Premium
Impact of Dynamic Bond Concentration on the Viscoelastic and Mechanical Properties of Dynamic Poly(alkylurea‐ co ‐urethane) Networks
Author(s) -
Chen Lifeng,
Zhang Longhe,
Griffin Philip J.,
Rowan Stuart J.
Publication year - 2020
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201900440
Subject(s) - viscoelasticity , covalent bond , stress relaxation , dynamic mechanical analysis , polymer chemistry , materials science , rheometry , polymer , relaxation (psychology) , isocyanate , dynamic covalent chemistry , chemical engineering , chemistry , composite material , organic chemistry , molecule , polyurethane , supramolecular chemistry , creep , psychology , social psychology , engineering
Polymer networks containing dynamic covalent bonds do not exhibit traditional thermoset material properties. Such dynamic covalent networks have the ability to undergo stress relaxation processes associated with dynamic covalent bond exchange, imparting these materials with adaptive/responsive properties. Reported herein is an investigation on the effect that changing the amount of dynamic hindered alkylurea bonds has on the viscoelastic behavior of a series of poly(alkylurea‐ co ‐urethane) networks prepared by reacting a trifunctional isocyanate crosslinker with varying ratios of an N ‐isopropyl amine endcapped poly(propylene glycol) and a poly(propylene glycol). Films that contain >50% dynamic alkylurea bonds (wrt. alkylurea + urethane bonds) exhibit facile reprocessability, while those films with <50% dynamic alkylurea bonds exhibit poor reprocessability under these same conditions. Analysis of the temperature‐dependent shear rheometry and uniaxial stress relaxation measurements demonstrates that the primary stress relaxation mode in these materials is linked to the dynamic bond exchange process. Interestingly, these films exhibit an increasingly rich viscoelastic spectrum with increasing fraction of non‐dynamic urethane bonds. In addition to the primary relaxation process an order‐of‐magnitude slower relaxation emerges, which is identified as being related to the relaxation of larger, permanently crosslinked polymeric clusters in an otherwise dynamic matrix.