SynopsisA description is given of an analytical temperature-rising elution fractionation (TREF) system for the purpose of determining short-chain branching (SCB) or copolymer distributions in polyethylenes and ethylene copolymers. The system achieves fractionation on the basis of crystallhbility and is shown to be very little influenced by molecular weight in the normal high polymer range. Sample preparation by slow cooling from relatively dilute solution followed by continuous elution with a simultaneous and fairly rapid rate of temperature rise proves to be an efficient fractionation process. An on-line detector and data system allows application of a calibration curve to give realistic SCB distribution data in a convenient manner. The potential value of the TREF technique for providing structural information is illustrated by examples which include low-density high-pressure resins made by both tubular and autoclave reactors, high-and low-density resins made by lowpressure processes, and copolymers of ethylene with vinyl acetate and ethyl acrylate.

No abstract

Melt How data has been determined for a series of fractionated and whole low density polyethylenes which has been characterized in terms of their molecular weights and degree of long‐chain branching, (LCB). The resulting data indicate that low LCB influences melt flow both through a reduction in molecular size and an increased level of intermolecular interaction. Die swell measurements on whole polymers indicate an increase in melt elasticity with increase in degree of LCB for samples of similar melt flow (MI). Comparison of GPC data with observed die swell characteristics indicates that die swell is a molecular size dependent property and independent of intermolecular entanglement effects, suggesting that the measurement of elastic properties of LDPE melts will provide a means of determining relative degrees of LCB for commercial resins.

A method is described and a computer program outlined whereby gel‐permeation chromatographic analysis of fractions from gradient‐elution fractionation of branched polyethylenes provides a complete molecular weight evaluation of each fraction and the parent resin. The procedure involves the use of the universal calibration concept of Benoit et al. in a way that eliminates the ambiguities present in attempts to apply it directly to whole polymers. The resultant molecular weight data for fractions, when related to their solution viscosity and low‐shear melt viscosity and to their infrared analysis, provides a total structural evaluation of a branched polyethylene resin, including molecular weight molecular weight distribution and the distribution of both long‐and short‐chain branching. The potential of this method for providing a comprehensive structural evaluation of branched polyethylene is illustrated by examples of its application in the analysis of some commercial resins.

The development of a fractional crystallization technique for characterization of polypropylenes with respect to stereoregularity is described. It is a simple technique which is attractive for routine analysis and under suitable conditions yields quantitative data with good reproducibility. Separation by fractional crystallization from hot xylene solution is shown to take place according to polymer crystallizability and is relatively independent of molecular weight. It thus represents an alternative and in some ways superior approach to the more commonly used fractional extraction method. Preliminary work indicates that the fractional crystallization method may prove of value in establishing correlations between the stereoregular nature of polypropylenes and their physical properties.