Characterization of Polymers by GPC-LALLS. III. Branching Structure of EPDM

Abstract

Abstract Gamma ray-irradiated EPM's, as the model polymers of branched EPDM, are investigated using the relationship g′=gb, where g′ is the ratio of intrinsic viscosities of the branched and the linear molecules of equal molecular weight, [η]br/[η]l, and g, the ratio of the mean square radii of gyration of the two, 〈s2〉br/〈s2〉l. The molecular weight distributions measured by GPC-LALLS coincide well with theoretical curves of tetrafunctionally and statistically branched polymers obtained by the ideal degradation and crosslinking of the raw EPM, which was assumed to have the most probable molecular weight distribution, and the b-value is then determined to be 1.1. EPDM samples, polymerized with a soluble vanadium compound—alkyl aluminum halide type catalyst in a continuous well-stirred pilot-reactor, are characterizedas to the number of branching points per molecule for various molecular weights by using the b-value. The higher the molecular weight, the smaller the distance between neighboring crosslinking points. The reason is discussed. The unsaturated bond of dicyclopentadiene crosslinks more readily in the manufacturing process than 5-ethylidene-2-norbornene. The largest high molecular weight portion and the broadest molecular weight distribution are observed in the EPDM with the maximum dicyclopentadiene content.