Nonisothermal crystallization behavior of exfoliated poly(ethylene terephthalate)‐layered silicate nanocomposites in the presence and absence of organic modifier

Exfoliated poly(ethylene terephthalate) (PET)‐layered silicate nanocomposites (P_etLSNs) excluding (P_etLSN_eom) and including (P_etLSN_iom) organic modifiers were obtained by solution methods with and without solvent‐nonsolvent system, respectively. From wide angle X‐ray diffraction and high resolution transmission electron microscopy, both P_etLSNs were found to have exfoliated structure attributed to sufficient dispersion of silicate in prepared solvents, regardless of sample preparation method. However, organic modifier in P_etLSN_eom was confirmed to be well removed by elemental analysis, whereas organic modifier was still remained in P_etLSN_iom. Thus, the effect of the presence and absence of organic modifiers in P_etLSNs on the nonisothermal crystallization behavior was investigated by differential scanning calorimetry (DSC) on the basis of a modified Avrami analysis and polarized optical microscopy (POM). From DSC results, it was found that both P_etLSNs had higher degrees of crystallinity and shorter crystallization half‐times than neat PET, because of the dispersed silicate layers acted as nucleating agents in both P_etLSNs. However, P_etLSN_iom exhibited a lower degree of crystallinity and longer half‐time of crystallization than P_etLSN_eom. Difference of crystallization behavior between P_etLSN_eom and P_etLSN_iom was ascribed to organic modifier in P_etLSN_iom, which may act as crystallization inhibitors. POM measurements also revealed the results which were in good agreement with crystallization behavior observed from DSC measurement. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 989–999, 2008     

Mesomorphic and conducting properties of dendritic‐linear copolymers via ion‐doped additives

We studied the conducting and mesomorphic behavior of a dendritic‐linear copolymer on adding hydrophilic additives and lithium salts. For the preparation of the pristine block copolymer ( A ), a click reaction of a hydrophobic Y‐shaped dendron block and a hydrophilic linear poly(ethylene oxide) coil with M_n = 750 g mol^?1 was performed. For ionic block copolymer samples ( 1–3 ), a hydrophilic compound ( B ) bearing two tri(ethylene oxide) chains was used as the additive. In all ionic samples, the lithium concentration per ethylene oxide was chosen to be 0.05. As characterized by polarized optical microscopy and small angle X‐ray scattering techniques, copolymer A showed a hexagonal columnar mesophase. On addition of lithium‐doped additives, ionic samples 1 and 2 with the additive weight fractions (f_w) of 10 and 20%, columnar and bicontinuous structures coexisted in the liquid crystalline phase. On the other hand, ionic sample 3 with f_w = 30% displayed only a bicontinuous cubic mesophase. Based on the impedance results, with increasing the amount of additives, the conductivity value increased from 3.80 × 10^?6 to 2.34 × 10^?5 S cm^?1 at 35 °C. The conductivity growth could be explained by the interplay of the plasticization effect of the mobile additive and the morphological transformation from 1D to 3D of the ion‐conducting cylindrical cores. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Tunable cross-linked copolymer networks for improvement of physical performance

The ability to tune the physical properties of polymeric materials through the different compositions in copolymer networks is suitable for the strategy of materials accompanied by combined high mechanical strength and stretchability simultaneously. Here, we developed a practical and straightforward strategy of a copolymer network structure via controlling the compositions of the acrylic-based urethane copolymers of diurethane acrylate (DUA) and diurethane cyclic acrylate (DUCA) with hydrogen-bonds through photo-polymerization. The copolymer networks led to the development of a physically cross-linked structure between the amide groups of DUA and/or DUCA and the hydroxyl groups of pentaerythritol ethoxylate (PEEL) by hydrogen-bonds. Based on the rheological analysis, the composition of the copolymer networks had a significant effect on the control of physical properties and development of cross-linked structure and thus led to the tunable comprehensive properties including high elastic modulus, high chain mobility and high recovery performance with a higher proportion of DUCA in the copolymer networks. Consequently, the tunable copolymer networks based on the developed physically cross-linked structure can improve the elastic properties, recovery performance, and healing ability simultaneously, providing significant progress in the fields of coating and adhesive.     

Cross-Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

In this article, the cross-coupling reaction (CCR) of exocyclic, axially chiral, and acyclic alkenyl (N-methyl)sulfoximines with alkyl- and arylzincs is described_. The CCR generally requires dual Ni catalysis and MgBr₂ promotion, which is effective in diethyl ether but not in THF. NMR spectroscopy revealed a complexation of alkenyl sulfoximines by MgBr₂ in diethyl ether, which suggests an acceleration of the oxidative addition through nucleofugal activation. The CCR of alkenyl sulfoximines generally proceeds in the presence of Ni(dppp)Cl₂ as a precatalyst and MgBr₂ with alkyl- and arylzincs with a high degree of stereoretention at the C and the S atom. CCR of axially chiral alkenyl sulfoximines with Ni(PPh₃)₂Cl₂ as a precatalyst and ZnPh₂ does not require salt promotion and is stereoretentive. The reaction with Zn(CH₂SiMe₃)₂, however, demands salt promotion and is not stereoretentive. CCR of axially chiral α-methylated alkenyl sulfoximines afforded persubstituted axially chiral alkenes with high selectivity. Alkenyl (N-triflyl)sulfoximines engage in a stereoretentive CCR with Grignard reagents and Ni(PPh₃)₂Cl₂. Ni-Catalyzed and MgBr₂-promoted CCR of E-configured acyclic alkenyl sulfoximines and aminosulfoxonium salts with ZnPh₂ and Zn(CH₂SiMe₃)₂ is stereoretentive with Ni(dppp)Cl₂ and Ni(PPh₃)₂Cl₂. CCRs of acyclic alkenyl sulfoximines and alkenyl aminosulfoxonium salts, carrying a methyl group at the α position, take a different course and give alkenyl sulfinamides under stereoretention at the S and C atom. CCR of acyclic, exocyclic, and axially chiral alkenyl sulfoximines has been successfully applied to the stereoselective synthesis of homoallylic alcohols, exocyclic alkenes, and axially chiral alkenes, respectively.