2.3.1. Synthesis of Poly(caprolactone dimethacrylate)

Poly(caprolactone-dimethacrylate) (PCL700-DMA) Mn = 700 gmol−<sup>1</sup> was synthesized as described in the literature (Supplementary Scheme S1) [51]. In brief, poly-ε-caprolactone (PCL) diol (50 g, 96.22 mmol) was added to an oven-dried round-bottom flask. The reaction flask was sealed with a rubber septum and backfilled with nitrogen (N2). Anhydrous dichloromethane (DCM, 200 mL) and triethylamine (TEA, 222.5 mmol) were added and the flask was placed in an ice bath. A 10% molar excess of methacryloyl chloride (210 mmol) in 100 mL DCM was added dropwise at 0 ◦C over the course of 1 h and the reaction was stirred for 24 h at room temperature (RT). The TEA.HCl salt formed was removed by filtration and the filtrate was diluted 3 times with DCM, washed three times with a NaCl solution and three times with deionized water. The organic layer was collected, dried over magnesium sulfate, and filtered through a fritted funnel. DCM was removed under reduced pressure using a rotatory evaporator.
