Infrared spectral absorption study of the formation kinetics of polypyromellitimide (PPMI)

Laius, L. A.; Bessonov, M.I.; Kallistova, Ye.V.; Adrova, N.A.; Florinskii, F.S.

doi:10.1016/0032-3950(67)90254-7

Cited by 48 publications

(19 citation statements)

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“…The bands which have been most widely used are imide absorptions near 1780 cm -1 (symmetrical stretch, c = 0), 1380 cm -1 (C-N stretch) and 725 cm -I (bending of c = 0) [5]. The degree of imidisation is determined by comparing the intensities ofthese bands in a treated sample to those in a sample that is heated until no changes in the band intensities occur [61,62]. The majority of studies have been carried out on film samples.…”

Section: Thermal Imidisation Of Poly( Amic Acids)mentioning

confidence: 99%

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Synthesis of aromatic polyimides from dianhydrides and diamines

Harris¹

1990

Polyimides

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Section: Thermal Imidisation Of Poly( Amic Acids)mentioning

confidence: 99%

“…The bands at 1015 and 1500cm-1 appear to be the most satisfactory. Heating at ~ 300°C for at least 0.5 hours is normally required to obtain the reference sample, which is considered to be 100% imidised [61][62][63][64].…”

Section: Thermal Imidisation Of Poly( Amic Acids)mentioning

confidence: 99%

Synthesis of aromatic polyimides from dianhydrides and diamines

Harris¹

1990

Polyimides

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“…Whereas Laius et al 4 and Kreuz et als followed only the increase in imide bandlintensity, we al&Otracked the decrease in two amide bands near 3325 and 1540 cm-1 • Thus, our kinetic equations are based on the average of two data sets for the two different types of chemical changes which should be in a 1:1 correspondence lf no side reactions occur, e.g., amide loss by hydrolysis rather than cyclization to imide.…”

Section: Introductionmentioning

confidence: 97%

“…Laius et al 4 studied by IR the reaction of 4,4 '-diaminodiphenyl ether--with pyromellitic dianhydride. They used a preliminary thermal treatment for placing their films in an initial standard state.…”

Section: Introductionmentioning

confidence: 99%

The Interplay between Solvent Loss and Thermal Cyclization in LARC-TPI

Frayer

1984

Polyimides

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Isothermal reaction kinetics are reported for the thermal cyclization of the poly (amide-acid) based on benzophenone tetra-carboxylic acid dianhydride reacted with 3,3'-diaminobenzophenone. Isothermal solvent loss kinetics are also reported. The data suggest a strong interdependence between the rate of imidation and the rate of solvent loss. Additional reactions may occur for isothermal reaction temperatures above about 180°C. Infrared analysis showed the presence of moisture even at elevated temperatures; hence, hydrolysis is one possible side reaction. Infrared spectra of films exposed to elevated temperatures further suggest that complete solvent removal is difficult. The infrared band assignments are proposed. The kinetic data were fitted to a modified absolute reaction rate theory equation where the time dependence of the reaction rate constant may be explained by entropic changes which follow a continuous function of time. The reaction kinetics yielded reasonable values for the frequency of vibration of the activated complex transition state and the activation energy. Low values for the activation entropy may be explained by solvent effects. The solvent loss kinetic model yields an estimate of the polymer-solvent interactions. 273K. L. Mittal (ed.), Polyimides

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“…When the glass trasition temperature (Tg) of the reacting medium reaches imidization temperature, the chain becomes immobile and the amic acid unit would be difficult to attain favorable conformation for imidization, which results in the lowering of the reaction rate. 17 Unfortunately, the experimental confirmation of the above consideration by measuring the Tg with thermal analysis is impossible, because the unreacted amic acid is transformed into imide near the Tg, resulting in the gradual increase of Tg during the measurement. The initial imidization rate and the final level of degree of imidization were found to increase with imidization temperature.…”

Section: Degree Of Imidization (%)mentioning

confidence: 99%

Development of In-Plane Orientation in Pyromellitic Dianhydride-Oxydianiline Polyimide Film on Substrate during Thermal Imidization

Kim

Park

1999

Polym J

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ABSTRACT:The development of in-plane orientation in pyromellitic dianhydride-oxydianiline (PMDA-ODA) polyimide film coated on silicon substrate during thermal imidization was investigated by means of FT-IR spectroscopy. The increase in thermal imidization temperature caused the decrease in the degree of in-plane orientation in spite of the increased chain rigidity. It suggests that the chain immobilization limit the development of the in-plane orientation during thermal imidization. The residual solvent was found to decrease the degree of in-plane orientation probably due to the increase of the chain immobilization rate as indicated by the quantitative measurements of the degree of imidization and the residual solvent content as a function of imidization time at various temperatures.KEY WORDS Pyromellitic Dianhydride-Oxydianiline I Thermal lmidization I Chain Rearrangement I In-Plane Orientation I Residual Solvent I Chain Immobilization IThe chain orientation in polyimide coated on substrate is characterized by the term 'in-plane orientation' which means that the director of polyimide chain is parallel to substrate. 1 -3 Since various anisotropic properties of dielectric constant, refractive index, and coefficient of thermal expansion depend on degree of in-plane orientation,4-8 the development of in-plane orientation during thermal imidization is a matter of concern.Since the in-plane orientation of polymer film coated on substrate is originated from the restricted chain rotation near the substrate, a polymer of higher chain rigidity shows stronger tendency for developing in-plane orientation, when polymers of different rigidity are compared. 9 · 10 However, we previously found in a study on the effect of imidization condition on the in-plane orientation of polyimide that degree of in-plane orientation of polyimide was, in some cases, found to be higher at lower chain rigidity_ll This behavior was explained in terms of the chain immobilization which is caused by the increase of the chain rigidity during thermal imidization. Even though the driving force for developing in-plane orientation would increase as imidization proceeds, the long-range motion of the chain leading to in-plane orientation could be limited by the decreased chain mobility. In this work, we changed the chain immobilization rate for pyromellitic dianhydride-oxydianiline (PMDA-ODA) polyamic acid cast on silicon wafer by varying the imidization temperature and the residual solvent content, and investigated the corresponding changes in the in-plane orientation of polyimide by means of FT-IR spectroscopy to obtain better understanding on the development of in-plane orientation during thermal imidization. EXPERIMENTAL Materials and P AA Cast PreparationPyralin® (DuPont), the mixture of the polyamic acid ( 4,4' -oxydiphenylene pyromellitamic acid), N-methylt To whom all correspondence should be addressed. 154 pyrrolidinone (NMP), and petroleum ether, was poured into excess methanol to precipitate the polyamic acid. The precipitates were washed with...

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Infrared spectral absorption study of the formation kinetics of polypyromellitimide (PPMI)

Cited by 48 publications

References 1 publication

Synthesis of aromatic polyimides from dianhydrides and diamines

Synthesis of aromatic polyimides from dianhydrides and diamines

The Interplay between Solvent Loss and Thermal Cyclization in LARC-TPI

Development of In-Plane Orientation in Pyromellitic Dianhydride-Oxydianiline Polyimide Film on Substrate during Thermal Imidization

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