Thermal Decomposition of Poly(butylene

RICHARD M. LUM, Bell Laboratories, Murray Hill,New Jersey 07974

Detailed results of the overall thermal degradation of poly(buty1ene terephthalate) are reported.
Laser microprobe analysis and dynamic mass spectrometric techniques were used to identify the
primary volatile degradation products and initial pyrolysis reactions that control polymer degra-
dation. A complex multistage decomposition mechanism was observed which involves two major
reaction pathways. Initial degradation occurs by an ionic decomposition process that results in the
evolution of tetrahydrofuran. This is followed by concerted ester pyrolysis reactions that involve
an intermediate cyclic transition state and yield 1,3-butadiene. Simultaneous decarboxylation re-
actions occur in both decomposition regimes. Finally, the latter stages of polymer decomposition
were characterized by evolution of CO and complex aromatic species such as toluene, benzoic acid,
and terephthalic acid. Activation energies of formation for the main pyrolysis products were de-
termined from the dynamic measurements of the major ion species and indicate values of E = 27.9
kcal/mole for the production of tetrahydrofuran and E = 49.7 kcal/mole for the production of bu-

Poly(buty1ene terephthalate) (PBT) is a polyester thermoplastic material
used in the fabrication of a wide variety of molded components. The polymer
chain consists of a mixed aliphatic-aromatic structure:

PBT is prepared by condensation polymerization of dimethyl terephthalate with
1,4-butanediol. The resulting polymer possesses a high degree of crystallinity132
(-30%), average molecular weight M,, = 25,000, glass transition temperature3
Tg = 50°C, and melting temperaturel~~ T,,, = 226-228OC.
During processing high melt temperatures and moisture can result in polymer
degradati~n.~ Although investigation of the initial weight-loss behavior of PBT
has been reported: no work has appeared on the characterization of the volatile
products of thermal degradation. Measurements of the composition and rates
of evolution of the volatile products provide important information from which
details of the decomposition process may be determined.
This article presents the first detailed studies of the overall thermal degra-
dation (inuacuo) of PBT. Laser microprobe analysis7is used to determine the
primary volatile degradation products and initial pyrolysis reactions that control
polymer degradation. Dynamic mass spectrometric sampling techniques are
used to complement the laser microprobe measurements by providing detailed
temperature profiles of the partial pressures of the various evolved species. From

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 17,203-213 (1979)
0 1979 John Wiley & Sons, Inc. 0360-6376/79/0017-0203$01.00

initial polymer de- composition is characterized by the elimination of tetrahydrofuran-contrary to the results reported by Passalacqua et aL6 Formation of significant amounts of carbon dioxide by decarboxylation reactions and carbon monoxide are also observed. Focused radiation (beam diameter = 1 mm) from a COz laser (A = 10. Evolved gas analysis measurements as a function of temperature were made by using the modified apparatus described by Lum. as well as volatile aromatic compounds that evolve during the latter stages of polymer degradation. Experimental schematic of dynamic sampling MS apparatus. Although butadiene is the major volatile product. On laser irra- diation a plume of volatile products is generated from the polymer surface. Polymer samples are heated in BUFFER ANALYSIS CHAMBER CHAMBER GAS THERMOCOU BACKGROUND Fig. Details of the laser microprobe apparatus appear elsewhere718and only a brief description is given here. Sample weights ranged from 20 to 30 mg.6 pm) was used to probe the polymer samples.5-mm diameter orifice and is evacuated through this orifice by the MS vacuum pumps. Detection sensi- tivity is increased by mechanical modulation of the molecular beam which con- sists solely of the volatile pyrolysis fragments. im- mediately formed into a molecular beam. Activation energies for the production of volatile species from the main pyrolysis reactions characteristic of PBT degradation are determined from the dynamic measurements of the major ion signals. 1. ionized by electron impact (70-eV electron energy). In addition. and analyzed with a quadrupole mass filter. These are compared with reported values for PBT and lower member homologs. the overall course of thermal decomposition is directly followed with measurements of the dynamic variations in total pressure in the pyrolysis chamber as a function of temperature.204 LUM these data kinetic parameters of the decomposition reactions may be determined. PBT undergoes degradation by a complex multistage decomposition mecha- nism. These samples contained no flame-retardant or filler (glass fiber) additives. EXPERIMENTAL PBT samples for the laser microprobe and dynamic mass spectrometric (MS) analyses were obtained from virgin resin pellet stock without further preparation.9 A schematic of the ex- perimental arrangement is shown in Figure 1. . Laser beam intensities a t the sample surface were varied from 200 to 500 W/cmz. The sample cell is directly coupled to the inlet of an MS system via a 0.

