Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites To Form Acrylate Graft Copolymers

Abstract

Internally plasticized PVC copolymers were prepared by grafting PVC with butyl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate by atom-transfer radical polymerization, resulting in well-behaved polymers with a wide range of glass transition temperatures (–54 °C to 54 °C). When the grafted side chains made up more than 50% of the polymer by weight, the glass transition temperatures were below 0 °C. The covalent attachment of the plasticizing grafts requires one simple procedure starting from commercial PVC, making this strategy an industrially relevant and environmentally friendly alternative to the use of conventional small-molecule plasticizers.

Revisiting poly(vinyl chloride) reactivity in the context of chemical recycling

“…For example, atom transfer radical polymerization (ATRP) is the most common approach, leveraging tertiary alkyl and allylic chlorides in PVC as macroinitiator sites (Scheme 4A). Previous work has utilized numerous monomers-methyl methacrylate, styrene, acrylonitrile, glycidyl methacrylate-for various applications such as hydrogen-bonded macromolecules, 93,94 dye-sensitized solar cells, [95][96][97] membranes, [98][99][100][101][102] covalent plasticizers, 103 and polymeric sorbents. 104 In particular, photoinitiated ATRP has gained attention due to its spatial and temporal control.…”