P-plastomers

Structurally, plastomers straddle the property range between elastomers and plastics. Plastomers inherently contain some level of crystallinity due to the predominant monomer in a crystalline sequence within the polymer chains. The most common type of this residual crystallinity is ethylene (for ethylene-predominant plastomers or E-plastomers) or isotactic propylene in meso (or m) sequences (for propylene-predominant plastomers or P-plastomers). Uninterrupted sequences of these monomers crystallize into periodic strucmres, which form crystalline lamellae. Plastomers contain in addition at least one monomer, which interrupts this sequencing of crystalline mers. This may be a monomer too large to fit into the crystal lattice. An example is the incorporation of 1-octene into a polyethylene chain. The residual hexyl side chain provides a site for the dislocation of the periodic structure required for crystals to be formed. Another example would be the incorporation of a stereo error in the insertion of propylene. Thus, a propylene insertion with an r dyad leads similarly to a dislocation in the periodic structure required for the formation of an iPP crystal. In uniformly back-mixed polymerization processes, with a single discrete polymerization catalyst, the incorporation of these intermptions is statistical and controlled by the kinetics of the polymerization process. These statistics are known as reactivity ratios. 

FIGURE 6.1 A set of consistent stress-strain data for P-plastomers with ethylene content between 8.2 wt% (highest) and 16.0 wt% (lowest). The data for P-plastomers with intermediate composition is intermediate within these extremes. 

FIGURE 6.2 Heat of fusion and melting point for a set of P-plastomers made under similar process conditions but with difference in the composition. 

The new polymers are intermediate in composition and crystallinity between the essentially amorphous EPR and the semicrystalhne iPP. The presence of the complementary blocks of elastomers for both ethylene and propylene crystallinity should not indicate a similarity, beyond the levels of the crystallinity in the properties of the E-plastomers and the P-plastomers. The E-plastomers and the P-plastomers differ in their stmctural, rheological, as well as their thermal, mechanical, and elastic properties. In a comparison of the tensile strength and tensile recovery (tension set) from a 100% elongation for a range of P-plastomers and E-plastomers, the former have lower tension set than EPR and iPP. However, for comparative E-plastomers and P-plastomers at equivalent tensile strength, the latter have significantly better tension set. In summary, P-plastomers are tough polyolefins which are uniquely soft and elastic. 

P-plastomers are semicrystalline, elastomeric copolymers composed predominantly of propylene with limited amounts of ethylene [21]. The concentration of ethylene is typicaUy less than 20 wt%. The placement of the propylene residues is predominantly in a stereoregular isotactic manner. This leads to the crystallinity (which is critical) in the copolymer. The extent of the crystallinity is attenuated by errors in the placement of the propylene and by the incorporation of ethylene. These two strucmral feamres contribute to lower the crystallinity, as measured by the heat of fusion, to less than 40 J g . Copolymers of propylene and ethylene, which have higher levels of crystallinity are... 

The melting point of the P-plastomers decreases monotonicaUy with the introduction of ethylene, except at ethylene levels of >12 wt% it shows no further decrease though the heat of fusion does decrease throughout this range. It is believed that these discordant behaviors could be due to either, or both, of the factors given below ... 

The Tg of P-plastomers changes as a function of ethylene content. The Tg decreases with increasing ethylene content, primarily due to an increase in chain flexibility and loss of pendant methyl residues due to incorporation of ethylene units in the backbone. It is well known that PP has a Tg of 0°C, and polyethylene a Tg< —65°C. The addition of ethylene to a propylene polymer would therefore be expected to decrease the Tg, as is observed here. A secondary effect would be the reduction in the level of crystallinity associated with increasing ethylene content, which is expected to reduce the constraints placed upon the amorphous regions in proximity to the crystallites. Thus, an increase in ethylene content will result in a lower T as well as an increase in magnitude and a decrease in breadth of the glass transition. 

P-plastomers provide a unique combination of ease of processing, such that conventional thermoplastic-processing routines and arid equipment can be adapted to this polymer as weU as for a final fabricated product that is elastic. This combination of properties leads to the easy fabrication of elastic materials such as fibers and films, which traditionally have only been made inelastic by the use of thermoplastics. This advance opens the pathway to the introduction of desirable elastic properties to a host of fabrication processes very different from either the conventional rubber-processing equipment or the conventional rubber products, such as tires. P-plastomers and their fabricated products are not only soft, but also elastic. 

P-plastomers, even more than the E-plastomers, have been blended with a number of substrates [23]. The most-important one is blend with iPP which forms compatible blends with P-plastomer for a wide range of relative weights fractions of P-plastomer and iPP as well as a wide range of molecular weights for both of the components. The formation of the blends with iPP leads to changes in the elastic and tensile response with elongation modulus, monotonicaUy increasing with the amount of iPP. 

One of the important aspects of the development of P-plastomers was the expectation that these materials were amenable to plastics processing such as fiber and film formation and yet would yield soft elastic fabrication. This combination was hitherto unknown [24]. The formation of nonwoven fabrics including spun-bond and melt-blown nonwoven fabrics as well as their laminated forms has been documented. Similarly, cast film operation to form elastic monolithic films or composite structures which are not only amenable to these processes, but also to a variety of postfabrication processes have been described. 

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