tetrahydrofuran (THF).72 doublet can be attributed to volatile tetramethylene oxide. which is a heterocyclic compound: H&-CH. it is clear that the m/e = 71. Heating rates of 3-lO"C/min were used. The total pressure data provide information on the overall course of polymer thermal degradation similar to that obtained from derivative thermo- gravimetric measurements (rate of weight loss versus temperature or time). as. From the structure of PBT. 1is the first spectrum obtained after exposure of PBT sample to the laser beam. apparent activation energies of product formation). 0 SCAN # 1 17 .I XI0 71. Scan time = 2 min. for instance. and mass analyzed. Repetitive mass spectral scans from m/e = 12-150 were automatically obtained at 3-min intervals. RESULTS Laser Microprobe Analysis Results from laser irradiation of PBT are shown in the modulated mass spectra in Figure 2. Details of complex reactions may be unraveled by exact identification of product species. order of product evolution.CH. Laser microprobe spectra: scan No. 54 SCAN C 5 I I I I I I I 20 30 40 50 60 70 00 m/e (amu) Fig. that is. gases evolved from the degrading polymer are dynamically sampled via a 0.5-mm diameter orifice. . and determination of kinetic pa- rameters (e. rate of evolution. Measurements of both total and partial pressure variations permit detection and identification of simultaneously occurring decomposition reactions. formed into a modulated molecular beam. Time.. / \ HF. THERMAL DECOMPOSITION OF PBT 205 a Pyrex glass tube attached directly to the inlet flange of the MS system.and temperature-resolved partial pressure profiles of the pyrolysis fragment ion signals were thus obtained. are the series of fragment peaks appearing at m/e = 25-31 and 39-43. In addition to the partial pressure measurements. The two peaks at mle = 71 and 72 form a distinctive doublet not usually observed in the mass spectra of organic com- pounds. (l ). .g. The upper scan represents the first spectrum obtained after expo- sure of the sample to the laser beam. The sample-tube volume (-60 cm3) is evacuated through the sampling orifice by the MS pumps to a background pressure of Torr.72 K . As the sample tube is heated. 2. the dynamic variation in total pressure in the sample tube is monitored with an MKS Baratron pressure gauge. as given in eq.

but not shown in these spectra. Also detected. The peaks at mle = 105. whereas the peaks at mle = 121. it is seen that 1. Subsequent pyrolysis reactions include formation of COn by decarboxylation.122 (and mle = 77) form the characteristic ion fragmentation pattern of benzoic acid.3-butadiene (mle = 54). however. On continued irradiation.149 and 166 are indic- ative of terephthalic acid. reveal the presence of several high-molecular-weightcompounds. 3. namely terephthalic acid mono-3-butenyl (I): 0 0 Ho. Trace amounts of aromatic fragments in the volatile degradation products are indicated by the peaks at rnle = 77- 79. THF is now only a minor species. for it involves several separate decomposition reactions. The presence of water is indicated by the rnle = 17 signal (overloading the lock-in amplifier causes the irregular peak shape exhibited by the HzO+ parent ion signal). as shown in scan No. which is the molecular weight of PBT monomer species. Details of these reactions are discussed separately in another section. !!+!!-o-c~2--cH2--cH=cHI (3) On electron impact this species would be expected to yield the parent minus OH (mle = 203) as the most intense ion peak. Laser microprobe spectra: mass range 100-230 amu scanned at increased sensitivity. 5. and polymer chain scission which result in the evolution of 1. are toluene ( m / e = 92) and phenol (mle = 94). Spectra obtained at increased sensitivity in a higher mass range. Initial degradation involves splitting off the glycol portion of the polyester followed by cyclization to form THF. plus minor amounts of benzene (mle = 78). shown in Figure 3. NMR data6 indicate that this volatile species may be an unsaturated ester of terephthalic acid. The highest mass peak observed in the laser micro- probe spectra occurs at mle = 220. 203 149 n 100 120 140 160 180 200 220 m/e (omu) Fig. COz. and CO become the dominant volatile products. From laser vaporization of PBT it is clear that polymer thermal degradation is rather complex.206 LUM Initial decomposition of PBT is thus characterized by the elimination of THF from the polymer chain.3-butadiene and various aromatic compounds. .

