Terminal and Internal Unsaturations in Poly(ethylene-<i>co</i>-1-octene)

Unsaturated structures in polyolefin polymers are important in many respects. In this work, new vinyl and vinylidene structures were identified in poly­(ethylene-<i>co</i>-1-octene) copolymers. The combination of careful sample selection and model compounds provided clear evidence for the assignment of these structures. More importantly, a new method was developed to differentiate and quantify for the first time terminal and internal unsaturations in ethylene-<i>co</i>-1-octene copolymers. The method described here will be generally applicable to many different polyolefins

Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors

Chemical composition distribution (CCD) is a fundamental metric for representing molecular structures of copolymers in addition to molecular weight distribution (MWD). Solvent gradient interaction chromatography (SGIC) is commonly used to separate copolymers by chemical composition in order to obtain CCD. The separation of polymer in SGIC is, however, not only affected by chemical composition but also by molecular weight and architecture. The ability to measure composition and MW simultaneously after separation would be beneficial for understanding the impact of different factors and deriving true CCD. In this study, comprehensive two-dimensional chromatography (2D) was coupled with infrared absorbance (IR5) and light scattering (LS) detectors for characterization of ethylene–propylene copolymers. Polymers were first separated by SGIC as the first dimension chromatography (D1). The separated fractions were then characterized by the second dimension (D2) size exclusion chromatography (SEC) with IR5 and LS detectors. The concentrations and compositions of the separated fractions were measured online using the IR5 detector. The MWs of the fractions were measured by the ratio of LS to IR5 signals. A metric was derived from online concentration and composition data to represent CCD breadth. The metric was shown to be independent of separation gradients for an “absolute” measurement of CCD breadth. By combining online composition and MW data, the relationship of MW as a function of chemical composition was obtained. This relationship was qualitatively consistent with the results by SEC coupled to IR5, which measures chemical composition as a function of logMW. The simultaneous measurements of composition and MW give the opportunity to study the SGIC separation mechanism and derive chain architectural characteristics of polymer chains