Synthesis, characterization, and photopolymerization of (meth)acrylate‐functional polyisobutylene macromers produced by cleavage/alkylation of butyl rubber

Abstract

Linear, multi‐functional polyisobutylene (PIB) macromers bearing pendent and terminal (meth)acrylate moieties were prepared via electrophilic cleavage/alkylation of butyl rubber in the presence of (3‐bromopropoxy)benzene, followed by displacement of the resulting bromide moieties with potassium (meth)acrylate. Number average functionality (Fn) ranged from 2.8–7.9; functional equivalent weights ranged from 2.3–4.7 kg/mol. For comparison, a three‐arm, end‐functional PIB triacrylate with equivalent weight of 3.3 kg/mol was also synthesized via living polymerization and end quenching with 4‐phenoxy‐1‐butyl acrylate. All polymers were photocured using Darocur 1173 photoinitiator, and curing kinetics were monitored by real time Fourier‐transform infrared spectroscopy. All systems reached ~100% conversion by 1,800 s, but the linear macromers displayed slower curing rates compared to the PIB triacrylate. The curing rate of linear macromers increased as molecular weight decreased. Cured networks were characterized using dynamic mechanical analysis and tensile testing. Tensile strength varied from 0.15–0.80 MPa. Young's modulus varied from 0.13–1.8 MPa. Strain at break for most networks ranged from 34–54%, but the network derived from the lowest molecular weight PIB reached 113% at failure. Percent extractables, measured using solvent extraction, was about 2% for linear macromers and about 4% for PIB triacrylate.