Phenylethyl bromide phebr

Styrene (St) (Sigma, Aldrich, 99 %) and t-butyl acrylate (tBA) (Sigma-Aldrich, 98 %) were distilled under reduced pressure over calcium hydride prior to use. Copper (I) bromide (CuBr) (Sigma-Aldrich, 98%), 2,2'-bipyridyl (bipy) (Sigma-Aldrich, 99 %), N,N,N',N'',N'',pentamethyldiethylenetriamine (PMDETA) (Sigma-Aldrich, 99 %), phenylethyl bromide (PhEBr) (Sigma-Aldrich, 97 %), and other solvents were used as received. The diblock copolymers were prepared by atom-transfer radical polymerization (ATRP) in two steps following previously reported procedures [39] .
Polystyrene filaments were purchased from Impresoras 3D (ESUN HIPS). According to the supplier contains around 85 wt% of PS, 10 wt% acrylonitrile and 5 wt% butadiene. High molecular weight polystyrene (Aldrich, Mw =2.50•10 5 g/mol) was used as polymeric matrix. Chloroform (CHCl3) was purchased from Scharlau.

The monomers, t-butyl acrylate (tBA) (Sigma-Aldrich, 98 %) and styrene (St) (Sigma, Aldrich, 99 %), required purification by first dried over calcium hydride and distilled using vacuum techniques. The following list of compounds were used as received: 2,2'-bipyridyl (bipy) (Sigma-Aldrich, 99 %), phenylethyl bromide (PhEBr) (Sigma-Aldrich, 97 %), N,N,N',N'',N'',pentamethyldiethylenetriamine (PMDETA) (Sigma-Aldrich, 99 %), Copper (I) bromide (CuBr) (Sigma-Aldrich, 98%) and other solvents. Coupling reactions were carried out using N-Hydroxysuccinimide (NHS) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (Sigma-Aldrich -USA). The polystyrene-b-poly(acrylic acid) diblock copolymers were prepared following the procedures already reported by our group [39] .