## 2 Materials and Methods  
### SIBS Synthesis  
Stabilized styrene (Sigma-Aldrich, St. Louis, MO, USA, \(>\)99%) was treated with 10% KOH aqueous solution, repeatedly washed with water, dried first with CaCl\({}_{2}\) and then with CaH\({}_{2}\), and, finally, distilled two times over CaH\({}_{2}\) under reduced pressure. Methylene chloride and hexane (both from Ekos-1, chemically pure grade) were treated with sulphuric acid, washed with aqueous sodium bicarbonate, dried over CaCl\({}_{2}\), and distilled twice from CaH\({}_{2}\) under an inert atmosphere Titanium tetrachloride (Sigma-Aldrich, St. Louis, MO, USA, 99.9%) was distilled before use. Isobutylene (Sigma Aldrich, St. Louis, MO, USA; 99%) was dried in the gaseous state by passing through the column packed with drierite and condensed into the Schlenk tube. 2,6-Di(_tert_-butyl)pyridine (Sigma-Aldrich, St. Louis, MO, USA; 97%) and dicumyl alcohol (Sigma Aldrich, St. Louis, MO, USA; 97%) were used as received. Dicumyl chloride was synthesized by passing gaseous HCl through solution of dicumyl alcohol in CH\({}_{2}\)Cl\({}_{2}\) at 0 \({}^{\circ}\)C [34]. The purity of dicumyl chloride was conformed by \({}^{1}\)H NMR spectroscopy to be \(>\)99%.  
Triblock copolymer of isobutylene and styrene (SIBS) was synthesized by the living cationic polymerization according to the method reported by [PERSON] et al. [34]. Polymerization was performed under inert argon atmosphere in a three-necked flask. The reactor was consequently charged with dicumyl chloride (0.095 mmol), 25 mL of solvents (hexane-methylene chloride mixture 60:40 _v/v_), 2,6-di(tert-butyl)pyridine (0.20 mmol), and isobutylene (24 mmol) at \(-\)60 \({}^{\circ}\)C. Then, the reaction mixture was cooled to \(-\)80 \({}^{\circ}\)C and 1.9 mmol of titanium tetrachloride was added to initiate the polymerization. After 25 min since the beginning of the polymerization, 9.2 mmol of a preliminarily cooled 2.0 M solution of styrene in a hexane-methylene chloride mixture 60:40 _v/v_ was added into the reactor. The reaction was quenched by 2.0 mL of prechilled methanol 50 min after the initiation. The product was precipitated twice into a tenfold excess of cooled ethanol. The cooled sample was separated by centrifugation, washed with a small amount of ethanol, and dried in a vacuum at 55-60 \({}^{\circ}\)C/2 mmHg to constant weight.  
The structure of newly synthesized SIBS was identified with the differential scanning calorimetry (DSC). The phase and relaxation transitions of the polymer were studied by differential scanning calorimetry on DSC 3+ (Mettler Toledo, Greifensee, Switzerland) with a liquid nitrogen cooling system in the range of \(-\)100-160 \({}^{\circ}\)C with a heating rate of 20 deg/min and a cooling rate of 20 deg/min and with a nitrogen flow of 50 mL/min. The first and second heating cycles were examined in thermograms, the glass transition temperature Tg was evaluated by analyzing the inflection point.  
Number-average molecular weight and polydispersity of SIBS were determined by gel permeation chromatography (GPC). Measurements were performed using an Ultimate 3000 (Thermo Fisher Scientific Dionex, Sunnyvale, CA, USA) device with a PLgel MIXED-C column (7.5 \(\times\) 300 mm, particle size 5 um, Agilent Technologies, Santa Clara, CA, USA) column and one precolumn (PLgel 5 um Guard, Agilent Technologies, Santa Clara, CA, USA) thermostated at 30 \({}^{\circ}\)C. GPS traces were achieved using a refractometer or a UV-detector (\(\lambda\) = 255 nm). Tetrahydrofuran was used as a mobile phase with a flow rate of 1.0 mL min\({}^{-1}\). The molecular weights and polydispersity were calculated based on polystyrene standards (EasiCal, Agilent Technologies, Santa Clara, CA, USA) with M\({}_{\text{w}}\)/M\({}_{\text{n}}\)\(\leq\) 1.05 and using Chromleleon 7.0 program (Thermo Fisher Scientific Dionex, Sunnyvale, CA, USA).