TY - JOUR
T1 - Impact of dynamic covalent chemistry and precise linker length on crystallization kinetics and morphology in ethylene vitrimers
AU - Soman, Bhaskar
AU - Go, Yoo Kyung
AU - Shen, Chengtian
AU - Leal, Cecilia
AU - Evans, Christopher M.
N1 - Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2022/1/14
Y1 - 2022/1/14
N2 - Vitrimers, dynamic polymer networks with topology conserving exchange reactions, have emerged as a promising platform for sustainable and reprocessable materials. While prior work has documented how dynamic bonds impact stress relaxation and viscosity, their role on crystallization has not been systematically explored. Precise ethylene vitrimers with 8, 10, or 12 methylene units between boronic ester junctions were investigated to understand the impact of bond exchange on crystallization kinetics and morphology. Compared to linear polyethylene which has been heavily investigated for decades, a long induction period for crystallization is seen in the vitrimers ultimately taking weeks in the densest networks. An increase in melting temperatures (Tm) of 25-30 K is observed with isothermal crystallization over 30 days. Both C10 and C12 networks initially form hexagonal crystals, while the C10 network transforms to orthorhombic over the 30 day window as observed with wide angle X-ray scattering (WAXS) and optical microscopy (OM). After 150 days of isothermal crystallization, the three linker lengths led to double diamond (C8), orthorhombic (C10), and hexagonal (C12) crystals indicating the importance of precision on final morphology. Control experiments on a precise, permanent network implicate dynamic bonds as the cause of long-time rearrangements of the crystals, which is critical to understand for applications of semi-crystalline vitrimers. The dynamic bonds also allow the networks to dissolve in water and alcohol-based solvents to monomers, followed by repolymerization while preserving the mechanical properties and melting temperatures.
AB - Vitrimers, dynamic polymer networks with topology conserving exchange reactions, have emerged as a promising platform for sustainable and reprocessable materials. While prior work has documented how dynamic bonds impact stress relaxation and viscosity, their role on crystallization has not been systematically explored. Precise ethylene vitrimers with 8, 10, or 12 methylene units between boronic ester junctions were investigated to understand the impact of bond exchange on crystallization kinetics and morphology. Compared to linear polyethylene which has been heavily investigated for decades, a long induction period for crystallization is seen in the vitrimers ultimately taking weeks in the densest networks. An increase in melting temperatures (Tm) of 25-30 K is observed with isothermal crystallization over 30 days. Both C10 and C12 networks initially form hexagonal crystals, while the C10 network transforms to orthorhombic over the 30 day window as observed with wide angle X-ray scattering (WAXS) and optical microscopy (OM). After 150 days of isothermal crystallization, the three linker lengths led to double diamond (C8), orthorhombic (C10), and hexagonal (C12) crystals indicating the importance of precision on final morphology. Control experiments on a precise, permanent network implicate dynamic bonds as the cause of long-time rearrangements of the crystals, which is critical to understand for applications of semi-crystalline vitrimers. The dynamic bonds also allow the networks to dissolve in water and alcohol-based solvents to monomers, followed by repolymerization while preserving the mechanical properties and melting temperatures.
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U2 - 10.1039/d1sm01288f
DO - 10.1039/d1sm01288f
M3 - Article
C2 - 34913939
AN - SCOPUS:85122952130
SN - 1744-683X
VL - 18
SP - 293
EP - 303
JO - Soft Matter
JF - Soft Matter
IS - 2
ER -