ABSTRACT:This study compared a series of experimental propylene/ethylene copolymers synthesized by a transition metal-based, postmetallocene catalyst (xP/E) with homogeneous propylene/ethylene copolymers synthesized by conventional metallocene catalysts (mP/E). The properties varied from thermoplastic to elastomeric over the broad composition range examined. Copolymers with up to 30 mol % ethylene were characterized by thermal analysis, density, atomic force microscopy, and stress-strain behavior. The xP/Es exhibited noticeably lower crystallinity than mP/Es for the same comonomer content. Correspondingly, an xP/E exhibited a lower melting point, lower glass transition temperature, lower modulus, and lower yield stress than an mP/E of the same comonomer content. The difference was magnified as the comonomer content increased. Homogeneous mP/Es exhibited space-filling spherulites with sharp boundaries and uniform lamellar texture. Increasing comonomer content served to decrease spherulite size until spherulitic entities were no longer discernable. In contrast, axialites, rather than spherulites, described the irregular morphological entities observed in xP/Es. The lamellar texture was heterogeneous in terms of lamellar density and organization. At higher comonomer content, embryonic axialites were dispersed among individual randomly arrayed lamellae. These features were characteristic of a copolymer with heterogeneous chain composition.
Miscibility of homogeneous propylene/ethylene (P/E) copolymers of relatively narrow molecular weight distribution was studied as a function of constituent comonomer content. Polymers with up to 31 mol % ethylene were blended in pairs in order to vary the comonomer content difference. Binary blends were rapidly quenched from the melt to retain the phase morphology, and the phase volume fractions were obtained from AFM images. Copolymers of molecular weight about 200 kg mol-1 were miscible if the difference in ethylene content was less than about 18 mol % and immiscible if the ethylene content difference was greater than about 20 mol %. Blends with constituent composition difference in the range of 18−20 mol % exhibited partial miscibility in the melt as indicated by a phase volume fraction that was different from the blend volume fraction. The temperature dependence of blend morphology confirmed the UCST behavior of P/E copolymer blends. The phase composition and the χ interaction parameter were extracted by using an approach that considered the molecular weight distribution. The compositional dependence of χ conformed to the copolymer equation and depended on comonomer content difference only, not on comonomer content per se.
The elastic behavior of a propylene-ethylene copolymer was investigated. An initial ''conditioning'' tensile extension up to 800% strain resulted in an elastomer with low initial modulus, strong strain hardening, and complete recovery over many cycles. Structural changes that occurred in the low crystallinity propylene-ethylene copolymer during conditioning, and that subsequently imparted elastomeric properties to the conditioned material, were investigated. Thermal analysis, wide and small angle X-ray diffraction, and atomic force microscopy measurements were performed at various strains during the conditioning process. Conditioning transformed crystalline lamellae into shish-kebab fibers by melting and recrystallization. The fibers, accounting for only 5% of the bulk, were interconnected by a matrix of entangled, amor-phous chains that constituted the remaining 95%. It was proposed that the shish-kebab fibers acted as a scaffold to anchor the amorphous rubbery network. Entanglements of the amorphous chain segments acted as network junctions and provided the elastic response. The stress-strain response of materials conditioned to 400% strain or more was described by the classical rubber theory with strain hardening. The extracted value of M c , the molecular weight between network junctions, was intermediate between the entanglement molecular weights of polypropylene and polyethylene.
Recent advances in catalyst technology make it possible to synthesize high molecular weight propylene copolymers with a high degree of isotacticity and high levels of an α-olefin comonomer. The primary objective of this study is to systematically characterize the rubbery amorphous phase of propylene/ethylene (P/E) copolymers over a range in comonomer content. A series of new experimental P/E copolymers prepared with a group IV transition metal-based post-metallocene catalyst are compared with a series of P/E copolymers prepared with a conventional metallocene catalyst. Positron annihilation lifetime spectroscopy (PALS) is used to obtain the temperature dependence of the free volume hole size. The PALS measurements are supplemented with bulk volume−temperature measurements. It is found that the free volume hole size and the amorphous phase density at ambient temperature strongly depend on crystallinity. Densification of the amorphous phase is attributed to constraint imposed on rubbery amorphous chain segments by attached chain segments in crystals. It is now possible to attribute the reported discrepancy between conventional measurements of crystallinity from density and crystallinity from heat of melting to the crystallinity dependence of the amorphous phase density. The fractional free volume (FFV) of the amorphous phase is obtained by combining the free volume hole size with the macroscopic volume−temperature measurement. At the glass transition temperature the FFV is constant across the crystallinity range of the P/E copolymers with a value of about 0.04, in agreement with iso-free volume concepts of the glass transition.
A series of particulate composites based on a new family of propylene/ethylene (P/E) copolymers produced by Dow Chemical Co. were studied with microscopy and differential scanning calorimetry (DSC). To understand the good processability exhibited by the composites, we studied the composite microstructure and the bulk rheological properties. Here we report the results of a study of the microstructure and thermal behavior. Electron micrographs of the composites showed a uniform dispersion of the particles in the copolymer matrices at all experimental concentrations with very little particle agglomeration. The images suggested low adhesion between the matrices and the particles. The copolymers were semicrystalline, and their morphologies changed with the ethylene content. An increase in the ethylene content led to a decrease in the crystallinity and changes in the shape and size of the crystallites. Tapping-mode atomic force microcopy images of a 9 wt % ethylene copolymer contained spherulites, lamellae, and a crosshatched structure characteristic of a-isotactic polypropylene. The crosshatched structure was not present at higher ethylene contents. A DSC study of the pure copolymers and their composites revealed that only very small modifications to the thermal behavior of the P/E copolymers were induced by calcium carbonate particles.
A stretching process to enhance the stiffness of an elastomeric propylene-ethylene copolymer through orientation was examined. The tensile extension was performed at various temperatures within the unusually broad melting range of the copolymer. Stretching transformed the unmelted lamellar crystals into shishkebab fibers that acted as a scaffold for an elastomeric matrix of entangled, amorphous chains. Density measurements indicated that the process did not significantly affect the amount of crystallinity, which was about 23%. If the specimen was recrystallized by cooling after it recovered from the stretched state, the amount of orientation decreased with increasing stretching temperature. How-ever, if recrystallization occurred in the stretched state, it led to the formation of a second crystalline network that prevented contraction of the oriented crystalline structure during strain recovery. It was suggested that the second network was anchored by a 0 -PP daughter lamellae that crystallized epitaxially on the a-PP mother crystals of the extended fibrils. Although the manner in which the films were stretched and recrystallized strongly affected the modulus, good elasticity of the stretched films revealed the persistence of an elastomeric network.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.