Synthesis, Characterization, and Crystallization of Syndiotactic Alternating Ethylene-Propylene Crystalline Copolymer and its Blends.

A syndiotactic alternating ethylene-propylene (SYN-ALT-EP) crystalline copolymer was synthesized by complete hydrogenation, using a diimide reduction, of syndiotactic cis-1,4-poly(pentadiene-1,3) (CIS-PPD). The microstructure was studied by both high resolution nuclear magnetic resonance (NMR) spectroscopy and also fourier transform infra-red (FTIR) spectroscopy. The number average length of syndiotactic sequences is about 69 which indicates a high degree of syndiotacticity (97%) in the microstructure of this copolymer. The single FTIR absorbance at 733 cm^{ -1} without any splitting suggests an alternating arrangement of ethylene and propylene units. The solution state characterization of SYN-ALT -EP was studied by gel permeation chromatography using on -line measurements of multi-angle laser light scattering (MALLS), single capillary viscosities (VISC), and concentrations by differential refractive index (DRI) detectors. The Mark-Houwink-Sakurada parameters of "K" and "a" in THF at 30^circC are determined to be 8.99 times 10^ {-5} and 0.8, respectively. The universal GPC calibration curve can be applied to this copolymer in THF at 30^circC. Two different molecular relaxation processes ( alpha and beta relaxations) were found via dynamic mechanical (DM) analysis below room temperature: an alpha relaxation (around -60^ circC) and a beta relaxation (around -125^circ C). The apparent activation energy of the alpha relaxation is 285 kJ/mol, and the activation energy of the beta relaxation is 43 kJ/mol based on the Arrhenius equation. Molecular motion in SYN-ALT-EP copolymer was probed by solid state ^{13}C NMR experiments. At temperatures above T_{rm g} there are two major molecular motions in this copolymer: a backbone motion (the rotational motion about single bonds) and a methyl side group rotation. The backbone motion is frozen below T_{rm g}, but the methyl rotation still occurs. As the temperature is further decreased to about -175 ^circC, well below the beta -transition observed in DM analysis, the methyl side group rotation slows down, suggesting that the methyl rotation may be associated with the observed beta relaxation process. The equilibrium melting temperature is 55 +/- 1^circC; the equilibrium heat of fusion is 8.8 +/- 0.3 kJ/mol. The overall crystallization kinetics show an Avrami exponent (n) that qualitatively increases with crystallization temperature during primary crystallization. The transition from Regime II to Regime III is observed near T_{rm c} = 26 ^circC based on linear crystal growth rate experiments. The fold surface free energy ( sigma_{rm e}) is determined to be 33 erg/cm^2. A monoclinic crystal unit cell was determined (a = 11.19A b = 11.82A c = 9.00A gamma = 67.03^circ) from the fiber pattern via wide angle x-ray diffraction experiments (WAXD). A banded spherulitic morphology was observed by polarized light microscopy (PLM) and transmission electron microscopy (TEM). Such texture is characteristic of the co-twisting of growing lamellae. The morphology changes from regularly banded spherulites to non-regularly banded spherulites and may be correlated with the Regime III to Regime II transition. A plate-like single crystal morphology was also observed by polarized light microscopy after a melt crystallization at small supercooling conditions. Blends of SYN-ALT-EP/IPP, SYN-ALT-EP/HDPE, and SYN-ALT-EP/LDPE were made and examined. Neither T _{rm g} shifting nor co-crystallization using different blending compositions were observed. Therefore, only limited, if any, miscibility exists in these blends.