Hydrophobically-Modified PEG Hydrogels with Controllable Hydrophilic/Hydrophobic Balance

This work reports on a novel method to synthesize hydrophobically-modified hydrogels by curing epoxy monomers with amines. The resulting networks contain hydrophilic poly(ethylene glycol) (PEG) segments, poly(propylene glycol) (PPG) segments, and C18 alkyl segments. By varying the content of C18 segments, networks with different hydrophilic-lipophilic balance (HLB) are obtained. All networks show an amphiphilic behavior, swelling considerably both in organic solvents and in aqueous media. In the latter they display a thermosensitive behavior, which is highly affected by the network HLB and the pH of the solution. A decrease in HLB results in an increment of the polymer weight content (wp) due to hydrophobic association. Furthermore, a reduction in HLB induces a remarkable increase in initial modulus, elongation at break and tensile strength, especially when wp becomes greater than about 10%. Low field nuclear magnetic resonance (LF-NMR) experiments evidence that, when HLB decreases, a sudden and considerable increase in hydrogel heterogeneity takes place due to occurrence of extensive physical crosslinking. Available data suggest that in systems with wp ≳ 10% a continuous physical network superimposes to the pre-existing chemical network and leads to a sort of double network capable of considerably improving hydrogel toughness.