Block Copolymers Based on Ethylene Glycol, Glycidol and β-Butyrolactone with Tunable Thermal Properties, Solubility,...

We report di- and triblock copolymers that combine hydrophilic polyethers-poly(ethylene glycol) monomethyl ether (mPEG) and polyglycidol (PGl)-with a hydrophobic, degradable polyester, poly(β-butyrolactone) (P(β-BL)). A mild hydrolysis method was developed to selectively remove acetal protecting groups from poly(ethoxy ethyl glycidyl ether) (PEEGE) without cleaving the β-butyrolactone polyester backbone, enabling the preparation of PGl-b-P(β-BL) and mPEG-b-PGl-b-P(β-BL) block copolymers. Thermal analysis revealed that the glass transition temperatures (T_g) of the copolymers could be tuned by varying block composition and length. Diblock copolymers containing the PGl segment were amorphous, with T_g values ranging from -2.7 to -19.9 °C. The presence of an mPEG segment in the triblock copolymers resulted in a further decrease in T_g, reaching values between -32.3 and -38.9 °C. Solubility and water affinity studies demonstrated that incorporation of hydrophilic polyether blocks enhances copolymer-solvent interactions, leading to increased wettability of the polymer-coated surface. The water contact angle for films formed from PGl-b-P(β-BL) decreased to 53 °C, while for mPEG-b-PGl-b-P(β-BL) copolymers, it was further reduced to 43 °C compared with the hydrophobic P(β-BL) film. Hydrolytic degradation experiments showed accelerated cleavage of the P(β-BL) segment in copolymers containing hydrophilic blocks compared to the P(β-BL) homopolymer, which is attributed to increased water accessibility and surface hydrophilicity. The most pronounced decrease in molar mass, reaching at least 50% relative to the initial non-degraded sample, was observed for the diblock copolymers, whereas the P(β-BL) sample showed only a marginal weight reduction of a few percent. Overall, this study demonstrates that the combination of hydrophilic mPEG and PGl blocks with P(β-BL) enables the design of block copolymers with tunable thermal properties, solubility, and degradation behavior, offering potential for a wide range of applications.