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Linear Rheology of a Series of Second-Generation Dendronized Wedge Polymers

Qian, Zhiyuan and Koh, Yung P. and Pallaka, Madhusudhan R. and Chang, Alice B. and Lin, Tzu-Pin and Guzmán, Pablo E. and Grubbs, Robert H. and Simon, Sindee L. and McKenna, Gregory B. (2019) Linear Rheology of a Series of Second-Generation Dendronized Wedge Polymers. Macromolecules, 52 (5). pp. 2063-2074. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20190225-152923058

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Abstract

A series of second-generation dendronized wedge polymers were synthesized by ring-opening metathesis polymerization, and the linear viscoelastic response over a wide range of temperatures was investigated. From 0 to 90 °C the dynamic moduli (G′(ω) and G″(ω)) were determined, and frequency–temperature superposition was used to create master curves that showed behavior from the terminal zone to the glassy regime. An apparent extremely low rubbery plateau of ∼10 kPa was observed in both the dynamic response and in the corresponding van Gurp–Palmen plot. However, further investigation shows that the apparent rubbery plateau is related to the steady-state recoverable compliance, not the onset of entanglements. In addition, these wedge polymers exhibit an extremely low glassy modulus of ∼100 MPa at 0 °C, which is shown to increase at 1 Hz to ∼700 MPa at −80 °C for the wedge polymer 2G-EHW-311. In addition, both small- and wide-angle X-ray scattering patterns were obtained for all of the polymers investigated, and these showed that the polymer molecules adopt an extended cylinder conformation. Furthermore, based on calorimetric measurements, the polymers were found to exhibit two glass transition temperatures, with a 100 K difference between the higher (T_(g,hi) = 26.8 ± 0.7 °C) and lower glass transition temperatures (T_(g,lo) = −76.1 ± 1.1 °C) for the 2G-EHW-311 material. Hence, an intermediate regime extends to well below the T_(g,hi) to T_(g,lo), providing an explanation for the low glassy modulus of ∼100 MPa at 0 °C and its increase to ∼700 MPa when measured at T_(g,hi) – 100 °C and approaching the T_(g,lo).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.macromol.8b02122DOIArticle
ORCID:
AuthorORCID
Chang, Alice B.0000-0001-5036-2681
Lin, Tzu-Pin0000-0001-7041-7213
Grubbs, Robert H.0000-0002-0057-7817
Simon, Sindee L.0000-0001-7498-2826
McKenna, Gregory B.0000-0002-5676-9930
Additional Information:© 2019 American Chemical Society. Received: October 4, 2018; Revised: February 18, 2019; Published: February 25, 2019. Z.Q. and G.B.M. thank the Texas Tech University Graduate School and the John R. Bradford endowment at Texas Tech University, each for partial support of the project. S.L.S. and M.R.P. thank the National Science Foundation under Grant DMR-1610614 for partial support for the project. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Texas Tech UniversityUNSPECIFIED
NSFDMR-1610614
Issue or Number:5
Record Number:CaltechAUTHORS:20190225-152923058
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190225-152923058
Official Citation:Linear Rheology of a Series of Second-Generation Dendronized Wedge Polymers. Zhiyuan Qian, Yung P. Koh, Madhusudhan R. Pallaka, Alice B. Chang, Tzu-Pin Lin, Pablo E. Guzmán, Robert H. Grubbs, Sindee L. Simon, and Gregory B. McKenna. Macromolecules 2019 52 (5), 2063-2074. DOI: 10.1021/acs.macromol.8b02122
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93237
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Feb 2019 23:39
Last Modified:03 Oct 2019 20:52

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