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The crystallization behavior of two chemically identical but physically different co-crystallizing poly( l-lactic acid) (PLLA)-based blends is studied. The first set studied involves an all- l unit polymer (PLLA) co-crystallizing with a PDLA-miscible soft polyether-PDLA triblock copoly­mer, where d refers to the d isomer. The second set studied involves homopolymer blends of PLLA/miscible soft polyether/PDLA with compositions identical to the first set. Crystallization is performed under isothermal and non-isothermal crystallization conditions and the crystallization kinetics, crystal perfection, and the blend morphology are investigated. It is clear that the stereocomplex crystallization is significantly slower in the triblock copolymer blends in comparison with the homopolymer blends. Furthermore, based on diffraction, spectroscopic, and thermal data, it is found that the stereocomplex crystals formed in the homopolymer blends achieve higher order and perfection, with a melting temperature 15-20 °C higher than those formed in the triblock blends. [ABSTRACT FROM AUTHOR]

Block copolymers of polystyrene- b-poly(vinyl benzyl trimethylammonium tetrafluoroborate) (PS- b-[PVBTMA][BF4]) were synthesized by sequential monomer addition using atom transfer radical polymerization. Membranes of the block copolymers were prepared by drop casting from dimethylformamide. Initial evaluation of the microphase separation in these PS- b-[PVBTMA][BF4] materials via SAXS revealed the formation of spherical, cylindrical, and lamellar morphologies. Block copolymers of polystyrene- b-poly(vinyl benzyl trimethylammonium hydroxide) (PS- b-[PVBTMA][OH]) were prepared as polymeric alkaline anion exchange membranes materials by ion exchange from PS- b-[PVBTMA][BF4] with hydroxide in order to investigate the relationship between morphology and ionic conductivity. Studies of humidity [relative humidity (RH)]-dependent conductivity at 80 °C showed that the conductivity increases with increasing humidity. Moreover, the investigation of the temperature-dependent conductivity at RH = 50, 70, and 90% showed a significant effect of grain boundaries in the membranes against the formation of continuous conductive channels, which is an important requirement for achieving high ion conductivity. © 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1751-1760, 2013 [ABSTRACT FROM AUTHOR]

Abstract: A method to overcome the brittleness of poly (l-lactic acid) (PLLA) by kinetically trapping a continuous low T g amorphous phase is presented. This morphology is accomplished by exploiting the significant difference in the crystallization temperatures of PLLA vs its stereocomplex with the poly (d-lactic acid) (PDLA) isomer. In our studies, the D isomer is the end block of a triblock copolymer with a configuration of the form PDLAn–Soft Blockm–PDLAn. As demonstrated in this study, when blended with PLLA, the obtained morphology, and improvement in the sample toughness and flexibility, strongly depend on the miscibility of the midblock in the triblock copolymer with the matrix PLLA. The difference in the chemical nature of the midblock clearly affected the stereocomplex crystallization between the PDLA end blocks, the PLLA matrix polymer, and the morphology formed. It is found that the miscible midblock gives rise to a soft continuous amorphous phase while in the case of an immiscible midblock, a glassy phase separated amorphous phase is formed. Dramatically different physical properties can be obtained for various PLLA/triblock copolymer blends giving access to tough, yet flexible, semicrystalline PLLA blends. [Copyright &y& Elsevier]

The slurry homopolymerization of propylene catalyzed by the isospecific metallocene rac-Et(Ind)2ZrCl2/MAO was investigated using a semi-batch reactor. A full factorial design with three temperatures (50, 65 and 75°C) and four monomer partial pressures (1.5, 2.5, 3.2, and 3.8 atm) was performed. Analysis by ¹H NMR revealed the formation of vinylidene, cis-2-butenyl and 4-butenyl end-groups. A kinetic model based on a coordination-insertion mechanism was developed to predict instantaneous reaction rate, molecular weights and polymer chain ends. The kinetic rate constants were estimated using a systematic optimization strategy. The model predicts that the insertion of the first propylene molecule is rate limiting with respect to propagation. Molecular weight decreases with temperature due to the high activation energy of the main chain transfer reaction (101 kJ/mol) relative to propagation (52 kJ/mol). The percentage of butenyl end-groups with respect to vinylidene decreases with temperature, thus predicting a lower activation energy for the β-hydride elimination after secondary insertion (27 kJ/mol). [ABSTRACT FROM AUTHOR]

