Methacrylic Copolymers for Controlled Phase Separation and Complex Coacervation

Abstract

<p> It is well known that complex coacervates can be prepared by combining aqueous solutions of oppositely charged biopolymers, such as gelatin and gum arabic. There are few examples of synthetic polyelectrolytes that produce complex coacervates, however. Two series of anionic copolymers capable of forming complex coacervates with branched polyethylenimine (PEI) in water have been prepared. One series consists of binary copolymers containing methacrylic acid (MAA) and poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMA) in molar ratios ranging from 20:80 to 80:20, as well as the two homopolymers, poly(MAA) and poly(PEGMA). Another series contains an equimolar amount of MAA and PEGMA, together with between one and ten percent of a third, hydrophobic monomer, butyl methacrylate (BMA).</p> <p> Both binary and ternary copolymers show lower critical solution temperatures, LCST's, ranging from 60.8°C to 1.5°C depending on composition. Furthermore, complex coacervation occurs upon addition of aqueous PEI to aqueous solutions of these copolymers. The percent volume of the liquid coacervate phase is independent of copolymer composition. However, with increasing MAA to PEGMA ratio in the binary copolymer, the concentration of the coacervate increases, reflecting an increased coacervation efficiency. The coacervate composition was not significantly affected by the BMA in the ternary copolymer series.</p>