Branched methacrylate copolymers from multifunctional comonomers: the effect of multifunctional monomer functionality on polymer architecture and properties

Soluble. branched (meth)acrylic copolymers have been synthesised via facile, one-step, batch solution polymerisations taken to high conversion. Methyl methacrylate has been copolymerised with a number of multifunctional comonomers using a chain transfer agent to prevent gelation. A variety of soluble, branched copolymer architectures have been synthesised using multifunctional monomers containing between two and six acrylate functional groups. Independent of polymer composition, all copolymers were proven to be branched with broader molecular weight distributions compared to linear analogues. The molecular weights, Mark-Houwink constants and T-g's all varied systematically depending on the functionality and concentration of the multifunctional monomer copolymerised. Although the polymer architectures are complex, this methodology is pragmatic, highly practical and very convenient. The need for high control of polymer architecture via controlled radical polymerisation for satisfying applications is questioned. It is proposed that precise control may not be necessary for many applications, whereas new, heterogeneous structures via pragmatic routes may be sufficient and more easily exploited.