Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

Ingrid N. Haugan; Michael J. Maher; Alice B. Chang; Tzu Pin Lin; Robert H. Grubbs; Marc A. Hillmyer; Frank S. Bates

doi:10.1021/acsmacrolett.8b00116

Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

Ingrid N. Haugan, Michael J. Maher, Alice B. Chang, Tzu Pin Lin, Robert H. Grubbs, Marc A. Hillmyer, Frank S. Bates

Research output: Contribution to journal › Article › peer-review

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Abstract

The linear viscoelastic behavior of poly(norbornene)-graft-poly(±-lactide) was investigated as a function of grafting density and overall molar mass. Eight sets of polymers with grafting densities ranging from 0 to 100% were synthesized by living ring-opening metathesis copolymerization. Within each set, the graft chain molar mass and spacing between grafts were fixed, while the total backbone length was varied. Dynamic master curves reveal that these polymers display Rouse and reptation dynamics with a sharp transition in the zero-shear viscosity data, demonstrating that grafting density strongly impacts the entanglement molar mass. The entanglement modulus (G_e) scales with inverse grafting density (n_g) as G_e ∼ n_g ^1.2 and G_e ∼ n_g ⁰ in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.

Original language	English (US)
Pages (from-to)	525-530
Number of pages	6
Journal	ACS Macro Letters
Volume	7
Issue number	5
DOIs	https://doi.org/10.1021/acsmacrolett.8b00116
State	Published - May 15 2018

Bibliographical note

Funding Information:
This work was funded by the NSF through the Center for Sustainable Polymers (CHE-1413862) and under award number CHE-1502616. This research used resources of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Part of this work was performed at the DuPont−Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University.

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Copyright © 2018 American Chemical Society.

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abstract = "The linear viscoelastic behavior of poly(norbornene)-graft-poly(±-lactide) was investigated as a function of grafting density and overall molar mass. Eight sets of polymers with grafting densities ranging from 0 to 100% were synthesized by living ring-opening metathesis copolymerization. Within each set, the graft chain molar mass and spacing between grafts were fixed, while the total backbone length was varied. Dynamic master curves reveal that these polymers display Rouse and reptation dynamics with a sharp transition in the zero-shear viscosity data, demonstrating that grafting density strongly impacts the entanglement molar mass. The entanglement modulus (Ge) scales with inverse grafting density (ng) as Ge ∼ ng 1.2 and Ge ∼ ng 0 in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.",

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note = "Funding Information: This work was funded by the NSF through the Center for Sustainable Polymers (CHE-1413862) and under award number CHE-1502616. This research used resources of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Part of this work was performed at the DuPont−Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University. Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

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N2 - The linear viscoelastic behavior of poly(norbornene)-graft-poly(±-lactide) was investigated as a function of grafting density and overall molar mass. Eight sets of polymers with grafting densities ranging from 0 to 100% were synthesized by living ring-opening metathesis copolymerization. Within each set, the graft chain molar mass and spacing between grafts were fixed, while the total backbone length was varied. Dynamic master curves reveal that these polymers display Rouse and reptation dynamics with a sharp transition in the zero-shear viscosity data, demonstrating that grafting density strongly impacts the entanglement molar mass. The entanglement modulus (Ge) scales with inverse grafting density (ng) as Ge ∼ ng 1.2 and Ge ∼ ng 0 in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.

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Consequences of Grafting Density on the Linear Viscoelastic Behavior of Graft Polymers

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