Bioengineering Functional Copolymers. IX. Poly[(maleic anhydride‐co‐hexene‐1)‐g‐poly(ethylene oxide)]

Abstract

Abstract Summary: Amphiphilic bioengineering copolymers having a combination of hydrophilic/hydrophobic linkages and polyelectrolyte behavior, along with an ability to interact with biomacromolecules, in particular with the invertase enzyme, have been synthesized by (a) complex‐radical copolymerization of maleic anhydride (MA, the acceptor) and hexene‐1 (H‐1, the donor) monomers with benzoyl peroxide as the initiator in 1,4‐dioxane at 65 °C under high‐conversion conditions and (b) subsequent grafting (polyesterification) of synthesized poly(MA‐ alt ‐H‐1) with α ‐methoxy‐ ω ‐hydroxy‐poly(ethylene oxide) (PEO). Copolymerizations were also carried out in the steady state, in order to essentially reduce the effect of copolymer composition drift. The values of the monomer reactivity ratios ( r 1 and r 2 ) determined by using the known terminal models of Fineman‐Ross (FR) and Kelen‐Tüdös (KT), as well as by nonlinear regression (NLR) analysis, are: r 1 = 0.16 and r 2 = 0.30 (FR), r 1 = 0.14 and r 2 = 0.27 (KT), and r 1 = 0.15 and r 2 = 0.29 (NLR), respectively. All the copolymers and graft copolymers were characterized by FTIR spectroscopy, 1 H{ 13 C} NMR spectroscopy, viscometric measurements, and chemical (acid number), thermal (DSC and TGA), and X‐ray diffraction analyses. Unlike poly(MA‐ alt ‐H‐1)s, PEO macrobranched graft copolymers exhibit expressed polyelectrolyte and swelling behavior in diluted and concentrated dioxane solutions, respectively. The copolymer and its PEO hyperbranched derivatives can be used as carriers for enzyme immobilization. Schematic representation of the chemical structure of hyperbranched poly[(MA‐ alt ‐H‐1)‐ g ‐PEO]. image Schematic representation of the chemical structure of hyperbranched poly[(MA‐ alt ‐H‐1)‐ g ‐PEO].