In this work, the optimal electrospinning conditions of trans-polyisoprene (TPI) solutions were evaluated nevertheless its lower glass transition temperature than the room temperature. Subsequently, chemical crosslinking of TPI nonwovens was firstly investigated by vulcanizing at high temperatures in the case of the persistence of nanofiber structure. For this purpose, curing agents of TPI were embedded in TPI nanofibers by co-electrospinning, and then a protect layer was coated on TPI nanofibers by filtering gelatin solution going through TPI nonwoven before the vulcanization at 140-160 ℃. The results showed that the vulcanization of TPI fibrous nonwoven at high temperatures did not destroy the fiber morphology. Interestingly, TPI fibrous nonwovens after vulcanization showed excellent mechanical properties (N17 MPa of tensile strength) that could be comparable to or even higher than that of some bulk rubber materials.
The effects of weight-average molecular (Mw), molecular weight distribution (MWD), and isotacticity on the linear viscoelastic behavior of polybutene-1 melts are studied. It is observed that the linear viscoelastic region becomes slightly narrower with increasing frequency. In frequency sweeps, the transition of the polymer melts flow from Newtonian flow to power-law flow can be observed. The melts with higher Mw and:or broader MWD, as well as higher isotacficity exhibit higher complex viscosity, zero shear viscosity, viscoelasticity moduli, relaxation modulus, broader transition zone, while lower critical shear rate, non-Newtonian index, and the frequency at which elasticity begins to play an important role. The relationship of zero shear viscosity on Mw has been established, which agrees with the classical power law. Furthermore, it is found that the cross-over frequency decreases with increasing Mw and the cross-over modulus increases with narrowing MWD.
Diphenyl (4-hydroxyphenyl) hexadecyl phosphonium bromide (POH) -modified montmorillonite (POHMMT) was used to prepare a novel TiC14/MgC12/POHMMT compound catalyst and exfoliated iPP/POHMMT nanocomposites were prepared by the in situ intercalative polymerization of propylene with the TiC14/MgC12/POHMMT compound catalyst. The POH surfactants don't change the catalytic characteristic of the Z-N catalyst and the obtained PP presents high isotacticity, normal molecular weight and molecular weight distribution. The WAXD, SAXS and TEM results demonstrate the highly exfoliated iPP/POHMMT nanocomposites were produced by the in situ polymerization with this novel catalyst, while the intercalated iPP/Na+MMT nanocomposites were produced with the TiC14/MgC12/Na+MMT compound catalyst. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with high isotacticity and molecular weight, but also to highly exfoliated PP nanocomposites.
Solvent annealing is a facile method for changing the aggregated microstructure and physical properties of polymer materials. In this paper, we addressed the effects of solvent vapor annealing, including chloroform and water vapor, on the polymorphic transformation in both hot-pressed film and electrospun nonwoven of isotactic polybutene-1 (PB-1) by means of in situ Fourier transform infrared spectroscopy (FTIR). The pretty rapid transition rate caused by the increased motion of molecular chains under chloroform vapor is associated with a lowest crystallinity. Also, a decreased crystallinity with the crystal transition occurred in electrospun nonwovens resulting from the relaxation of the stretched molecular chains into amorphous state rather than realignment into crystal form I predominating the crystal transition process.
A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al(i- Bu)3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tiid6s (K-T) method and the Mao-Huglin (M-H) method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers' composition distribution.