Macromolecules
Article
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CONCLUSION
■
The thermal-induced curing of norbornenyl-functionalized
castor oil with a controlled amount of 0.8 norbornene rings
per fatty acid chain via ROMP was investigated rheologically
under different curing time, temperature, and angular frequency
conditions.
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A dramatic increase in the viscoelastic material functions (G′,
G″, and η*) at the onset of the ROMP process was observed
during the dynamic temperature ramp experiments. The
temperature dependence of zero-shear viscosity, η0, was
found to follow the same trend as the one observed in the
temperature ramps of G′ and G″ (i.e., a dramatic increase in η0
is observed at Tgel). The Tgel determined by the crossover point
of G′ and G″ was in good agreement with the value obtained
from the temperature dependence of η0. The real-time
evolution of the ROMP process of NCO was also investigated
by measuring G′, G″, η*, and tan δ at constant different
temperatures (40, 45, 50, and 55 °C) and angular frequencies.
The value of tgel determined by the time dependence of tan δ
(the point at which all curves of tan δ coincide and are angular
frequency independent) was found to be applicable over a wide
range of angular frequencies according to the Winter−
Chambon method and identical to the value obtained from
the crossover point of G′ and G″. Furthermore, both G′ and G″
were found to follow a power law behavior as a function of
angular frequency (G′ ∼ G″ ∼ ωn) with exponents n′ and n″
that are strongly dependent on curing time in good agreement
with that predicted theoretically based on the percolation
theory. Both η0 and Geq were also expressed in power law
scaling functions with the relative distance from the gel point,
η0 ∼ ε−k and Geq ∼ εz with k = 0.75 and z = 2.1. The value of
the exponent n obtained from the slopes k and z is 0.73, in
close agreement with the value predicted theoretically from the
percolation theory (n = 2/3). The cured sample was thermally
stable up to 200 °C and showed only one α-relaxation process
as confirmed by TGA and DMA measurements, respectively.
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AUTHOR INFORMATION
■
(36) Adolf, D.; Martin, J. R.E. Macromolecules 1991, 24, 6721−6724.
(37) Zhao, Y.; Cao, Y.; Yang, Y.; Wu, C. Macromolecules 2003, 36,
855−859.
Corresponding Author
Notes
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The authors declare no competing financial interest.
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̈
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dx.doi.org/10.1021/ma301458n | Macromolecules 2012, 45, 7729−7739