The molecular, thermodynamic, and kinetic factors that govern the formation and concentration of the α and γ polymorphs in metallocene-catalyzed isotactic poly(propylenes) have been studied with a set of polymers that have a wide range in molecular weight and defect contents. With these polymers it was possible to investigate the influence of molecular weight on γ formation at a fixed defect concentration, as well as the role of the defect concentration at constant molecular weight. The major experimental techniques used were wide-angle X-ray scattering and differential scanning calorimetry complemented by microscopy. From these studies the role of chain microstructure, the crystallization temperature, and the thermodynamic and kinetic requirement for the formation of the γ form could be established in more quantitative detail than heretofore. A particular important finding was the fact that at fixed defect concentration the fractional content of the γ polymorph goes through a maximum with crystallization temperature. The results that were obtained establish a quantitative framework within which the underlying bases that lead to formation of the γ form, and its unique crystalline structure, are discussed.

We report the effect of molecular weight and comonomer content on melt crystallization of model random ethylene 1-butene copolymers. A large set of narrowly distributed linear polyethylenes (PE) was used as reference of unbranched molecules. The samples were crystallized from a melt state above the equilibrium melting temperature and cooled at a constant rate. The exothermic peaks of the melt-solid transition are reported as the crystallization temperatures (T c ). Following expectations, the T c of unbranched PE samples was constant and independent of the initial melt temperature. The same independence was observed for copolymers (2.2 mol % ethyl branches) with molar mass below 4500 g/mol. Moreover, the T c of copolymers with higher molar mass depends on the temperature of the initial melt, T c increases as the temperature of the melt decreases. We attribute the increase in T c to a strong crystallization memory in the melt above the equilibrium melting, and correlate this phenomenon with remains in the melt of the copolymer’s crystallizable sequence partitioning. Albeit molten, long crystallizable sequences remain in the copolymer’s melt at a close proximity, lowering the change in free energy barrier for nucleation. The residual sequence segregation in the melt is attributed to restrictions of the copolymer crystalline sequences to diffuse upon melting and to reach the initial random topology of the copolymer melt. Erasing memory of the prior sequence selection in copolymer melts requires much higher temperatures than the theoretical equilibrium value. The critical melt temperature to reach homogeneous copolymer melts (T onset ), and the comonomer content at which melt memory above the equilibrium melting vanishes are established. The observed correlation between melt memory, copolymer crystallinity and melt topology offers strategies to control the state of copolymer melts in ways of technological relevance for melt processing of LLDPE and other random olefin copolymers.

Four sets of random propylene-based copolymers with 1−10 mol % of ethylene, 1-butene, 1-hexene, or 1-octene as co-units, synthesized with the same metallocene catalyst, were investigated by differential scanning calorimetry and wide-angle X-ray scattering following rapid and isothermal crystallization. Parameters related to defect concentration, defect type, and microstructure and thermodynamic and kinetic factors were evaluated as to their role in developing the γ polymorph. The effect of the comonomer in enhancing the fractional content of the γ polymorph is akin to the role of defects in the homo-poly(propylene) chain. However, differences in the partitioning of the comonomer between the crystalline and noncrystalline regions leads to contents of the γ phase that differ among the copolymers at any given crystallization temperature. Qualitatively, these differences can be used to assess the degree to which a counit participates in the crystallite. The experimental results suggest that there is no discrimination of the defects that enter the crystal lattice (stereo, regio, ethylene, or butylene units) between the α or γ crystallites. The results with copolymers establish that the bases that lead to the formation of the γ polymorph are the same for homo-poly(propylene) and its copolymers.

A series of four propylene/ethylene, metallocene-catalyzed random copolymer samples, with ethylene mole fractions ranging from 0.8% to 7.5% and melt crystallization histories of cooling at 1 °C/min, were studied by 13C solid-state NMR techniques. The principal objective of the study was to determine the partitioning of the ethylene “defect” residues within the semicrystalline morphology of these isotactic poly(propylene/ethylene) copolymers. Signals from the crystalline (CR) and the noncrystalline (NC) regions were separated on the basis of contrasting T 1 ρ H behaviors. Four new resonances, three distinct and one strongly overlapping, were identified in the spectrum of the CR regions. The assignment of these new defect resonances to specific carbons at or near the ethylene defect site was made principally on the basis of quantum mechanical chemical shift calculations. These calculations were performed on two methyl-terminated oligomers of about 6.5 monomers in length with a 31 helical backbone conformation, characteristic of the iPP backbone conformation in the CR state. One oligomer was the pure iPP chain, and the other contained one centrally located ethylene repeat unit. Good agreement between the experimental shifts associated with the ethylene defect and the computed shifts supported the assumption that the chain conformation in the CR regions in the vicinity of the ethylene defect remained a 31 helix. This good agreement between shifts was obtained when the computed shifts were not used directly, but used in a difference mode. This mode was based on the computed shift differences for corresponding carbons on the two oligomers where these differences were applied to the experimental shifts of the main iPP peaks with the same chemical identity. The assignment of the defect resonances, along with the loss of chemical shift equivalences seen in solution-state spectra, was also rationalized in the context of γ-gauche and vicinal−gauche interactions as applied to the 31 helical structure. Defect line width differences that parallel the line width differences of the main iPP resonances also aid in assigning the defect resonances to particular types of carbons. Over the range of ethylene concentrations studied herein, the partitioning coefficient, P CR(eth), given by the ratio of the concentration of ethylene residues in the CR region to the sample-average concentration of ethylene residues, is found to be constant, taking a value of 0.42 with a standard uncertainty of 0.03. On the basis of measurements of the NMR crystallinities, this partitioning translates to a fraction of the total ethylene residues in CR regions ranging from 0.24 to 0.30 and an average concentration of ethylenes in the NC region about twice the overall concentration. We also looked for evidence that the ethylene residues become highly concentrated at the CR/NC interface. While we cannot say whether this is happening on the NC side of the interface, since we cannot identify any NC defect resonances, we can claim that a high concentration of et...