Crystallization behavior and resultant crystalline structure of a series of temperature-rising elu-tion-fractionated specimen of a Ziegler-Natta catalyst-synthesized propylene-ethylene random co-polymer were studied by DSC, WAXD and AFM. The experimental results indicate that both crystalliza-tion temperature and propylene sequence length exhibit great influence on the crystallization behavior and crystalline structure of the copolymer. It was found that the ethylene co-monomers acting as point defects inserted into the polypropylene chains play an important role in the formation of γ-iPP. As the co-monomer content increases, the crystallizable sequence length of iPP decreases, which produces an appropriate condition for its γ crystallization. At the same time, the existence of chain defects leads to a lower crystallinity of the copolymer and imperfection of the resultant crystals. For each individual sample with certain propylene sequence length or ethylene content, the increment of γ-iPP crystal content with increasing crystallization temperature demonstrates that higher crystallization tempera-ture is in favor of the γ-iPP crystallization. Pure γ-iPP crystals have been got in samples with propylene sequence length lower than 21 under suitable crystallization conditions.
Hyperbranched polymer-cored star polyfluorenes with high molecular weights and narrow molecular weight distribution were prepared by palladium-catalyzed one-pot Suzuki polycondensation of multi- functional cores and an AB-type monomer. The optical, electrochemical and thermal properties of the hyperbranched polymer-cored star polymers were investigated. These polymers exhibited good ther- mal and color stability in solid state, and there was no significant blue-green emission after the poly- mers had been annealed in air for 2.5 h. Their three-dimensional hyperbranched structures could ef- fectively reduce the aggregation of the peripheral rigid linear conjugated polyfluorene chains.
Morphology of synthetic imogolite nanotubes formed in droplet evaporation was investigated by transmission electron microscopy and electron diffraction. The nanotubes form a dense entangled network at higher concentrations,while at lower concentrations the nanotubes are liable to form ori-ented bundles. Under enthanol atmosphere,individual dispersion of nanotubes was observed for the first time,which reveals the length polydispersity of synthetic imogolite nanotubes.
The isothermal and non-isothermal crystallization kinetics of LCBPP and linear-iPP was investigated by optical microscopy and differential scanning calorimetry (DSC). The optical microscopy results in the isothermal crystallization process show that the crystals of LCBPP grow slower than the crystals of the linear-iPP. This originates from the low chain mobility, or in other words, the lower chain diffusion rate of LCBPP due to the existence of long side chains. The DSC results in the isothermal crystallization process show that the LCBPP exhibits, however, a higher overall crystallization rate with respect to the linear-iPP. This is related to the higher nucleation ability of LCBPP since the isothermal crystallization process of both LCBPP and linear-iPP are nucleation-dominated. Avrami analysis indicates that the nucleation nature and crystal growth manner of LCBPP and linear-iPP are about the same. The analy- ses of the non-isothermal crystallization processes indicate an increment in crystallization rate with increasing cooling rate. But at any cooling rate, the linear-iPP crystallizes more quickly than the LCBPP. This implies that the non-isothermal crystallization processes of LCBPP and linear-iPP are diffu- sion-dominated, in which the lower chain diffusion rate of LCBPP results in the slower crystallization of it.
Porphyrin-containing conjugated poly- mers with fluorene or carbazole as spacer groups were prepared by Sonogashira cross-coupling reac- tions. The polymers were of high molecular weight and the flexible alkyl chains on fluorene or carbazole units made the conjugated polymers soluble in common organic solvents, such as THF and methyl- ene chloride. The polymers could form high quality durable films from solution casting. Their optical and photocurrent responsive properties were investigated. It was found that the photocurrent response was di- rectly proportional to the content of porphyrin. The incorporation of carbazole units into the polymer chains also gave positive contribution to the photo- current generation in some extent.
Highly oriented ultrathin polyethylene (PE) films were prepared by a melt-draw technique. Transmission electron microscopy study on the obtained ultrathin films indicates that the melt drawn PE thin films consist of highly oriented edge-on lamellae aligned perpendicular to the drawing direction. Electron diffraction confirms that the PE chains in crystal-line phase are highly oriented in film plane along the drawing direction, while only a random orientation of the crystallographic a-and b-axes can be described through electron diffraction. The IR results on the melt-drawn ultrathin PE films demonstrate that the PE molecular chains in both crystalline and amorphous phases of the melt drawn thin films are well oriented along the drawing direction. Moreover, the IR results indicate that in the crystalline phase, the crystallographic b-axis tend to lie in the thin film plane, while in the amorphous phase, the skeleton plane of some local chains prefers to parallel the film plane. The alignment of b-axis of PE crystals in ultrathin films originates from the fact that the b-axis is the fastest growth direction of the PE crystals.
