A poly(styrene-ran-cinnamic acid) (SCA) containing 6.8 mol% of CA, with a M w ($217 000) comparable to commercial polystyrene (PS), was successfully synthesised via emulsion free-radical copolymerisation as evidenced by 1744 and 1703 cm À1 infrared peak occurrences, respectively characteristic of free and dimeric carboxyl C]O stretches. Upon the interchain hydrogen bond cross-linking by CA, the impact toughness of the SCA was considerably improved by 47.2% against PS, the glass transition, heat deflection and Vicat softening temperatures were significantly enhanced until 117.0, 108.0 and 118.3 C, respectively, compared with PS (95.2, 87.6 and 96.0 C), while the extensional viscosities were near one order-of-magnitude higher than PS by which the temperature window required for appropriate meltstrengths would be greatly broadened. Meanwhile, the SCA displayed other properties basically analogous to PS. This work presents a modified PS, SCA, with enhanced toughness, heat resistance and melt strength that potentially extend its styrofoam and commodity applications.
A half-critical weight-average molecular weight ( M ¯ w ) (approximately 21,000 g mol−1), high-ion-content Zn-salt poly(styrene–ran–cinnamic-acid) (SCA–Zn) ionomer was successfully synthesized by styrene–cinnamic-acid (10.8 mol %) copolymerization followed by excess-ZnO melt neutralization. At 220 °C, the SCA–Zn’s viscosity was only approximately 1.5 magnitude orders higher than that of commercial polystyrene (PS) at 102 s−1, and the PS/SCA–Zn (5–40 wt %) melt blends showed apparently fine, two-phased morphologies with blurred interfaces, of which the 95/5 and 90/10 demonstrated Han plots suggesting their near miscibility. These indicate that any PS–(SCA–Zn) processability mismatch was minimized by the SCA–Zn’s half-critical M ¯ w despite its dense ionic cross-links. Meanwhile, the SCA–Zn’s Vicat softening temperature (VST) was maximized by its cross-linking toward 153.1 °C, from that (97.7 °C) of PS, based on its half-critical M ¯ w at which the ultimate glass-transition temperature was approximated. Below approximately 110 °C, the PS/SCA–Zn (0–20 wt %) were seemingly miscible when their VST increased linearly yet slightly with the SCA–Zn fraction due to the dissolution of the SCA–Zn’s cross-links. Nevertheless, the 60/40 blend’s VST significantly diverged positively from the linearity until 111.1 °C, revealing its phase-separated morphology that effectively enhanced the heat resistance by the highly cross-linked SCA–Zn. This work proposes a methodology of improving PS heat resistance by melt blending with its half-critical M ¯ w , high-ion-content ionomer.
When a small-molecule ionic crystal is group-substituted with polymer
chain-segments to form an ionomer, do its constrained ionic aggregates
maintain ordered internal structures? This work presents, for a Na-salt
sulfonated-polystyrene ionomer, reconciled TEM electron-diffraction
schlieren textures and WAXS Bragg-type reflections from the ionic-aggregate
nanodomains, which solidly prove the aggregates’ internal (mono)crystalline
order. The observed DSC endotherm of the ionomer, identified by WAXS
as an order–disorder transition interior to its aggregates,
gradually becomes enhanced over a 3-month, room-temperature physical
aging process, indicating that the aggregates’ ordering is
a slow relaxation process in which the degree of order increases with
time. This work corroborates an uncommon form of order, i.e., polymer-bound
small-molecule ionic (quasi)crystal, which is supplementary to the
order phenomena in small molecules, polymers, and liquid crystals.
PurposeThis study aimed to examine whether aerobic exercise exerts mood-modulating effects through an estrogen signaling mechanism.MethodThe experiment was divided into two parts. The first part is to compare the three modeling methods to obtain the most obvious method of depression-like phenotype for further study in the second part. The first part of ovariectomized rats (age, 13 weeks) was tested when rats were 14 or 22 weeks old or in the sixth week after 3 weeks of chronic restraint stress. The second part was to treat the animals with the most obvious depression-like phenotype in different ways, placebo treatment or estradiol (E2) replacement therapy was administered, aerobic training, or estrogen receptor antagonist treatment. The cognitive (Barnes maze and 3-chamber social tests), anxiety-like (open-field and elevated plus maze tests) and depression-like (sucrose preference and forced swim tests) behaviors of rats in both parts were analyzed to study the effects of estrogen depletion and aerobic exercise.ResultsRats did not develop depressive symptoms immediately after ovariectomy, however, the symptoms became more pronounced with a gradual decrease in ovarian hormone levels. Compared with the placebo or control groups, the exercise and E2 groups showed improved performance in all behavioral test tasks, and the antidepressant effects of aerobic exercise were comparable to those of estrogen. Moreover, the estrogen receptor antagonist has markedly inhibited the antidepressant effects of aerobic exercise.ConclusionEstrogen receptors may mediate the antidepressant effects of aerobic exercise. In addition, an increasingly fragile ovarian hormonal environment may underlies chronic restraint stress-induced depression.
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