Abstract

The impact of force field models on the thermal and mechanical characteristics of polyimides was comprehensively examined for the first time. Polyimides (PI) are heterocyclic polymers with outstanding thermal and chemical stabilities and excellent dielectric properties. In this study, we used all-atom molecular dynamics (MD) simulations to examine how the flexibility of the dianhydride fragment affects the thermal and mechanical properties of three polyimides: PMDA-ODA, ODPA-ODA, and R-ODA. The considered polyimides have different dianhydride fragments based on pyromellitic acid (PMDA), tetracarboxylic acid diphenyl oxide (ODPA) and 1,3-bis(3′,4-dicarboxyphenoxy)benzene acid (R), with a constant diamine: 4,4′-oxydianiline (ODA). Models were built using five classical force fields (OPLS-AA, Amber/GAFF, Gromos, Charmm/CGenFF, and UFF). For each polyimide, eight models were generated using different force fields and charge schemes: (i) OPLS-AA with 1.14*CM1A charges, (ii) OPLS-AA with HF/6-31G* (RESP) charges, (iii) GAFF with AM1-BCC charges, (iv) GAFF with HF/6-31G* (RESP) charges, (v) CGenFF (version 4.6) with native charges, (vi) CGenFF (version 5.0) with native charges, (vii) Gromos54a7 with native charges, and (viii) UFF with QEq charges. The difference in the chemical structures of the polyimide repeating unit leads to differences in the thermodynamic and kinetic flexibilities that affect the thermal and mechanical properties. Simulations of glass transition temperatures (Tg) for three polyimides PMDA-ODA, ODPA-ODA, and R-ODA mostly replicate the experimental order Tg(PMDA-ODA) > Tg(ODPA-ODA) > Tg(R-ODA), except for the CGenFF (version 4.6) force field. The experimental density ratio ρ(PMDA-ODA) > ρ(ODPA-ODA) > ρ(R-ODA) is most accurately replicated by OPLS-AA (RESP) and CGenFF (version 5.0) polyimide models. The coefficients of thermal expansion (CTE) correspond with the experimental trend, exhibiting an increase in the following order: PMDA-ODA < ODPA-ODA < R-ODA. Gromos54a7 precisely delineates both the ratio and absolute values CTE for all polymers. OPLS-AA (RESP), OPLS-AA (CM1A), CGenFF (version 4.6), and UFF (QEq) models replicate PMDA-ODA’s CTE, while GAFF (RESP) and GAFF (AM1-BCC) models replicate ODPA-ODA and R-ODA CTE values. The ratio between the simulated values of Young’s modulus, yield strength, and strain-hardening modulus followed the sequence PMDA-ODA > ODPA-ODA > R-ODA for the OPLS-AA (RESP) and CGenFF (version 5.0) models.

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