The kinetics of formation of polyimides by high-temperature polycyclization

Gerashchenko, Z.V.; Vygodskii, Ya. S.; Slonimskii, G.L.; Askadskii, А.A.; Папков, В. С.; Виноградова, С. В.; Dashevskii, V. G.; Klimova, V. A.; Sherman, F. B.; Korshak, V.V.

doi:10.1016/0032-3950(73)90406-1

Cited by 15 publications

(9 citation statements)

References 5 publications

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“…The kinetics of one‐step polyimide formation has received much less study to date 2–7. However, because of an increasingly wide variety of applications in advanced composites, there is an impending requirement to deeply understand and study the one‐step polyimide formation kinetics for the sake of optimizing the processing cycle and reducing the production cost of polyimide composites.…”

Section: Introductionmentioning

confidence: 99%

“…When the steady‐state approximation is applied to the amic acid, imidizations are expected to follow second‐order kinetics. However, nonlinearities in second‐order plots begin at low conversion of less than 30% 5. To solve the problem, Lauver7 used two first‐order models to describe the kinetic behavior of polymerization of monomer reactants (PMR)‐15 (a polyimide with molecular weight of 1500).…”

Section: Introductionmentioning

confidence: 99%

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Diffusion-limited kinetics modeling of one-step polyimide formation

Zhou

2001

J. Appl. Polym. Sci.

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A diffusion‐limited kinetic model was developed to describe the imidization of one‐step polythioetherimide formation based on an endgroup diffusion model. The changes of conversion and viscosity during the imidization were monitored with thermogravimetric analysis and dynamic stress rheometry, respectively. It was observed that the imidization rate began to decelerate after a fast early stage, whereas the viscosity in the system increased dramatically after a period of low value. Amic acid and imide formations concurrently take place in the one‐step polyimide formation, but the formation of amic acid is much slower than that of imide and is the rate‐limiting step of imidization. When a second‐order kinetic model was used to describe the imidization, the effect of viscosity on the diffusion resistance of reactive groups needed to be included. In order to predict the change of viscosity during the imidization, the Lipshitz‐Macosko model was modified and introduced into the diffusion‐limited kinetic model by the Stokes‐Einstein equation. The comparison of the modeled results with experimental data indicated that the diffusion‐limited kinetic model and the modified Lipshitz‐Macosko model were able to efficiently predict the changes of conversion and viscosity with temperature and time during the one‐step polythioetherimide formation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2052–2059, 2001

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Diffusion-limited kinetics modeling of one-step polyimide formation

Zhou

2001

J. Appl. Polym. Sci.

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“…The degree of imidisation attained is essentially 100%. However, one group of workers have claimed to have determined two distinct rate constants, one for propagation and one for imidisation [102,103]. These workers also found that the initial rate constant remains constant only in the initial stages of the reaction.…”

Section: Mechanism and Kinetics Of The One-step Methodsmentioning

confidence: 93%

“…For example, kinetic studies have shown that the ratedetermining step in imide formation is the second-order reaction between the anhydride and the amine [102,103]. Thus, imidisation occurs either simultaneously with propagation, or very quickly thereafter.…”

Section: Mechanism and Kinetics Of The One-step Methodsmentioning

confidence: 97%

Synthesis of aromatic polyimides from dianhydrides and diamines

Harris¹

1990

Polyimides

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“…It is noteworthy that the ready solubility of cardo polyimides has led to the possibility of their synthesis by different procedures: by the two-stage polycyclisation of tetracarboxylic acid dianhydrides and diamines 2~4 -4ft 146 -174 ~1 77 -2m -210 ~ 213> 218 " 22°-223> 228 ' 25Qi 258 ' 262> 263 -26S with thermal and catalytic imidisation of polyamidoacids, by a single-stage polycyclisation in solution both in the presence of catalysts and without them (see, for example, 49,146,[171][172][173][178][179][180][181][182][183][211][212][213][214]217,222,223,225,250,258,261,263), by the reaction of tetracarboxylic acid dichloride diesters and diamines, 2 -4 ' 49 .' 83 -i85.2oo,2ii,26i and by the polycyclisation of tetracarboxylic acid dianhydrides and trimethylsilyl derivatives of diamines.…”

Section: Polyimidesmentioning

confidence: 99%