Flash pyrolysis of hydroxyl-terminated polybutadiene (HTPB) I: Analysis and implications of the gaseous products

Abstract Flash pyrolysis of structurally different hydroxyl-terminated polybutadiene polymers (HTPB) was conducted at 600°C/s to constant temperatures in the 450°–609°C range under 2 and 11 atm of applied pressure. T-Jump/FTIR spectroscopy was used. With chemometric procedures based on the entire mid-IR spectrum, 13 gaseous products representing at least 70% of the polymer were identified and quantified. Contrary to previous indications that butadiene and 4-vinyl-l-cyclohexene dominate, the trans-butadiene oligomers are major products. These oligomers are probably responsible for smoke formation. The product concentrations are sensitive to the temperature below 500°–530°C and 2 atm Ar, but are relatively insensitive to the temperature above 500°–530°C.

[1]  R. Gritter,et al.  Thermal decomposition and volatilization of poly(α‐olefins) , 1977 .

[2]  T. Shono,et al.  Determination of the microstructure of polybutadiene by pyrolysis-gas chromatography , 1971 .

[3]  R. F. Mcalevy,et al.  ENERGETICS AND CHEMICAL KINETICS OF POLYSTYRENE SURFACE DEGRADATION IN INERT AND CHEMICALLY REACTIVE ENVIRONMENTS. , 1965 .

[4]  P. Vervisch,et al.  The spectral transmission of 0.4–4.5-μm of fire smokes , 1981 .

[5]  R. F. Mcalevy,et al.  Linear pyrolysis of thermoplastics in chemically reactive environments , 1964 .

[6]  S. Bulusu.  Chemistry and physics of energetic materials , 1990 .

[7]  D. Lin-Vien.  The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules , 1991 .

[8]  D. Tingfa,et al.  Thermal decomposition studies of solid propellant binder HTPB , 1989 .

[9]  H. Keskkula,et al.  Effect of thermal crosslinking on decomposition of polybutadiene , 1979 .

[10]  T. Brill.  Connecting the chemical composition of a material to its combustion characteristics , 1992 .

[11]  D. Dlott,et al.  Direct measurement of polymer temperature during laser ablation using a molecular thermometer , 1992 .

[12]  T. S. Radhakrishnan,et al.  Thermal degradation of functionally terminated polybutadienes: Pyrolysis gas chromatography and thermogravimetric studies , 1990 .

[13]  N. Cohen,et al.  Role of Binders in Solid Propellant Combustion , 1974 .

[14]  R. Long,et al.  Eighth symposium (International) on combustion: Published for the Combustion Institute. Baltimore: The Williams & Wilkins Company; London: Baillière, Tindall and Cox, 1962. xxviii+1164 pp. $31.00 or 248s , 1962 .

[15]  C. Fong,et al.  The mechanism of burning rate catalysis in composite HTPBAP propellant combustion , 1986 .

[16]  Walter H. Beck,et al.  Pyrolysis studies of polymeric materials used as binders in composite propellants: A review , 1987 .

[17]  V. N. Krishnamurthy,et al.  Thermogravimetric and mass-spectrometric study of the thermal decomposition of PBCT resins , 1979 .

[18]  C. Lawson,et al.  Solving least squares problems , 1976, Classics in applied mathematics.

[19]  H. Jellinek,et al.  Aspects of degradation and stabilization of polymers , 1978 .

[20]  T. Brill,et al.  T-Jump/FT-IR Spectroscopy: A New Entry into the Rapid, Isothermal Pyrolysis Chemistry of Solids and Liquids , 1992 .

[21]  J. H. Hedges,et al.  Polymer pyrolysis over a wide range of heating rates , 1977 .

[22]  B. Schneider,et al.  Study of thermal degradation of polybutadiene in inert atmosphere: 1. Evidence of temperature and time of heating in i.r. and n.m.r. spectra , 1993 .

[23]  O. F. Shlensky,et al.  Limiting temperatures of the thermal decomposition of polymers and their determination by rapid thermal analysis , 1986 .

[24]  John Aurie Dean,et al.  Lange's Handbook of Chemistry , 1978 .

[25]  J. Schooten,et al.  Pyrolysis—Hydrogenation—GLC of poly-α-olefins , 1965 .

[26]  N. Schwartz,et al.  The effect of heating rate on the thermal degradation of polybutadiene , 1978 .

[27]  Thomas B. Brill,et al.  Chemistry and kinetics of hydroxyl-terminated polybutadiene (HTPB) and diisocyanate-HTPB polymers during slow decomposition and combustion-like conditions , 1991 .

[28]  I. Ericsson.  Sequential Pyrolysis Gas Chromatographic Study of the Decomposition Kinetics of Cis-1,4-Polybutadiene , 1978 .