Multiphase Adhesive Coacervates Inspired by the Sandcastle Worm

Water-borne, underwater adhesives were created by complex coacervation of synthetic copolyelectrolytes that mimic the proteins of the natural underwater adhesive of the sandcastle worm. To increase bond strengths, we created a second polymer network within cross-linked coacervate network by entrapping polyethylene glycol diacrylate (PEG-dA) monomers in the coacervate phase. Simultaneous polymerization of PEG-dA and cross-linking of the coacervate network resulted in maximum shear bond strengths of ∼1.2 MPa. Approximately 40% of the entrapped PEG-dA polymerized based on attenuated total reflectance-Fourier transform infrared spectroscopy. The monomer-filled coacervate had complex flow behavior, thickening at low shear rates and then thinning suddenly with a 16-fold drop in viscosity at shear rates near 6 s(-1). The microscale structure of the complex coacervates resembled a three-dimensional porous network of interconnected tubules. The sharp shear thinning behavior is conceptualized as a structural reorganization between the interspersed phases of the complex coacervate. The bond strength and complex fluid behavior of the monomer-filled coacervates have important implications for medical applications of the adhesives.