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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Rheology of Crystallizing LLDPE.

Marat Andreev1, David Nicholson1, Anthony Kotula2

  • 1Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA.

Journal of Rheology
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Summary

This study models polymer crystallization in linear low-density polyethylene (LLDPE) using rheology and Raman spectroscopy. A slip-link model, incorporating dangling segments, accurately captures viscosity and elasticity changes during LLDPE crystallization.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Rheology

Background:

  • Polymer crystallization is crucial in plastic manufacturing.
  • Linear low-density polyethylene (LLDPE) properties are tunable via short-chain branching (SCB).
  • Understanding LLDPE crystallization dynamics is key for process optimization.

Purpose of the Study:

  • To simultaneously measure rheology and Raman spectra during LLDPE crystallization.
  • To model the rheological behavior of entangled LLDPE melts as a function of crystallinity.
  • To refine the slip-link model for entangled polymers with SCB.

Main Methods:

  • Utilized a Rheo-Raman microscope for simultaneous measurements.
  • Employed a slip-link model to describe rheological behavior.
  • Characterized industrial-grade LLDPEs with broad polydispersity and SCB.

Main Results:

  • The slip-link model was adapted to include dangling segments for LLDPE.
  • The modified model quantitatively captured viscosity and elasticity evolution with crystallization.
  • Model successfully described rheological data across the linear regime for two LLDPE grades.

Conclusions:

  • The slip-link model, with modifications, effectively describes LLDPE crystallization.
  • Dangling segments are necessary to accurately model rheology in branched polymers like LLDPE.
  • This approach provides quantitative insights into polymer melt behavior during processing.