TY - JOUR
T1 - Synthesis of zwitterionic copolymers via copper-mediated aqueous living radical grafting polymerization on starch
AU - Fan, Yifei
AU - Migliore, Nicola
AU - Raffa, Patrizio
AU - Bose, Ranjita K.
AU - Picchioni, Francesco
PY - 2019/1/22
Y1 - 2019/1/22
N2 - [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) is a well-studied sulfobetaine-methacrylate as its zwitterionic structure allows the synthesis of polymers with attractive properties like antifouling and anti-polyelectrolyte behavior. In the present work, we report the Cu0-mediated living radical polymerization (Cu0-mediated LRP) of SBMA in sodium nitrate aqueous solution instead of previously reported solvents like trifluoroethanol and sodium chloride aqueous/alcoholic solution. Based on this, starch-g-polySBMA (St-g-PSBMA) was also synthesized homogeneously by using a water-soluble waxy potato starch-based macroinitiator and CuBr/hexamethylated tris(2-aminoethyl)amine (Me6TREN) as the catalyst. The structure of the macroinitiator was characterized by 1H-NMR, 13C-NMR, gHSQC, and FT-IR, while samples of PSBMA and St-g-PSBMA were characterized by 1H-NMR and FT-IR. Monomer conversion was monitored by 1H-NMR, on the basis of which the reaction kinetics were determined. Both kinetic study and GPC results indicate reasonable controlled polymerization. Furthermore, a preliminary study of the thermal response behavior was also carried through rheological tests performed on aqueous solutions of the prepared materials. Results show that branched zwitterionic polymers are more thermal-sensitive than linear ones.
AB - [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) is a well-studied sulfobetaine-methacrylate as its zwitterionic structure allows the synthesis of polymers with attractive properties like antifouling and anti-polyelectrolyte behavior. In the present work, we report the Cu0-mediated living radical polymerization (Cu0-mediated LRP) of SBMA in sodium nitrate aqueous solution instead of previously reported solvents like trifluoroethanol and sodium chloride aqueous/alcoholic solution. Based on this, starch-g-polySBMA (St-g-PSBMA) was also synthesized homogeneously by using a water-soluble waxy potato starch-based macroinitiator and CuBr/hexamethylated tris(2-aminoethyl)amine (Me6TREN) as the catalyst. The structure of the macroinitiator was characterized by 1H-NMR, 13C-NMR, gHSQC, and FT-IR, while samples of PSBMA and St-g-PSBMA were characterized by 1H-NMR and FT-IR. Monomer conversion was monitored by 1H-NMR, on the basis of which the reaction kinetics were determined. Both kinetic study and GPC results indicate reasonable controlled polymerization. Furthermore, a preliminary study of the thermal response behavior was also carried through rheological tests performed on aqueous solutions of the prepared materials. Results show that branched zwitterionic polymers are more thermal-sensitive than linear ones.
KW - Anti-polyelectrolyte behavior
KW - Cu-mediated living radical polymerization
KW - Starch copolymer
KW - Zwitterionic polymer
KW - PROTEIN
KW - POLYZWITTERION
KW - RESISTANCE
KW - BEHAVIOR;
KW - ATRP
UR - http://www.scopus.com/inward/record.url?scp=85060445197&partnerID=8YFLogxK
U2 - 10.3390/polym11020192
DO - 10.3390/polym11020192
M3 - Article
C2 - 30960176
AN - SCOPUS:85060445197
VL - 11
JO - Polymers
JF - Polymers
SN - 2073-4360
IS - 2
M1 - 192
ER -