SYNOPSISA new technique to analyze the short-chain branching distribution (SCBD) in linear lowdensity polyethylene has been developed. The technique referred as crystallization analysis fractionation is based on a stepwise precipitation approach. By monitoring the polymer solution concentration during crystallization, the cumulative and differential SCBD can be obtained without the need of physical separation of fractions. The new technique has been shown to provide similar results to temperature rising elution fractionation but in a shorter time and with a simplified apparatus. It allows the simultaneous analysis of various samples and could also be used for analysis of polypropylene and other semicrystalline polymers that can be fractionated on the basis of crystallizability. 0 1994 John Wiley & Sons, Inc.

Summary: New crystallization procedures have been developed for the analysis of the chemical composition distribution in polyolefins by pumping a small flow of solvent during the crystallization cycle. One of the new techniques, crystallization elution fractionation (CEF) combines the separation power of TREF and CRYSTAF and has been shown to provide very fast analysis of the composition distribution.

Summary: The chemical composition distribution has been shown to be the most critical and discriminating parameter in understanding the performance of industrial polyolefins with non homogeneous comonomer incorporation. The chemical composition distribution is being analyzed by well known techniques such as temperature rising elution fractionation, TREF, crystallization analysis fractionation, CRYSTAF and crystallization elution fractionation, CEF. These techniques separate according to crystallizability and provide a powerful and predictable separation of components based on the presence of branches, irregularities or tacticity differences, independently of the molar mass. TREF, CRYSTAF and CEF can not be used, however, for the separation of more amorphous resins, and may not always provide the best solution for complex multi‐component resins due to the existence of some co‐crystallization. The application of high temperature interactive HPLC to polyolefins opened a new route to characterize these types of polymers. The use of solvent gradient HPLC for separation of polyethylene and polypropylene and the developments in HPLC on carbon based columns extended further the application of high temperature HPLC in polyolefins. A new approach has been developed recently using the carbon based column but replacing solvent gradient by a thermal gradient which facilitates the analysis of polyethylene copolymers and provides a powerful tool for the analysis of elastomers. Thermal gradient interaction chromatography (TGIC) is being compared with TREF and CEF with the analysis of model samples. The advantages/disadvantages of each technique are being investigated and discussed. The combination of TGIC and TREF/CEF provides an extended range of separation of polyolefins.

Summary Since the introduction of high temperature interaction chromatography for the analysis of polyolefins the technique has demanded a particular interest in the analysis of elastomers where crystallization techniques will meet a limitation given the low crystallinity of these polymers. In this paper the introduction of non carbon adsorption supports such as molybdenum sulfide, boron nitride and tungsten sulfide with equivalent separation to graphitized carbon packing in TGIC analysis of polyolefins is presented. A mechanism for the separation of polyolefins by adsorption chromatography on layered substrates is proposed. The influence of solvent polarity in interaction chromatography is discussed.

Systematic investigation on the compositional heterogeneity, phase structure, the crystallization and subsequent melting behavior of two commercial in-reactor alloys EB-P and EP-P (ethylene-co-butylene polypropylene and ethylene-co-propylene polypropylene) from Basell were conducted. The composition of the alloys and the chain structure of each component were characterized by combinatorial using of preparative TREF and 13 C NMR technique. The compositional heterogeneities of both samples were further studied by SSA technique, and possible thermal fractionation mechanisms were then inferred. Correlations between the mechanical properties and the molecular architectures and phase structures were discussed. The results show that the excellent balance between toughness and rigidity of sample EB-P primarily benefits from the crystalline polyethylene homopolymer (HPE) phase and the amorphous ethylene-R-olefin copolymer (EC) component, which is proved to be enriched at the interface between the dispersed polypropylene homopolymer phase (HPP) and the matrix (HPE). As for EP-P sample, the very high amorphous EC content, and the homogeneous and interpenetrating cocontinuous phase structure in the alloy are considered to be mainly responsible for the outstanding low-temperature impact toughness.