Copper(I)‐catalyzed azide‐alkyne cycloaddition‐assisted polymerization of linear glucose‐derived co/polymers

The synthesis of linear and controllable oligomers and polymers using sugar‐derived monomers is still highly challenging. Herein, we present a method allowing the linear polymerization of a bifunctional glucose derivative as monomer, which contained an azide group at C1 and a propargyl group at C4 position of the glucose ring. The reaction conditions were optimized by grafting the monomer onto the surface of silica nanoparticles (SiNPs) and at the end‐modified polyethylene glycol (PEG). For grafting the surface of SiNPs with the monomer, an azide‐bearing chlorosilane linker was synthesized and introduced onto SiNPs surface. The copper(I)‐catalyzed azide‐alkyne cycloaddition using the glucose‐derived monomer led to the growth of linear triazole‐linked oligosaccharide‐mimics on the surface of SiNPs with a degree of polymerization up to 13 and the formation of cyclic trimers and tetramers in the solution. Furthermore, during polymerization of the monomer at end‐modified PEG, various linear diblock‐copolymers pseudo‐cellulose‐ block ‐PEG and triblock‐copolymers pseudo‐cellulose‐ block ‐PEG‐ block ‐pseudo‐cellulose were obtained. The polymerization reactions expired with nearly complete consumption of the monomer and high yields between 88 and 94% were achieved. Obtained block‐copolymers showed amphiphilic properties that helped to fractionate obtained polymers into lower and higher molecular weight fractions with narrow polymer dispersity Đ .