TY - JOUR
T1 - Curing Kinetics of Ultrahigh-Temperature Thermosetting Polyimides Based on Phenylethynyl-Terminated Imide Oligomers with Different Backbone Conformations
AU - Kim, Minju
AU - Khim, Seongjun
AU - Lee, Joon Hyuk
AU - Jeon, Eunkyung
AU - Song, Jungkun
AU - Choi, Jaeho
AU - Yeo, Hyeonuk
AU - Nam, Ki Ho
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/11/8
Y1 - 2024/11/8
N2 - A series of phenylethynyl-terminated imide (PETI) oligomers with varying chemical backbones and calculated number-average molecular weights were successfully synthesized via chemical imidization. These PETI oligomers exhibited exceptional solubility (>50 wt %) in both the high-boiling-point solvent N-methyl-2-pyrrolidinone (NMP) and low-boiling-point solvents tetrahydrofuran (THF) and 1,4-dioxane (dioxane). The curing reactivities of the PETI oligomers were assessed based on the dianhydride structure using a nonisothermal differential scanning calorimetry (DSC) method. Kinetic parameters, including the preexponential factor (A), activation energy (Ea), reaction order (n), and reaction rate constant (k), were determined using Kissinger, Ozawa, Crane, and Arrhenius equations. All PETI oligomers followed a first-order kinetic reaction model below 90% conversion. The curing process was characterized by two distinct stages: initiation and propagation. PETI oligomers containing electron-donating linkages (−O−) exhibited the lowest curing reactivity. In contrast, despite its slower initiation, the PETI oligomer containing electron-withdrawing groups (−CF3) exhibited the highest curing reactivity. Thermally cured resin derived from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and 2,2′-bis(trifluoromethyl)benzidine is expected to exhibit excellent processability and thermal stability due to their high solubility, relatively low Tm (237.4-263.1 °C), and remarkable Td5% of 595.3 °C. This study provides a comprehensive understanding of the properties of PETI oligomers, enabling informed material selection for high-performance resin-based composite applications.
AB - A series of phenylethynyl-terminated imide (PETI) oligomers with varying chemical backbones and calculated number-average molecular weights were successfully synthesized via chemical imidization. These PETI oligomers exhibited exceptional solubility (>50 wt %) in both the high-boiling-point solvent N-methyl-2-pyrrolidinone (NMP) and low-boiling-point solvents tetrahydrofuran (THF) and 1,4-dioxane (dioxane). The curing reactivities of the PETI oligomers were assessed based on the dianhydride structure using a nonisothermal differential scanning calorimetry (DSC) method. Kinetic parameters, including the preexponential factor (A), activation energy (Ea), reaction order (n), and reaction rate constant (k), were determined using Kissinger, Ozawa, Crane, and Arrhenius equations. All PETI oligomers followed a first-order kinetic reaction model below 90% conversion. The curing process was characterized by two distinct stages: initiation and propagation. PETI oligomers containing electron-donating linkages (−O−) exhibited the lowest curing reactivity. In contrast, despite its slower initiation, the PETI oligomer containing electron-withdrawing groups (−CF3) exhibited the highest curing reactivity. Thermally cured resin derived from 2,3,3′,4′-biphenyltetracarboxylic dianhydride and 2,2′-bis(trifluoromethyl)benzidine is expected to exhibit excellent processability and thermal stability due to their high solubility, relatively low Tm (237.4-263.1 °C), and remarkable Td5% of 595.3 °C. This study provides a comprehensive understanding of the properties of PETI oligomers, enabling informed material selection for high-performance resin-based composite applications.
KW - curing kinetics
KW - fiber-reinforced plastic
KW - phenylethynyl-terminated imide
KW - processability
KW - structure parameters
KW - thermal durability
KW - thermosetting polyimides
UR - http://www.scopus.com/inward/record.url?scp=85206999633&partnerID=8YFLogxK
U2 - 10.1021/acsapm.4c02851
DO - 10.1021/acsapm.4c02851
M3 - Article
AN - SCOPUS:85206999633
SN - 2637-6105
VL - 6
SP - 13401
EP - 13412
JO - ACS Applied Polymer Materials
JF - ACS Applied Polymer Materials
IS - 21
ER -