Shear-Induced Crystallization of Star and Linear Poly(L-lactide)s

The influence of macromolecular architecture on shear-induced crystallization of poly(L-lactide) (PLLA) was studied. To this aim, three star PLLAs, 6-arm with Mw of 120 and 245 kg/mol, 4-arm with Mw of 123 kg/mol, and three linear PLLAs with Mw of 121, 240 and 339 kg/mol, were synthesized and examined. The PLLAs were sheared at 170 and 150 °C, at 5/s, 10/s and 20/s for 20 s, 10 s and 5 s, respectively, and then cooled at 10 or 30 °C/min. Shear-induced crystallization during cooling was followed by a light depolarization method, whereas the crystallized specimens were examined by DSC, 2D-WAXS, 2D-SAXS and SEM. The effect of shear depended on the shearing conditions, cooling rate and polymer molar mass but it was also affected by the macromolecular architecture. The shear-induced crystallization of linear PLLA with Mw of 240 kg/mol was more intense than that of the 6-arm polymer with similar Mw, most possibly due to its higher Mz. However, the influence of shear on the crystallization of the star polymers with Mw close to 120 kg/mol was stronger than on that of their linear analog. This was reflected in higher crystallization temperature, as well as crystallinity achieved during cooling.

Effective End-Group Modification of Star-Shaped PNVCL from Xanthate to Trithiocarbonate Avoiding Chemical Crosslinking

In this study, six-arm star-shaped poly(N-vinylcaprolactam) (PNVCL) polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization were subjected to aminolysis reaction using hexylamine. Chemically crosslinked gels or highly end-functionalized star polymers can be obtained depending mainly on the type of solvent used during the transformation of the RAFT functional group. An increase in the viscosity of the solution was observed when the aminolysis was carried out in THF. In contrast, when the reaction was conducted in dichloromethane, chain-end thiol (PNVCL)6 star polymers could be obtained. Moreover, when purified (PNVCL-SH)6 star polymers are in contact with THF, the gelation occurs in just a few minutes, with an obvious increase in viscosity, to form physical gels that become chemically crosslinked gels after 12 h. Interestingly, when purified (PNVCL-SH)6 star polymers were stirred in distilled water, even at high aqueous solution concentration (40 mg/mL), there was no increase in the viscosity or gelation, and no evident gels were observed. The analysis of the hydrodynamic diameter (Dh) by dynamic light scattering (DLS) did not detect quantifiable change even after 4 days of stirring in water. On the other hand, the thiol groups in the (PNVCL-SH)6 star polymers were easily transformed into trithiocarbonate groups by addition of CS2 followed by benzyl bromide as demonstrated by UV-Vis spectroscopical analysis and GPC. After the modification, the (PNVCL)6 star polymers exhibit an intense yellow color typical of the absorption band of trithiocarbonate group at 308 nm. To further demonstrate the highly effective new trithiocarbonate end-functionality, the PNVCL polymers were successfully chain extended with N-isopropylacrylamide (NIPAM) to form six-arm star-shaped PNIPAM-b-PNVCL block copolymers. Moreover, the terminal thiol end-functionality in the (PNVCL-SH)6 star polymers was linked via disulfide bond formation to l-cysteine to further demonstrate its reactivity. Zeta potential analysis shows the pH-responsive behavior of these star polymers due to l-cysteine end-functionalization. By this using methodology and properly selecting the solvent, various environment-sensitive star polymers with different end-groups could be easily accessible.

Iron Oxide/Polymer Core–Shell Nanomaterials with Star-Like Behavior

Embedding nanoparticles (NPs) with organic shells is a way to control their aggregation behavior. Using polymers allows reaching relatively high shell thicknesses but suffers from the difficulty of obtaining regular hybrid objects at gram scale. Here, we describe a three-step synthesis in which multi-gram NP batches are first obtained by thermal decomposition, prior to their covalent grafting by an atom transfer radical polymerization (ATRP) initiator and to the controlled growing of the polymer shell. Specifically, non-aggregated iron oxide NPs with a core principally composed of γ-Fe2O3 (maghemite) and either polystyrene (PS) or polymethyl methacrylate (PMMA) shell were elaborated. The oxide cores of about 13 nm diameter were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). After the polymerization, the overall diameter reached 60 nm, as shown by small-angle neutron scattering (SANS). The behavior in solution as well as rheological properties in the molten state of the polymeric shell resemble those of star polymers. Strategies to further improve the screening of NP cores with the polymer shells are discussed.