Synthesis, Hydrophilicity and Micellization of Coil-Brush Polystyrene-b-(polyglycidol-g-polyglycidol) Copolymer—Comparison with Linear Polystyrene-b-polyglycidol

Abstract

In this paper, an original method of synthesis of coil–brush amphiphilic polystyrene-b-(polyglycidol-g-polyglycidol) (PS-b-(PGL-g-PGL)) block copolymers was developed. The hypothesis that their hydrophilicity and micellization can be controlled by polyglycidol blocks architecture was verified. The research enabled comparison of behavior in water of PS-b-PGL copolymers and block–brush copolymers PS-b-(PGL-g-PGL) with similar composition. The coil–brush copolymers were composed of PS-b-PGL linear core with average DPn of polystyrene 29 and 13 of polyglycidol blocks. The DPn of polyglycidol side blocks of coil–b–brush copolymers were 2, 7, and 11, respectively. The copolymers were characterized by 1H and 13C NMR, GPC, and FTIR methods. The hydrophilicity of films from the linear and coil–brush copolymers was determined by water contact angle measurements in static conditions. The behavior of coil–brush copolymers in water and their critical micellization concentration (CMC) were determined by UV-VIS using 1,6-diphenylhexa-1,3,5-trien (DPH) as marker and by DLS. The CMC values for brush copolymers were much higher than for linear species with similar PGL content. The results of the copolymer film wettability and the copolymer self-assembly studies were related to fraction of hydrophilic polyglycidol. The CMC for both types of polymers increased exponentially with increasing content of polyglycidol.

Influence of hydrophilic block length on the aggregation properties of polyglycidol–polystyrene–polyglycidol copolymers

“…Similar behavior was noticed for PGL segments in polystyrene- b -polyglycidol and polystyrene- b -(polyglycidol- g -polyglycidol) films described in ref. 52. In the case of mentioned copolymers the increased film hydrophilicity was observed during first 48 hours of its water vapors saturation treatment.…”

“…As was shown in our previous papers on diblock PS-PGL and coil-brush PS-(PGL-g-PGL) copolymers, critical concentration vs. f (GL) curve shows exponential dependance. 50,52 In Fig. SI13 (ESI †) the comparison of CMC values obtained by DLS method for diand triblock copolymers is shown.…”

“…In the earlier papers selfassembly behavior of amphiphilic copolymers of polystyrene and polyglycidol with the same hydrophobic polystyrene block (DP n = 29) and hydrophilic polyglycidol blocks with linear and brush (polyglycidol-g-polyglycidol) structures were discussed. [50][51][52] Molar fraction of glycidol (f (GL)) in these copolymers varied in the range from 0.309 to 0.824 for polystyrene-b-polyglycidol and from 0.515 to 0.854 for polystyrene-b-(polyglycidol-g-polyglycidol). For both types of macromolecules the dependence of the critical aggregation/micellization concentration vs. f (GL) was well fitted by exponential function.…”

Synthesis and characterization of zwitter ion functionalized Poly(styrene) based random co-polymer: One pot method

“…Copolymer between styrene and benzaldehyde was reported in the literature [24] . Similarly, copolymers of styrene with 1,3-butadiene [25] , styrenesulfonicacid [26] and poly(glycidol) [27] were reported in the year 2022. Polyurethane-styrene triblock copolymer was reported in the literature [28] .…”