Self-Organization in Dilute Aqueous Solutions of Thermoresponsive Star-Shaped Six-Arm Poly-2-Alkyl-2-Oxazines and Poly-2-Alkyl-2-Oxazolines

The behavior of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines in aqueous solutions on heating was studied by light scattering, turbidimetry and microcalorimetry. The core of stars was hexaaza [26] orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. The arm structure affects the properties of polymers already at low temperatures. Molecules and aggregates were present in solutions of poly-2-alkyl-2-oxazines, while aggregates of two types were observed in the case of poly-2-alkyl-2-oxazolines. On heating below the phase separation temperature, the characteristics of the investigated solutions did not depend practically on temperature. An increase in the dehydration degree of poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines led to the formation of intermolecular hydrogen bonds, and aggregation was the dominant process near the phase separation temperature. It was shown that the characteristics of the phase transition in solutions of the studied polymer stars are determined primarily by the arm structure, while the influence of the molar mass is not so significant. In comparison with literature data, the role of the hydrophobic core structure in the formation of the properties of star-shaped polymers was analyzed.

Influence of Salt on the Self-Organization in Solutions of Star-Shaped Poly-2-alkyl-2-oxazoline and Poly-2-alkyl-2-oxazine on Heating

The water–salt solutions of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines were studied by light scattering and turbidimetry. The core was hexaaza[26]orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. NaCl and N-methylpyridinium p-toluenesulfonate were used as salts. Their concentration varied from 0–0.154 M. On heating, a phase transition was observed in all studied solutions. It was found that the effect of salt on the thermosensitivity of the investigated stars depends on the structure of the salt and polymer and on the salt content in the solution. The phase separation temperature decreased with an increase in the hydrophobicity of the polymers, which is caused by both a growth of the side radical size and an elongation of the monomer unit. For NaCl solutions, the phase separation temperature monotonically decreased with growth of salt concentration. In solutions with methylpyridinium p-toluenesulfonate, the dependence of the phase separation temperature on the salt concentration was non-monotonic with minimum at salt concentration corresponding to one salt molecule per one arm of a polymer star. Poly-2-alkyl-2-oxazine and poly-2-alkyl-2-oxazoline stars with a hexaaza[26]orthoparacyclophane core are more sensitive to the presence of salt in solution than the similar stars with a calix[n]arene branching center.

Synthesis and Conformational Characteristics of Thermosensitive Star-Shaped Six-Arm Polypeptoids

Star-shaped six-arm poly-2-alkyl-2-oxazine and poly-2-alkyl-2-oxazoline with hexaaza [26]orthoparacyclophane derivative core were synthesized successfully using cationic ring-opening polymerization. Conformational behavior of prepared polymer stars were investigated by the methods of molecular hydrodynamics and optics in molecular dispersed solutions. It was shown that conformation characteristics of star-shaped polypeptoids depends on arm length, while the chemical structure weakly affects the behavior of the studied polymers in solutions. This behavior is caused by the close equilibrium rigidity of arms. The star-shaped polypeptoids have relatively high intramolecular density. All synthesized stars exhibit LCST behavior. Phase separation temperature depends on arm structure. It is lower for poly-2-alkyl-2-oxazines, monomer units of which contains one methylene group more than monomers of poly-2-alkyl-2-oxazoline.

Performance of the Castor Oil in Methanol-Gasoline as a Bi-Functional Additive

In this paper, the castor oil, as additives, has been investigated on the phase separation temperature of M15, M30, M50 and M65 methanol gasoline at-25.0°C to 40.0°C, respectively. The effect of the additives on the phase stability and saturation vapour pressure was discussed. It was found that castor oil derivatives have good phase stability to various ratio methanol gasoline blends. Introducing water in the methanol gasoline blends need much amount of methyl castor oil to realize phase mixable. Besides, the castor oil can depress the saturation vapour pressure of methanol gasoline effective as well. With these data, it can be concluded that the castor oil have the great potential to be used gasoline-methanol additives.

Microstructural Evolution of Mg-4Al-2.5Ca Alloy during Solidification

In the present work, the microstructure evolution of Mg-4Al-2.5Ca alloy during solidification was investigated by means of scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and differential scanning calorimetry (DSC). The results showed that the as-cast microstructure was typical dendritic structure, consisting of α-Mg and the Al2Ca with a C15 structure formed at inter-dendritic regions. But during slow solidification, the sequence of phase formation of this alloy consisted of following stages: L→ L + α-Mg → L + α-Mg + (Mg, Al)2Ca → α-Mg + (Mg, Al)2Ca + Al2Ca → α-Mg + Al2Ca. Thermal analysis showed that the (Mg, Al)2Ca and Al2Ca phase separation temperature was about 520°C and 510°C respectively, which is different from thermodynamic calculation. With the temperature decreasing, the liquid (Mg, Al)2Ca phase with thick and continuous morphology transformed into lamellar-shaped eutectic phase, and parts of (Mg, Al)2Ca phase translated into Al2Ca phase with bone-shaped and needle-like.