1-pg weight loss of the sample. The resulting pressure profiles are presented in Figure 4 for two different heating rates: 3 and 7"C/min. 4. The total pressure measurements. Multiple pressure peaks indicate a complex decomposition process for PBT. The per- centage of decomposition up to 3OOOC is 3. the polymer degrades and its weight loss by volatilization results in a corresponding increase in system pressure. Fig. Maximum pressures recorded with a Baratron gauge (sen- sitivity 0. Figure 4 shows that initial volatilization occurs slightly below 15OOC at the lower heating rate. although some slight evidence of structure in the curve shape remains.6 for the 3"C/min heating rate and 1. which proved to be a sensitive indicator of the onset of thermal degradation. At the higher heating rate these peaks are not resolved. Total pressure profiles observed for heating rates of (-) 3 and ( . . An analysis of the degradation mechanisms involved in the separate stages of decomposition requires detailed knowledge of the partial pressure behavior of the major volatile species and is presented in the next section. The multiple pressure peaks observed a t the lower heating rate substantiate the laser microprobe findings of a multistage decomposition process for PBT. THERMAL DECOMPOSITION OF PBT 207 Total Pressure Data Measurements of the rate of pressure increase in the sample tube during py- rolysis of PBT yield information on the overall evolution rate of volatile species from the polymer. detected initial volatilization that corre- sponded to less than 0.8 for the 7"CImin heating rate.1 mTorr) during pyrolysis were on the order of 200 mTorr.0 ) 7"C/min. Before sample pyrolysis the pressure in the sample tube was approximately 1 X 10-7 Torr. As the temperature is increased.

49).-CH.1° both of which necessitate automated data acquisition. subsequent storage on magnetic tape was performed to permit digital processing of the raw data. with the exception of somewhat lower rel- ative intensities for the higher-molecular-weight aromatic compounds. selected ion sum or total ion sum to be generated by searching through each stored spectrum to retrieve the peak amplitudes at the specified mass values. 1. Continuous mass spectral scans (mle = 12-150) were performed au- tomatically throughout the pyrolysis experiment.50.-0-C I+. Maximum evolution for CO is observed at 350°C. A more quantitative comparison requires faster scanning rates or selected ion monitoring. CO (mle = 28). For runs at the 3"Clmin heating rate complete spectra were thus obtained approximately every 10°C. . COa (mle = 44). 1. This capability is presently . DISCUSSION Decomposition Reactions The observations suggest that initial polymer scission occurs via the following cyclic transition state (I). Although the spectra were acquired in analog form. (4) Both the laser microprobe and dynamic MS data suggest that subsequent PBT thermal decomposition proceeds along two different reaction pathways. The resulting ion current plots represent rate curves of evolution for the selected ion species. Plot routines were developed which enabled "mass chro- matograms" of a specific ion. Two peaks are detected in the evolution of Cop. Selected ion profiles for ion species characteristic of the major pyrolysis products observed are presented in the computer plots of Figure 5: THF (mle = 72.71. A Tektronix model 4051 interactive-graphics microcomputer system was used in the data analysis. Evolution of the major product. The general features of the mass spectra obtained were similar to those gen- erated by laser microprobe analysis.being implemented by additions to the apparatus already described.3-butadiene (mle = 54. These ion profiles are in excellent qualitative agreement with the variations observed in the total pressure (Fig. the first coincident with the maximum in THF evolution (290°C) and the second oc- curring at approximately 340°C. which is commonly invoked for ester pyrolysis. 4).51. THF is observed as the first species evolved (220OC) in agreement with the laser mi- croprobe results.ll -+ ---@XOH + CH.42).=CH-CH.53.208 LUM Dynamic MS Sampling of Pyrolysis Species During pyrolysis of PBT evolution of volatile products from the polymer was monitored simultaneouslywith a Baratron pressure gauge and a quadrupole mass analyzer.3-butadiene. begins at approximately 27OOC and reaches a maximum at about 340°C.

