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Two Chain-Packing Transformations and Their Effects on the Molecular Dynamics and Thermal Properties of α‑Form Isotactic Poly(propylene) under Hot Drawing: A Solid-State NMR Study
journal contribution
posted on 2014-05-13, 00:00 authored by Jia Kang, Toshikazu MiyoshiThe chain packing, crystal thickness,
molecular dynamics, and melting
temperature of α-form isotactic polypropylene
(iPP) drawn uniaxially at high temperatures of 100–150
°C were investigated using solid-state (SS) NMR and DSC. Two
types of iPP samples with disordered (α1) and relatively ordered (α2-rich) packing
structures were prepared via different thermal treatments and drawn
up to an engineering strain (e) of approximately
20. High-resolution 13C NMR detected continuous α2 → α1 transformations in the original
α2-rich samples over the entire deformation range
at all drawing temperatures (Tds). A sudden
α1 → α2 transformation was
found to occur in the original α1 sample in the small e range of approximately 3–7 at Td = 140 °C. Then, in the late stage, the newly grown
α2 structure reversely transformed into α1 structure with further increase in e, as
observed in the original α2-rich sample. These results
indicate that at least two different processes are involved in large
deformations. On the basis of crystallographic constraints, the continuous
α2 → α1 transformation over
the entire deformation range is attributed to molecular-level melting
and recrystallization facilitated by chain diffusion. The steep α1 → α2 transformation in the smaller e range is assigned to isotropic melting and recrystallization
induced by stress. After the large deformations (e ≈ 20) of the original α2-rich and α1 samples at Td = 150 and 140 °C,
respectively, 1H spin diffusion verified increases in the
crystal thickness in both the former (14.1 at e =
0 → 20.1 nm at e = 20) and the latter (9.2
→ 17.0 nm). Centerband-only detection of exchange (CODEX) NMR
at 120 °C demonstrated that the correlation time (⟨τc⟩) of the helical jump for the former drastically decreased
from ⟨τc⟩ = 52.4 ± 5.2 at e = 0 to 9.3 ± 1.8 ms at e = 20 but
slightly increased from 4.2 ± 1.3 to 7.1 ± 0.9 ms for the
latter. Additionally, DSC indicated that the melting temperature (Tm) for the former decreased considerably from
173 °C at e = 0 to 165 °C at e = 20, whereas the melting temperature (Tm) remained nearly invariant at 163 °C for the latter. On the
basis of these findings, we conclude that the local packing structure
plays a crucial role in determining the molecular dynamics of the
stems and Tm of largely deformed iPP materials. The established relations among the structures,
the dynamics, and the thermal properties provide a useful guide to
achieving improved properties of iPP materials under
processing.