Using Group Contribution Method and Molecular Dynamics to Predict the Glass Transition Temperature of Poly(p-phenylene isophthalamide)†

doi:10.7503/cjcu20180344

Abstract

Abstract:

Aramid fibers mainly include wholly aromatic polyamide and heterocyclic aromatic polyamide, while the wholly aromatic polyamides(aramids) are considered to be high-performance organic materials due to their outstanding thermal and mechanical properties. Their high-performances arise from their aromatic structure and amide linkages. The better known commercial aramids, poly(p-phenylene terephthalamide)(PPTA) and poly(m-phenylene isophthalamide)(MPDI), are used in advanced technologies and have been transformed into high-strength and flame-retardant fibers and coatings, with applications in the aerospace and armament industry. Poly(p-phenylene isophthalamide)(PPIA), a new aromatic polyamide, has not yet been commercialized and there are few reports about its comprehensive performance until nowadays. In this paper, Group Contribution(GC) method and molecular dynamics(MD) simulation were used to simulate the glass transition temperatures(T_g) of MPDI and PPTA. Then analysis and comparisons of the glass transition temperatures by GC method and MD simulation with their experimental values are presented. The results show that the glass transition temperature measured by GC method and MD simulation is very close to the experimental value, and that the change of the density, specific volume, radius of gyration and energy along with temperature can cha-racterize the glass transition temperature. Then these two methods were exploited to simulate the T_g of PPIA. The change of the density, specific volume, radius of gyration and energy interactions along with temperature were analyzed in the MD simulation. The results show that the free volume theory can explain the glass transition phenomenon of PPIA, and the change of the non-bond energy interactions with temperature is the essential reason. These results indicates that PPIA has the potential to become another high performance polyamide with its T_g lying between those of both MPDI and PPTA. It is of great significance to emphasize on the synthesis of PPIA with sufficiently high molecular weight. In general, the group contribution method and molecular dynamics simulation can predict the T_g of aromatic polyamide sucessfully, and they can contribute to a deeper understanding on the glass transition phenomenon of aromatic polyamides and the molecular motion behind.

Key words: Group contribution method, Molecular dynamics simulation, Glass transition temperature, Poly(p-phenylene isophthalamide)

CLC Number:

O631

TrendMD:

WU Hongmei,LI Huiting,LI Yongcheng,WANG Hongqing,WANG Meng. Using Group Contribution Method and Molecular Dynamics to Predict the Glass Transition Temperature of Poly(p-phenylene isophthalamide)^†[J]. Chem. J. Chinese Universities, 2019, 40(1): 180.

Figures/Tables 10

Fig.1 Chemical structures of MPDI and PPTA

Fig.2 Amorphous cell construction for a MPDI

Table 1 Tg of MPDI and PPTA from different methods

Method	T_g(MPDI)/K	T_g(PPTA)/K
Experiment value	545.2—548.2	600—618.2
GC	524.5	583.8
MD(Density-Temperature)	565.2	616.5
MD(Specific volume-Temperature)	566.9	616.3
MD(Radius of gyration-Temperature)	571.3	615.8
MD(Non-bond energy-Temperature)	567.4	617.4

Fig.3 Tg vs. degree of polymerization(DP) chart for PPIA at 300 K

Fig.4 Temperature(A) and energy fluctuation properties(B) vs. simulation time of PPIA(500 K, 200 ps NPT)

Fig.5 Density vs. temperature chart for an MD simulation of PPIA

Fig.6 Specific volume vs. temperature chart for an MD simulation of PPIA

Fig.7 Radius of gyration vs. temperature chart for an MD simulation of PPIA

Fig.8 Plots of energy components vs. temperature chart for an MD simulation of PPIA

Table 2 Tg of PPIA from different methods

Method	T_g/K
GC	554.4
MD(Density-Temperature)	593.6
MD(Specific volume-Temperature)	594.1
MD(Radius of gyration-Temperature)	592.2
MD(Non-bond energy-Temperature)	594.3

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