1 3 5 trioxane

N-isopropylacrylamide (NIPAM, >99%, Sigma, St. Louis, MO, USA) was recrystallized from n-hexane before use. Furthermore, 2, 2’-Azobisisobutyronitrile (AIBN, 98%) and 4,4’-Azobis(4-cyanovaleric acid) (ACVA, ≥98%) were obtained from Sigma (St. Louis, MO, USA) and recrystallized from methanol prior to use. Stearic acid (>98%) was purchased from TCI America (Tokyo, Japan) and used as received. Additionally, 4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (CDP, 97%), dicyclohexylcarbodiimide (DCC, 99%), 4-dimethylaminopyridine (DMAP, 99%), 2-hydroxyethyl methacrylate (HEMA, ≥99%) carbamazepine (CBZ, ≥98%), 1,3,5-trioxane (≥99%), pyrene (98%) and sodium sulphate anhydrous (Na₂SO₄, 99%) were purchased from Sigma (St. Louis, MO, USA) and used without any further purification. Then 1,4-Dioxane (99%, Fisher Scientific, Waltham, MA, USA) and tetrahydrofuran (THF, ≥99%, Sigma, St. Louis, MO, USA) was purified by being passed through a short alumina column before use. Chloroform-d (99.8 atom %D), dichloromethane (DCM, ≥99.5%) and ethyl acetate (EtOAc, ≥99.5%) were obtained from Sigma (St. Louis, MO, USA), while sodium bicarbonate (NaHCO₃, 99.8%) and sodium chloride (NaCl, 99.9%), diethyl ether (≥99%), methanol (99.8%) and hexane (98.5%) were purchased from Fisher Scientific (Waltham, MA, USA).

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), N-methyl-2-pyrrolidinone (NMP), 1,3,5-trioxane, chlorotrimethylsilane (TMCS), SnCl₄, chloroform, trimethylamine (TMA, 45 wt% in H₂O), potassium hydroxide (KOH), ferrous sulfate (FeSO₄), methanol, sodium chloride, and hydrogen were purchased from Sigma-Aldrich and used without further purification.

All manipulations were performed by Schlenk-line techniques under an inert atmosphere of dry argon. Solvents were dried by standard procedures and distilled under argon prior to use. 4,4′-azobis(4-cyanopentanoic acid) (ACPA, >98%, Fluka), sodium 4-vinylbenzenesulfonate (SS⁻Na⁺, >90%, Aldrich), poly(ethylene oxide) dimethyl ether (PEOMA, M_n = 950 g mol⁻¹, Sigma-Aldrich), diethylene glycol dimethacrylate (DEGDMA, 95%, Aldrich), and 1,3,5-trioxane (>99%, Aldrich), were used as received. Styrene (St, 99%, Acros) was distilled under reduced pressure prior to use. The RAFT agent 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) or R₀-SC(S)SnPr (R₀ = -C(CH₃)-(CN)-CH₂CH₂COOH), was prepared according to the literature [33 ]. The R₀-(SS⁻Na⁺)₁₄₀-SC(S)SnPr and R₀-(SS⁻Na⁺)₁₄₀-b-St₅₀-SC(S)SnPr macroRAFT agents were synthesized as described in our recent contribution [34 ]. The deionized water used for the syntheses and DLS analyses was obtained from a Purelab Classic UV system (Elga Lab-Water).

N-Cyanomethylacrylamide and ethyl 2-(butylthiocarbonothioylthio)propanoate (CTA-1) were synthesized according to previously described protocols [11 (link)]. 2,2′-Azobis(isobutyronitrile) (AIBN, ≥98%, Aldrich, France), 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044) (Aldrich, 98%), 1,3,5-trioxane (Aldrich, ≥99%) and N,N-dimethylformamide (DMF, Normapur, VWR, France) were used as received. N,N-Dimethylacrylamide (DMAm) (Aldrich, ≥99%) was distilled under reduced pressure before use. Deionized water was used for all aqueous polymerizations.

N-vinylcaprolactam (NVCL, kindly supplied by BASF) was distilled under reduced pressure. ε-caprolactone (ε-CL, 97%, Aldrich) was dried over CaH₂ and distilled under reduced pressure before use. AIBN was recrystallized from ethanol, and stored at 4 °C. Toluene (99.5%, Synth), triethylamine (TEA, 99%, Vetec), tetrahydrofuran (THF, 99%, Synth) and 1,4-dioxane (99%, Synth) were dried and fractionally distilled from sodium. Ethanol (95% Synth) was dried and fractionally distilled from calcium hydride. Stannous octoate (Sn(Oct)₂, 92.5–100%, Aldrich), 1,3,5-trioxane (≥99%, Aldrich), 4-(chloromethyl)phenyl methanol (CMPM, 99%, Aldrich), potassium ethyl xanthogenate (KEX, 96%, Aldrich), magnesium sulfate (MgSO₄ XH₂O, 98%, Vetec), pyrene (98%, Aldrich), dichloromethane (DCM, 99.5%, Synth), diethyl ether (98%, Synth) and acetone (99.5%, Synth) were used as received.