Thermodynamics Research Center / ThermoML | Thermochimica Acta

Contribution of blocking positions on the curing behaviors, networks and thermal properties of aromatic diamine-based benzoxazines

Zhang, L.[Lei], Zheng, Y.[Yiting], Fu, R.[Ruotian], Chen, Y.[Yingxin], Liu, X.[Xiangdong]
Thermochim. Acta 2018, 668, 65-72
ABSTRACT
To elucidate the contribution of blocking positions on aromatic diamine-based benzoxazines, we prepared several 4,4 -bis(3,4-dihydro-2H-1,3-benzoxazin-3-yl) diphenyl methane monomers with different phenols. The molecular chemical structures of the bi-functional monomers are characterized by FTIR and 1H-NMR. Particularly, the newly developed m-cresol based benzoxazine is further confirmed by 13C-NMR and ESI-MS and the oxazine ring position is verified. The curing behaviors are investigated by dynamic differential scanning calorimetry (DSC). Activation energies are analyzed by Kissinger, Ozawa and Starink methods at various heating rates. Due to structure difference in polymerized network, polymer with high amount of arylamine Mannich bridge shows low autocatalysis capability. The glass transition temperature (Tg) is closely related to the blocking position while thermal stability decreases comparatively regardless of the blocking position. High arylamine Mannich bridging leads to large amount of dangling groups, which reduces the decomposition peak temperature.
Compounds
# Formula Name
1 C29H26N2O2 bis(4-(2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane
2 C31H30N2O2 bis(4-(7-methyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane
3 C31H30N2O2 bis(4-(6-methyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane
4 C33H34N2O2 bis(4-(6,8-dimethyl-2H-benzo[e][1,3]oxazin-3(4H)-yl)phenyl)methane
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 2
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1