Synthesis of polystyrene microgel with glucose as hydrophilic segment via controlled free-radical polymerization

4-Vinylbenzyl glucoside peracetate (1) was copolymerized with divinylbenzene (DVB) using 1-phenyl-1-(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)ethane (2) as an initiator in m-xylene at 138 °C for 20 h (DVB]/2]=28; DVB]=0.62 mol L⁻¹). The copolymerizations were performed using the mole fraction of 1 in the total feed of 1 and DVB (F₁: 1]/1]+DVB]) ranging from 0.11 to 0.38 that produced the polystyrene (PSt) microgel with acetyl glucose, 3, in 46-53% yields. Dynamic laser light scattering (DLS) measurements showed that 3 was stably suspended in toluene as particles with average diameters (d's) ranging from 12 to 22 nm. A static laser light scattering (SLS) measurement gave the average molar mass, M_w,SLS, of 3 that ranged from 9.69×10⁴ to 6.96×10⁵. The numbers of the 1, 2, and DVB units in 3 (N₁, N₂, and N_DVB, respectively) were from 111 to 238, from 17 to 208, and from 350 to 4510, respectively. The deacetylation of 3 was achieved by treatment with sodium methoxide in dry 1,4-dioxane to produce the PSt microgel with glucose as the hydrophilic segment, 4. The solubilities of 4 in toluene, CHCl₃, THF, 1,4-dioxane, pyridine, DMF, DMSO, and H₂O, and the mixture of H₂O and 1,4-dioxane were examined, indicating that a hydrophilic property had been effectively introduced into 4.