Cyclic ketene acetals (CKAs) possess unique features in two aspects. On one hand, after the addition of a radical on the alkene, CKAs can undergo ring‐opening via radical rearrangement, enabling polyester preparation based on chain‐growth polymerization. On the other hand, the alkene connected with two electron‐donating oxygens in a strained form exhibit unique reactivities, resulting in complex reactions in the presence of electron deficient compounds. In this investigation, fundamental studies on CKA radical ring‐opening polymerization and charge‐mediated reactions were performed. Alternating copolymers of CKA and maleimides, or maleates, were prepared and characterized. Quantum chemistry modeling from the perspectives of reaction kinetics and thermodynamics enabled an in‐depth mechanistic study on the side reactions between CKA and maleic anhydride or itaconic anhydride, inspiring the techniques to minimize those side reactions in competition with radical copolymerization. After purifying the anhydride monomers with sublimation, the copolymerization with CKA successfully occurred. The anhydride containing polyester structures with an alternating sequence were confirmed with comprehensive characterizations. Facile post‐functionalization with an alcohol was performed, resulting in carboxylate containing polyesters. [ABSTRACT FROM AUTHOR]

The phase behavior of block copolymers (BCPs) at the water‐oil interface is influenced by the segmental interaction parameter (χ ${\chi }$) and chain architecture. We synthesized a series of star block copolymers (s‐BCPs) having polystyrene (PS) as core and poly(2‐vinylpyridine) (P2VP) as corona. The interaction parameters of block‐block (χ ${\chi }$ PS‐P2VP) and block‐solvent (χ ${\chi }$ P2VP‐solvent) were varied by adjusting the pH of the aqueous solution. Lowering pH increased the fraction of quaternized‐P2VP (Q‐P2VP) with enhanced hydrophilicity. By transferring the equilibrated interfacial assemblies, morphologies ranging from bicontinuous films at pH of 7 and 3.1 to nanoporous and nanotubular structure at pH of 0.65 were observed. The nanoporous films formed hexagonally packed pores in s‐BCP matrix, while nanotubes comprised Q‐P2VP as corona and PS as core. Control over pore size, d‐spacing between pores, and nanotube diameters was achieved by varying polymer concentration, molecular weight, volume fraction and arm number of s‐BCPs. Large‐scale nanoporous films were obtained by freeze‐drying emulsions. Remarkably, the morphologies of linear BCPs were inverted, forming hexagonal‐packed rigid spherical micelles with Q‐P2VP as core and PS as corona in multilayer. This work provides insights of phase behaviors of BCP at fluids interface and offer a facile approach to prepare nanoporous film with well‐controlled pore structure. [ABSTRACT FROM AUTHOR]

We show that for supergiants, net angular momentum is not a necessary condition for forming accretion discs during core collapse. Even absent net rotation, convective motions in the outer parts of supergiants generate mean horizontal flows at a given radius with velocities of |${\sim } 1 \, {\rm km \, s}^{-1}$|⁠ ; the direction of the mean flow will vary as a function of height through the convection zone. We confirm these analytic estimates using Cartesian Boussinesq convection simulations. These mean horizontal flows lead to a random angular momentum in supergiant convection zones that exceeds that of the last stable circular orbit of a black hole by a factor of ∼10. As a result, failed explosions of supergiants – in which the accretion shock on to the neutron star does not revive, leading to black hole formation – may often produce accretion discs that can power day–week (blue supergiants) or week–year (yellow and red supergiants) non-thermal and thermal transients through winds and jets. These transients will be especially time variable because the angular momentum of the accreting material will vary substantially in time. Observed sources such as Swift J1644+57, iPTF14hls, and SN 2018cow, as well as energetic Type II supernovae (OGLE-2014-SN-073), may be produced by this mechanism. [ABSTRACT FROM AUTHOR]

Hydroxide (OH−)-exchange membranes (HEMs) are important polymer electrolytes enabling the use of affordable and earth-abundant electrocatalysts for electrochemical energy-conversion devices such as HEM fuel cells, HEM electrolyzers, and HEM solar hydrogen generators. Many HEM cations exist, featuring desirable properties, but new cations are still needed to increase chemical stability at elevated temperatures. Here we introduce the permethyl cobaltocenium [(C5Me5)2Co(III)+ or Cp*2Co+] as an ultra-stable organic cation for polymer HEMs. Compared with the parent cobaltocenium [(C5H5)2Co(III)+ or Cp2Co+], Cp*2Co+ has substantially higher stability and basicity. With polysulfone as an example, we demonstrated the feasibility of covalently linking Cp*2Co+ cation to polymer backbone and prepared Cp*2Co+-functionalized membranes as well. The new cation may be useful in designing more durable HEM electrochemical devices. [ABSTRACT FROM AUTHOR]