Chemical synthesis of a biodegradable PEGylated copolymer from ε-caprolactone and γ-valerolactone: evaluation of reaction and functional properties

Abstract

This paper reports the chemical synthesis of methoxy poly(ethyleneglycol)-block-poly(ε-caprolactone-co-4-hydroxyvalerate) from ε-caprolactone and γ-valerolactone, a five-membered ring rarely used in chemical synthesis due to its low reactivity. This procedure enabled production of copolymers with controlled ratios of repeating units and molecular weights, as demonstrated by GPC, FT-IR and NMR characterization. Copolymer degradation rate was found to depend on macromolecular composition, and finely tuneable in a wide range of values. Similarly, hydrophilicity was dependent on γ-valerolactone content, and could be accurately controlled by varying the composition of the reaction feed. Importantly, this copolymer showed lower levels of acidic degradation products than other biodegradable polymers, thus resulting in improved biocompatibility. These encouraging results demonstrate the feasibility of the chemical synthesis of a novel and versatile material with interesting properties that fill a gap in the range of commercially available biodegradable polymers.

Preparation and Characterization of Poly(δ-Valerolactone)/TiO2 Nanohybrid Material with Pores Interconnected for Potential Use in Tissue Engineering

“…Pδ-VL has a semi-crystalline structure, low melting point (~−67 °C) and glass transition temperature fluctuates between 52 and 59 °C; in addition, it exhibits less elastomeric behavior compared to PCL [7]. Pδ-VL is slightly more hydrophilic than PCL, probably due to the presence of the polar carbonyl group, and fewer ethenyl groups (one group less) in the repetitive unit of Pδ-VL compared to that of PCL [8]. The degree of biodegradability of Pδ-VL (intermediate polyester) is in between that of poly(lactic-co-glycolic acid) (PLGA) and PCL.…”

Ring-opening copolymerization thermodynamics and kinetics of γ-valerolactone/ϵ-caprolactone

“…Another interesting GBL derivative is γ -valerolactone, which brings an exocyclic methyl group. Recently, the authors reported the GVL copolymerization with ϵ -caprolactone (ECL, Fig 1 ) to give polyesters with improved hydrophilicity and hydrolytic degradation kinetics [ 16 ]. Improved functional properties derived from the presence of the substituent methyl group that significantly modified molecule arrangement.…”

The Impact of Natural and Synthetic Polymers in Formulating Micro and Nanoparticles for Anti-Diabetic Drugs

“…Poly (d,l-lactic-co-glycolic acid)(PLGA) has been widely used as a therapeutic drug delivery system in protein or polypeptide formulations due to its good biocompatibility and biodegradability [5,16,17,18,19]. This polymer consists of various ratios of lactic acid and glycolic acid [8,18,20].…”

“…Poly(lactide-co-glycolide) (PLGA), polyglycolic acid, polylactide (PLA), and poly(caprolactone) (PCL) are the Food and Drug Administration (FDA) approved synthetic polyesters. They are generally classified into three groups based on the polymer degradation kinetics: fast (PLGA, 1-6 months), medium (polyglycolic acid), and slow (PLA and PCL, > 12 months) [14,15,16].…”