THERMAL DECOMPOSITION OF PBT 209 Decomposition of I1 via an ionic mechanism yields the initially observed py- rolysis product THF.6 0 ---t i. (7) bH The possibility of butadiene production by secondary reactions is countered by the double peaks observed in the evolution of C02. Formation of C02 in both cases arises from separate decarboxylation processes that involve the products accompanying reactions (5)-(6c) and (7). -+E'+v 0 In addition. acid-catalyzed hydrolysis of I11 may also be important in THF production. because the mle = 17 signal indicates the presence of water in the decomposition products. results in the elimination of 1. the first being coincident with the maximum in the rate of THF formation and the second correlating well with the butadiene maximum. 0 n bH At higher temperatures the second reaction pathway. which involves 11.3-butadiene by concerted ester pyrolysis.CH2=CH-CH=CH. .

I- H 2 I- 40 s 20 0 20200 0 w 258 300 TEMP CC) 358 400 TEMP CC) Fig.3-butadiene (selected ion sum: mle = 54.50.71. Ion profiles for fragments characteristic of the major pyrolysis products upper left-THF (selected ion sum: mle = 72. With the assumption that the rate of evolution and total weight of evolved gas are proportional to the weight-loss rate and the total weight. lower left-COz (m/e = 44). .3 RT Here I is the MS ion current for a given species.. These kinetic parameters can be determined from the ion signal profiles in Figure 5 by application of analysis techniques similar to those used in thermogravimetric measurements. St is the corresponding area between the initial reaction temperature and a given temperature T. (9) can be solved for various trial values of n in an Arrhenius-type plot. Computer plots of species evolution rates. for example.R is the gas constant.)" 2. constants. activation energy. So. 53. frequency factor.e.___ log (KSo .210 LUM 88 60 >. With the help of the dedicated data-handling system described earlier values for the parameters I . and reaction order). This technique is espe- cially valuable for complex decomposition processes involving simultaneously competing reactions.upper right-CO (mle = 28).KS. n. the activation energy. the following equation is derived. and K and C.42).49). So is the area under the MS ion current curve as a function of temperature. E . 5. Determination of Activation Energies Polymer thermal decomposition can often be represented by the following simplified reaction: - A(so1id) B(so1id) C(gas) + Details of the gas evolution profiles depend largely on the kinetic parameters (8) characteristic of the decomposition process (i.51.and St are readily obtained and eq. the reaction order.12 KI E = l0gC .loss. lower right-1.

however. however. which is usually taken as the sole degradation reaction.7 1. the two-stage evolution of C02 results in a calculated activation energy of 52. Arrhenius plots for the ion species characteristic of the major decomposition products from PBT are presented in Figures 6 and 7. As shown by the dashed line.6 kcal/mole for the high- temperature reaction. For the concerted ester pyrolysis reaction yielding butadiene.50. Finally. Decarbox- ylation most likely involves the COOH end groups produced by the separate -2 2 a -3 (3 J -s W -4 - l- a (L z f -5- a D a (L W -6- a W E -1 z a -7- 0 z I I I I I 1 -714 1.49). THERMAL DECOMPOSITION OF PBT 21 1 Conventional weight-loss measurements actually represent the composite effect of these two reactions.7 kcal/mole for the activation energy.51.6 1.6the data in Figure 6 indicate a value E = 49.1 kcal/mole is calculated for CO evolution.3-butadiene (selected ion sum: mle = 54. In Figure 6 an activation energy of 27. which indicates that production of COa occurs via the same mechanism in both stages. This compares with E = 41 kcal/mole determined by Passalacqua et a1. Arrhenius plots for (0) 1. 6.9 2 .53. Hence acti- vation energies can be directly calculated for the separate reactions (10a) and (lob).9 kcal/mole is calculated for production of THF.42) and (0) Fig.o 1000/T("K) THF (selected ion sum: mle = 72. the data agree reasonably well with the high-temperature determination of the activation energy. . The dynamic MS measurements.5 1. enable the evolution rates of C and E to be determined separately by following the behavior of the corresponding ion species characteristic of these products.6 (based on butadiene being the only volatile decomposition product) and is in good agreement with recent values reported for similar poly- esters such as poly(ethy1ene terephthalate).13J4 From Figure 7 a value E = 60.8 1. The scatter in the data of Figure 7 for the low-tempera- ture C02 reaction makes determination of the activation energy difficult.71.

