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Molecular chain heterogeneity of a branched polyethylene resin using cross-fractionation techniques

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Abstract

The typical standard long chain branching (LCB) polyethylene (PE) SRM1476 is issued by the American National Bureau of Standards, which is widely used as a standard reference material in chromatographic experiments. Although some works have been reported in literatures, they are not consistent, such as the data about its molecular weight and molecular weight distribution. Therefore, it is necessary to further investigate the microstructure features of SRM1476 in order to better serve as a reference object in comparison with other unknown resins. In this study, the molecular chain heterogeneity of SRM1476 is investigated extensively and compared with the linear PE SRM1475. Based on the characterization of the original sample, SRM1476 actually has both LCB and short chain branching (SCB) structures, as well as the SCB content is more than LCB content in 13C-NMR results. After successive self-nucleation and annealing (SSA) thermal fractionation, SRM1476 shows a broad-range endotherm with multiple melting peaks (more than eight peaks), which proves the molecular chain heterogeneity in SRM1476. SRM1476 is fractionated into nine fractions by preparative temperature rising elution fractionation (TREF). At the high elution temperature region, the amounts of fractions are more than 90 %, and their molecular weights are higher. At the low elution temperature region below 50 °C, molecular weights of fractions are lower and their amounts are less than 5 %. Differential scanning calorimetry (DSC) melting curves of TREF fractions with higher elution temperatures shift toward higher temperature with sharper melting peaks. In the results of TREF-SSA cross-fractionation, each fraction shows a broad-range endotherm with multiple melting peaks that shift toward the high elution temperature region with the elution temperature. The arithmetic mean methylene sequence lengths of TREF fractions gradually increase from 33 to 105 as elution temperature increases. Results from TREF-DSC and TREF-SSA cross-fractionations indicate that SRM1476 and its TREF fractions have both intramolecular and intermolecular heterogeneity.

The typical long chain branching PE SRM1476 is studied extensively using different cross-fractionation methods, which actually contains both LCB and SCB structures. Moreover, it is found that TREF can separates semi-crystalline polymers according to short branching chains, but also has a certain separating ability for long branching chains. The cross-fractionation methods from the combination of TREF with other techniques are very effective approaches in studying molecular chain heterogeneities of branched PE resins.

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Acknowledgments

This study was supported by the National Basic Research Program of China (2005CB623806) and National Natural Science Foundation of China (20734006, 50921062).

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  1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Yanhu Xue, Shuqin Bo & Xiangling Ji

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  1. Yanhu Xue
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  2. Shuqin Bo
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  3. Xiangling Ji
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Correspondence to Xiangling Ji.

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Xue, Y., Bo, S. & Ji, X. Molecular chain heterogeneity of a branched polyethylene resin using cross-fractionation techniques. J Polym Res 22, 160 (2015). https://doi.org/10.1007/s10965-015-0809-0

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