TY - JOUR
T1 - Influence of diosgenin structure on the polymerization kinetics of acrylamide
T2 - An experimental and theoretical approach
AU - Odio, Oscar F.
AU - Martínez, Ariel
AU - Martínez, Ricardo
AU - Crespo-Otero, Rachel
AU - Montero-Cabrera, Luis A.
N1 - Funding Information:
We acknowledge the Laboratorio de Productos Naturales from the Facultad de Química of Universidad de La Habana for diosgenin and cholestanol supplies. Computational studies were supported by the Universidad de La Habana (Cuba), the Universidad Autónoma de Madrid (Spain), and projects CTQ-63332BQU of MEC (Spain) and D/019558/08 of AECID (Spain).
PY - 2011/1/15
Y1 - 2011/1/15
N2 - The acrylamide polymerization in presence of diosgenin has been investigated by experimental and theoretical methods. NMR spectroscopy shows the absence of copolymerization. Viscosimetric and dilatometric experiments support the occurrence of transfer reactions that retard the polymerization. The mechanism was studied at the MPWB1K/6-31G(d,p)//B3LYP/6-31G(d,p) level of theory. Transfer, homopropagation, copolymerization and reinitiation reactions were considered either in gas or solution phase. According to results, the retardation seems to be originated by the formation of an allylic radical in the ring B of diosgenin that reinitiates acrylamide polymerization at slow rate.
AB - The acrylamide polymerization in presence of diosgenin has been investigated by experimental and theoretical methods. NMR spectroscopy shows the absence of copolymerization. Viscosimetric and dilatometric experiments support the occurrence of transfer reactions that retard the polymerization. The mechanism was studied at the MPWB1K/6-31G(d,p)//B3LYP/6-31G(d,p) level of theory. Transfer, homopropagation, copolymerization and reinitiation reactions were considered either in gas or solution phase. According to results, the retardation seems to be originated by the formation of an allylic radical in the ring B of diosgenin that reinitiates acrylamide polymerization at slow rate.
KW - DFT
KW - Diosgenin
KW - Kinetics
KW - Polyacrylamide
KW - Radical polymerization
KW - Transfer reaction
UR - http://www.scopus.com/inward/record.url?scp=84961983747&partnerID=8YFLogxK
U2 - 10.1016/j.molstruc.2010.10.006
DO - 10.1016/j.molstruc.2010.10.006
M3 - Artículo
SN - 0022-2860
VL - 985
SP - 34
EP - 47
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
IS - 1
ER -