RETRACTED ARTICLE: Pyrolysis study of waterborne polyurethane

Abstract

The thermal degradation of synthetic waterborne polyurethane (PU) based on toluenediisocyanate (TDI) was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetry (TG). The degradation profiles of cast films obtained from dispersions were evaluated. More than 20 characteristic volatile pyrolyzates reflecting the structure and pyrolysis mechanisms of the polymer have been identified by on-line MS. In helium atmosphere, the synthesized products of polyurethane were pyrolyzed at 350, 450, 550, 650 and 750 °C respectively, and the thermal decomposition products were analyzed on line using GC/MS. The product analysis reveals that the pyrolyzates distribution of the polyurethane depends strongly on the pyrolysis temperature. Based on the Py-GC/MS data, the thermal degradation mechanism of the polyurethane is discussed.

Keywords

waterborne polyurethane / pyrolysis-gas chromatography / mass spectrometry / pyrolysis / thermogravimetry

References

[1] Woods W. The ICI Polyurethanes Book[M], 1990 New York Wiley

[2] Coutinho F. M. B., Delpech M. C., Moura P. M. Q., . Synthesis and Molecular Weight Determination of Urethane-Based Anionomers[J]. Polym. Bull., 1996, 37(1): 1-5.

[3] Coutinho F. M. B., Delpech M. C. Some Properties of Films Cast from Polyurethane Aqueous Dispersions of Polyether-Based Anionomer Extended with Hydrazine[J]. Polym. Test, 1996, 15(2): 103-113.

[4] Coutinho F. M. B., Delpech M. C., Alves L. S. Anionic Waterborne Polyurethane Dispersions Based on Hydroxyl-Terminated Polybutadiene and Poly(propylene glycol): Synthesis Characterization[J]. J. Appl. Polym. Sci., 2001, 80(4): 566-572.

[5] Delpech M. C., Coutinho F. M. B. Waterborne Anionic Polyurethanes and Poly(urethane-urea)s: Influence of the Chain Extender on Mechanical and Adhesive Properties[J]. Polym. Test, 2000, 19(8): 939-952.

[6] Shao C. H., Huang J. J., Chen G. N., . Thermal and Combustion Behaviors of Aqueous-Based Polyurethane System with Phosphorus and Nitrogen Containing Curing Agent[J]. Polym. Degrad. Stab., 1999, 65(3): 359-371.

[7] Dieterich D., Rieck J. N. Aqueous Polyurethanes and Their Possible Uses[J]. Adhes Age, 1978, 21(2): 24-28.

[8] Satguru R., McMahon J., Padget J. C., . Aqueous Polyurethanes — Polymer Colloids with Unusual Colloidal, Morphological, and Application Characteristics[J]. J. Coat. Technol., 1994, 66(830): 47-55.

[9] Dyer E., Newborn G. E. J. Thermal Degradation of Carbamates of Methylenebis (4-Phenyl Isocyanate)[J]. J. Am. Chem. Soc., 1958, 80: 5 495-5 498.

[10] Dyer E., Wright G. C. Thermal Degradation of Alkyl N-Phenylcarbamates[J]. J. Am. Chem. Soc., 1959, 81: 2 138-2 143.

[11] Dyer E., Read R. E. Thermal Degradation of 1-Hexadecyl-1-Napthylcarbamate and 1-Hexadecyl Propyl(1-Naphthyl) Carbamate[J]. J. Org. Chem., 1961, 26: 4 388-4 394.

[12] Chang T. C., Chiu Y. S., Chen H. B., . Degradation of Phosphorus-Containing Polyurethanes[J]. Polym. Degrad. Stab., 1995, 47(3): 375-381.

[13] Boutin M., Lesage J., Ostiguy C., . Comparison of EI and Metastable Atom Bombardment Ionization for the Identification of Polyurethane Thermal Degradation Products[J]. J. Anal. Appl. Pyrol., 2003, 70(2): 505-517.

[14] Hepburn C. Polyurethane Elastomers[M], 1991 Second ed London Elsevier

[15] Rotival C., Renacco E., Arfi C., . Gases Emitted during Thermal Decomposition of a Polypropylene Film and a Polyurethane Adhesive[J]. J. Thermal. Anal., 1994, 41(6): 1 519-1 527.

[16] Coutinho F. M. B., Delpech M. C. Degradation Profile of Films Cast from Aqueous Polyurethane Dispersions[J]. Polym. Degrad. Stab., 2000, 70(1): 49-57.

[17] R Font, A Fullana, J A Caballero, et al. Pyrolysis Study of Polyurethane[J]. J. Anal. Appl. Pyrol., 2001(58–59): 63–77

[18] Herrera M., Matuschek G., Kettrup A. Thermal Degradation of Thermoplastic Polyurethane Elastomers (TPU) Based on MDI[J]. Polym. Degrad. Stab., 2002, 78(2): 323-331.

[19] Williamson J. E., Cocksedge M. J., Evans N. Analysis of Polyurethane and Epoxy Based Materials by Pyrolysis — Mass Spectrometry[ J]. J. Anal. Appl. Pyrol., 1980, 2(3): 195-205.

[20] Ohtani H., Kimura T., Okamoto K., . Characterization of Polyurethanes by High-Resolution Pyrolysis-Capillary Gas Chromatography[J]. J. Anal. Appl. Pyrol., 1987, 12(2): 115-133.

[21] Lattimer R. P., Polce M. J., Wesdemiotis C. MALDI-MS Analysis of Pyrolysis Products from a Segmented Polyurethane[ J]. J. Anal. Appl. Pyrol., 1998, 48(1): 1-15.

[22] Hileman F. D., Voorhees K. J., Wojcik L. H., . Pyrolysis of a Flexible Urethane Foam[J]. J. Polym. Sci. Polym. Chem. Ed., 1975, 13(3): 571-584.

[23] Lattimer R. P., Muenster H., Budzikiewicz H. Pyrolysis Tandem Mass Spectrometry (Py-MS/MS) of a Segmented Polyurethane[J]. J. Anal. Appl. Pyrol., 1990, 17(3): 237-249.