Physically cross-linked semicrystalline properties

PE-PEP diblock were similar to each other at high PE content (50-90%). This was because the mechanical properties were determined predominantly by the behaviour of the more continuous PE phase. For lower PE contents (7-29%) there were major differences in the mechanical properties of polymers with different architectures, all of which formed a cubic-packed sphere phase. PE-PEP-PE triblocks were found to be thermoplastic elastomers, whereas PEP-PE-PEP triblocks behaved like particulate filled rubber.The difference was proposed to result from bridging of PE domains across spheres in PE-PEP-PE triblocks, which acted as physical cross-links due to anchorage of the PE blocks in the semicrystalline domains. No such arrangement is possible for the PEP-PE-PEP or PE-PEP copolymers (Mohajer et al. 1982). 

The thermoplastic IPNs utilize physical cross-links, rather than chemical crosslinks. Usually, these materials will flow when heated to sufficiently high temperature (hence the terminology thermoplastic), but behave as thermosets at ambient temperature, with IPN properties, often possessing dual-phase continuity. Most often, physical cross-links are based on triblock copolymers (thermoplastic elastomers being the leading material), ionomers, or semicrystalline materials. 

Neutralization of ethylene copolymers containing up to 5%-10% acrylic or methacryUc acid copolymer with a metal salt such as the acetate or oxide of zinc, magnesium, and barium yields products referred to as ionomers. (Commercial products may contain univalent as well as divalent metal salts.) lonomers are marked by Du Pont under the trade name Surlyn. These have interesting properties compared with the nonionized copolymer. Introduction of ions causes disordering of the semicrystalline structure, which makes the polymer transparent. lonomers act like reversibly cross-linked thermoplastics as a result of microphase separation between ionic metal carboxylate and nonpolar hydrocarbon segments. The behavior is similar to the physical cross-linking in thermoplastic elastomers (see Chapter 1 of Industrial... 

The ability of the E-plastomers to participate in the peroxide-mediated chain-extension processes can be augmented in blends with EPDM, where the mixture is homogeneously cross-linked with free radicals [5]. The use of these blends of EPDM and E-plastomers leads to improved processing and physical properties of the combination, compared to the EPDM alone, though the resulting vulcanizates are somewhat harder than the EPDM vulcanizates alone due to the presence of the semicrystalline plastomers in the vulcanized mixture. 

Presently, some hybrid polyblends, such as the thermoplastic apparent interpenetrating polymer networks (AIPNs), call for a broader view, hi contrast to traditional IPNs, in thermoplastic AIPNs the components are cross-linked by means of physical, instead of chemical, bonds. These physical bonds are glassy domains of block copolymers, ionic clusters in ionomers, or crystalline domains in semicrystalline polymers. The components of thermoplastic AIPNs are capable of forming physical networks and are characterized by mutual penetration of phases. Thermoplastic AIPNs are intermediate between mixtures of linear polymers and true IPNs because they behave like chemically cross-Unked polymers at relatively low temperatures, but as thermoplastics at elevated temperature [208]. The blends based on combinations of physically cross-Unked polymer and Unear polymer, or physicaUy cross-Unked polymer and chemically cross-Unked (thermoset) polymer, where the physically cross-Unked polymer network constitutes the continuous phase and the other component disperses into domains, will also exhibit the properties of thermoplastic compositions. 

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