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Molecular characterization and crystallization behavior of peroxide-induced slightly crosslinked poly(L-lactide) during extrusion
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Molecular characterization and crystallization behavior of peroxide-induced slightly crosslinked poly(L-lactide) during extrusion
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Molecular characterization and crystallization behavior of peroxide-induced slightly crosslinked poly(L-lactide) during extrusion
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Journal Article
Molecular characterization and crystallization behavior of peroxide-induced slightly crosslinked poly(L-lactide) during extrusion
2010
Overview
Reactive extrusion of poly(
L
-lactide) (PLLA) was carried out in the presence of a small amount of various peroxides with relatively slow decomposition rates. The resulting crosslinked, four-armed randomly branched PLLA (χ-PLLA) was characterized by size exclusion chromatography equipped with multiangle laser light scattering (SEC-MALS), and the results were interpreted according to the type of peroxide used. A new component with a higher molecular weight than the original PLLA was observed in the SEC-MALS chromatograms of the χ-PLLA. The weight-averaged molecular weight (
M
w
) of the χ-PLLA was found to increase with increasing effective radical number per PLLA precursor (
n
), where
n
is the overall hydrogen abstraction ability of peroxide times the mole ratio of radical to PLLA precursor molecule. This implies that the hydrogen abstraction ability is a good index for the crosslinking efficiency of PLLA. The extent of branching of χ-PLLA was estimated by the shrinking factor,
g
=〈
R
g
2
〉
b
/〈
R
g
2
〉
l
, and rationalized with
n
, where 〈
R
g
2
〉
b
and 〈
R
g
2
〉
l
are the mean square radii of gyration of branched and linear polymers with the same molecular weight, respectively. The nucleation and overall crystallization rate of χ-PLLA in the nonisothermal crystallization from the melt was discussed from the viewpoints of branching and entanglement density.
Reactive extrusion of poly(
L
-latctide) (PLLA) was carried out in the presence of a small amount of various peroxides. The resulting crosslinked, four-armed randomly branched PLLA (χ-PLLA) was characterized by size exclusion chromatography fitted with multiangle laser light scattering and rationalized with the type of peroxide used. The extent of branching of χ-PLLA was estimated by the shrinking factor and was rationalized with the effective radical number per PLLA precursor
n
. The nucleation and overall crystallization rate of χ-PLLA in the nonisothermal crystallization from the melt was rationalized with branching and entanglement density.
Publisher
Springer Science and Business Media LLC,Nature Publishing Group UK,Nature Publishing Group
