TY - JOUR
T1 - How the Aliphatic Glycol Chain Length Determines the Pseudoeutectic Composition in Biodegradable Isodimorphic poly(alkylene succinate-ran-caprolactone) Random Copolyesters
AU - Safari, Maryam
AU - Torres, Juan
AU - Perez-Camargo, Ricardo A.
AU - de Ilarduya, Antxon Martinez
AU - Mugica, Agurtzane
AU - Zubitur, Manuela
AU - Sardon, Haritz
AU - Liu, Guoming
AU - Wang, Dujin
AU - Muller, Alejandro J.
PY - 2024/11/11
Y1 - 2024/11/11
N2 - We synthesize four series of novel biodegradable poly(alkylene succinate-ran-caprolactone) random copolyesters using a two-step ring-opening/transesterification and polycondensation process with ϵ-caprolactone (PCL) as a common comonomer. The second comonomers are succinic acid derivatives, with variations in the number of methylene groups (n
CH2) in the glycol segment, n
CH2 = 2, 4, 8, and 12. The obtained copolyesters were poly(ethylene succinate-ran-PCL) (ES
xCL
y), poly(butylene succinate-ran-PCL) (BS
xCL
y), poly(octamethylene succinate-ran-PCL) (OS
xCL
y), and poly(dodecylene succinate-ran-PCL) (DS
xCL
y). We discovered a new mixed isodimorphic/comonomer exclusion crystallization in ES
xCL
y copolymers. The BS
xCL
y, OS
xCL
y, and DS
xCL
y copolymers display isodimorphic behavior. Our findings revealed a significant variation in the pseudoeutectic point position, from mixed isodimorphism/comonomer exclusion crystallization to isodimorphism with pseudoeutectic point variation from 54% to up to 90%. Moreover, we established a link between the melting temperature depression slope variation and the comonomer inclusion/exclusion balance, providing valuable insights into the complex topic of isodimorphic random copolymers.
AB - We synthesize four series of novel biodegradable poly(alkylene succinate-ran-caprolactone) random copolyesters using a two-step ring-opening/transesterification and polycondensation process with ϵ-caprolactone (PCL) as a common comonomer. The second comonomers are succinic acid derivatives, with variations in the number of methylene groups (n
CH2) in the glycol segment, n
CH2 = 2, 4, 8, and 12. The obtained copolyesters were poly(ethylene succinate-ran-PCL) (ES
xCL
y), poly(butylene succinate-ran-PCL) (BS
xCL
y), poly(octamethylene succinate-ran-PCL) (OS
xCL
y), and poly(dodecylene succinate-ran-PCL) (DS
xCL
y). We discovered a new mixed isodimorphic/comonomer exclusion crystallization in ES
xCL
y copolymers. The BS
xCL
y, OS
xCL
y, and DS
xCL
y copolymers display isodimorphic behavior. Our findings revealed a significant variation in the pseudoeutectic point position, from mixed isodimorphism/comonomer exclusion crystallization to isodimorphism with pseudoeutectic point variation from 54% to up to 90%. Moreover, we established a link between the melting temperature depression slope variation and the comonomer inclusion/exclusion balance, providing valuable insights into the complex topic of isodimorphic random copolymers.
KW - GLASS-TRANSITION TEMPERATURE
KW - RANDOM COPOLYMERS
KW - EPSILON-CAPROLACTONE
KW - MECHANICAL-PROPERTIES
KW - POLY(ETHYLENE SUCCINATE)
KW - CRYSTALLIZATION
KW - BEHAVIOR
KW - DEGRADATION
KW - ISOMORPHISM
KW - POLYESTERS
U2 - 10.1021/acs.biomac.4c01073
DO - 10.1021/acs.biomac.4c01073
M3 - Article
SN - 1525-7797
VL - 25
SP - 7392
EP - 7409
JO - Biomacromolecules
JF - Biomacromolecules
IS - 11
ER -