however. .7 coz 250-295 52.212 LUM t - E l aB O y W -4 A0 \ 1000/T("K) Fig. benzoic acid. Arrhenius plots for ( 0 )CO (mle = 28) and (0) COz (mle = 44). This is followed by a concerted ester pyrolysis reaction involving an intermediate cyclic transition state that yields volatile butadiene species.6 co 325-360 60.1 decomposition processes [eqs. Volatilization of CO as well as more complex aromatic species such as toluene. (6c) and (7)] that yield THF and butadiene.9 1. Initial polymer degradation involves an ionic decomposition process that results in the evolution of T H F with an apparent activation energy of 27.9 kcal/mole. n = 2. 7. An activation energy of 49.6 coz 320-360 52. The dynamic behavior exhibited in the COz evolution profile provides confirming evidence that THF and butadiene arise from separate primary pyrolysis reac- tions. CONCLUSION Thermal decomposition of PBT proceeds along two distinct major reaction pathways. and terephthalic acid is observed during the latter stages of polymer decomposition. Aromatic species are detected only a t trace levels. In all cases the data were best represented by a second-order rate law: that is.3-butadiene 275-360 49.7 kcal/mole is calculated for butadiene production. TABLE I Calculated Activation Energies Temperature E Species range ("C) (kcallmole) THF 235-360 27. A summary of these values is presented in Table I.

M. Polym. who kindly shared his expertise in discussions of the various thermal decomposition processes. Starnes. Houseman and F.. 14. 285-294. 17. 10. Prepr. 8.. J. M. Gilbert and F. private communication (1977). Chem. B. G. Polym. M. J. J. Sci. F. 7.1209 (1976). K. 6.1977 Revised November 16. 18. 1969. Chemistry of High Polymer Degradation Processes. H. D. 5. M. R. 12. Zamboni. Polymer. Jr. Kelleher. D. Pilati. 12. and P. Polym.. Butterworths. E. 1. 4. Sci. 20. Pietrzak and J.875 (1974). Polym. Thermochim. Kelleher for informative discussions of the properties and applications of PBT that led to the initiation of this work and W. V. L. ACS Dio. 1956. Eur. Sci. Fortunato. Lum.73 (1977). H. TM76-1516-44 (1976). H. F. W. J. W. Appl. THERMAL DECOMPOSITION OF PBT 213 The author would like to thank P. 4. N. Manaresi. L. 18. J. Ed. R. Polymer. Polym.46 (1971). Hybart. and P. K. 13. Williams.1977 . in Thermal Analysis. 517. Znstrum. Wilson and F. Yip and H. M.. New York. p.. Hamaker. 1044 (1976). Vol. Eds.. Kroh. Polymer. 11. Acta. 13.. M. Jr. Chem. Hergenrother. 3. Passalacqua. 2. References 1.J. G.761 (1977).327 (1972). Bebbington. London. Appl. Lum.R. Garn.. G. Tomita. P.237 (1972). 18. 8.1635 (1976). R. Sci. J. Schwenker. Polym. Lum. V. 9. pp.295 (1977). Academic. private communication. Grassi. Hafner. 20. Received October 5.