Collaborative Research: Synthesis and Theology of Strategically-Designed Long-Chain-Branched Polymers

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TECHNICAL SUMMARY Understanding remains incomplete regarding the relaxation of complex branching structures in entangled polymer melts with multiple branch points, such as H- or comb-branched polymers, or for polymers with branches of differing lengths, such as asymmetric stars and asymmetric H polymers, or for hyperbranched polymers (i.e., with branch-on-branch topology). To address these issues, which are important both scientifically and for applications to commercial polymer manufacture, we are performing a combination of the following tasks: 1. Synthesis of high-quality model branched polymers with branches of the same or different length that are carefully designed to test physical theories. 2. Careful characterization of the molecular weight and branching properties of these polymers. 3. Measurement of the linear rheological properties over a wide frequency range. 4. Comparison of the measured viscoelastic properties with predictions derived from the various alternative proposed theories. We plan to accomplish these tasks through a collaborative framework, involving a collaborator, Jimmy Mays, who will use a novel route to synthesize 1) asymmetric H polymers; 2) asymmetric star-on-star polymers, based on a core star polymer, each branch of which terminates in two unequal length branches; and 3) combs with tetrafunctional branch points. These polymers will be carefully characterized by gel permeation chromatography and TGIC, and studied through rheological measurements, including careful long-time creep rheometry with the help of instrumentations and methods available in the laboratory of Prof. John Dealy, a collaborator at McGill University. Existing computational models for predicting the measured rheology will be employed in collaboration with Chinmay Das in the McLeish group at Leeds University. NON-TECHNICAL SUMMARY:To form advanced plastic fibers or thin plastic sheets used for packaging, molten plastic is pulled or stretched at extremely high speeds. The performance of this process depends on how the polymer molecules in the plastic are entangled with each other, and how they escape those entanglements. Polymers that branch into multiple long strands are exceptionally useful for industry, since they serve as netting that strengthens the plastic so that it does not rip or bursting when blown into shape. Larson?s team has found that changes to as few one branch in a million branch points can significantly impact the properties of the melt relevant to its strength as a melt. The reason for this is that branched polymers entangle extremely well with other branched polymers. To escape these entanglements, they must reconfigure by reeling branches towards the branch point, like Houdini dislocating his shoulder to escape a straight jacket. Therefore, the entanglements are long-lived and make the plastic easier to shape. Larson?s team is chemically synthesizing special branched polymers that are exceptionally useful in determining how branched polymers manage to perform their ?Houdini? acts and how to optimize this for advanced performance. Their measurements of the rates at which polymers escape entanglements is providing knowledge that is of great interest to collaborators at Dow Chemical Company and other plastics manufacturing companies. The research has been highly interdisciplinary and international with collaborators at the University of Tennessee, McGill University, the University of Leeds, and Dow Chemical Company.