In order to improve the mechanical
and oxygen barrier properties
of poly(butylene succinate) (PBS), two series of sugar-containing
PBS copolyesters with different molecular stiffness were synthesized
and comparatively investigated, in which a cyclic alditol, isosorbide
(Is) or 2,3-O-isopropylidene-l-threitol
(ITh) was, respectively, used as a comonomer. Both cyclic alditols
were easily available from biomass feedstock, such that Is is a bicyclic
compound derived from d-glucose, and ITh is a monocyclic
acetalized compound coming from naturally occurring l-tartaric
acid. All these copolyesters containing up to 30 mol % of sugar-based
units had satisfactory number-average molecular weights in the 16 000–83 000
g mol–1 range, and presented a random microstructure
together with excellent thermal stability. The sugar-containing copolyesters
were all semicrystalline and still possessed the monoclinic crystal
structure of PBS. The incorporation of either Is or ITh units with
rigid cyclic structure into PBS chain decreased the crystallinity
and crystallization rate of PBS, while it enhanced its glass transition
temperature. In addition, the partial replacement of 1,4-butanediol
by sugar-based units endowed PBS with steadily enhanced hydrophilicity.
Depending on the type and content of sugar units, the copolyesters
show different oxygen barriers and mechanical properties. It was found
that copolyester with bicyclic Is sugar units exhibited a better oxygen
barrier and mechanical property than that with monocyclic ITh units.
During combustion, 2π + π cycloaddition between phenylmaleimide moieties occurred as cross-linking reaction, which enhanced the char yield to achieve flame retardance and anti-dripping of the copolyester.
A series of phosphorus-containing
copolyester prepolymers were first sythesized from dimethyl terephthalate
(DMT), ethylene glycol (EG), and 2-carboxyethyl (phenyl)phosphinic
acid (CEPPA) by molten transesterification and polycondensation, and
then solid-state polymerization (SSP) was conducted for different
reaction times (t
SSP) so as to prepare
higher molecular weight copolymers. The intrinsic viscosity was increased
with the increase of t
ssp, but decreased
with the increase of CEPPA content. The sequence distribution of resultant
copolyesters was analyzed by 1H NMR. It was found that
the randomness of copolyesters was decreased after SSP, and the transesterification
occurred mainly at the ester bonds formed by CEPPA and EG, resulting
in the chain growth. DSC results showed that SSP treatment was favorable
to enhance the crystallization ability of the obtained copolyesters.
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