine dieser Gruppen bei der Polymerisation vollständig erhalten bleibt 2–4…”

Chimeric polymers formed from a monomer capable of free radical, oxidative and electrochemical polymerisation

“…S5c). w This monomer adds to the range of orthogonally polymerisable bifunctional monomers, for example the ''Jekyll and Hyde'' monomer glycidyl methacrylate, 16 and others. 17 These can be exploited via the differential reactivity of the two monomer species.…”