1712 Ind. Eng. Chem. Res.

2009, 48, 1712–1718

Photocatalytic and Thermal Degradation of Poly(methyl methacrylate), Poly(butyl

acrylate), and Their Copolymers
Vinod Kumar Konaganti and Giridhar Madras*
Department of Chemical Engineering, Indian Institute of Science, Bangalore 560012, India

The photocatalytic and thermal degradations of poly(methyl methacrylate), poly(butyl acrylate), and their
copolymers of different compositions were studied. The photocatalytic degradation was investigated in
o-dichlorobenzene in the presence of two different catalysts, namely, Degussa P-25 and combustion synthesized
nanotitania (CSN-TiO2). The samples were analyzed by using gel permeation chromatography (GPC) to obtain
the molecular weight distributions (MWDs) as a function of reaction time. Experimental data indicated that
the photodegradation of these polymers occurs by both random and chain end scission. A continuous distribution
kinetic model was used to determine the degradation rate coefficients by fitting the experimental data with
the model. Both the random and specific rate coefficients of the copolymers decreased with increasing
percentage of butyl acrylate (BA). Thermal degradation of the copolymers was investigated by thermo-
gravimetry. The normalized weight loss profiles for the copolymers showed that the thermal stability of the
copolymers increased with mole percentage of BA in the copolymer (PMMABA). The Ozawa method was
used to determine the activation energies at different conversions. At low acrylate content in the copolymer,
the activation energy depends on conversion, indicating multiple degradation mechanisms. At high acrylate
content in the copolymer, the activation energy is independent of conversion, indicating degradation by a
one-step mechanism.

Introduction photocatalytic degradation of these copolymers have not been

reported. In the present study, different compositions of PM-
The study of the degradation of polymers is very important MABA copolymers were synthesized, and the photocatalytic
to our understanding of the stability and longevity of the polymer degradation and thermal stabilities of these copolymers were
and for the design of plastic recycling processes.1 Several modes studied. The effect of combustion-synthesized nanotitania (CSN-
of degradation such as the application of heat, light, sound, and TiO2) and Degussa P-25 TiO2 on the photodegradation of these
enzymes are available. Poly(alkyl acrylates), poly(alkyl meth- polymers in solution was studied. Continuous distribution
acrylates), and their copolymers are used in several industries kinetics was applied to model the kinetics of the degradation
for paints, textiles, automobiles, fibers, lubricants, microelec- process and to determine the rate coefficients for photocatalytic
tronics,2 etc. because of their mechanical and electrical proper- degradation. The thermal stability of these polymers was
ties, optical clarity, and high chemical and thermal stabilities.3,4 investigated by thermogravimetric analysis. Kissinger and
Because the properties of copolymer systems mainly depend Ozawa methods were used to determine the kinetic parameters
on the number of individual sequences in the main chain, of these copolymers. This is the first detailed kinetic study to
copolymers with a wide range of properties from stiff plastics predict the effect of composition on the photocatalytic degrada-
to elastomeric materials can be prepared.5 The poly(methyl tion and thermal stability of poly(methyl methacrylate-co-butyl
methacrylate-co-butyl acrylate) (PMMABA) copolymers are acrylate) copolymers.
extensively used as adhesives and coatings.6 Polymers with
required properties for particular purposes can be obtained by
combining MMA, which can be considered as hard sequences Experimental Details
contributing stiffness, with BA, as soft sequences.7 Materials. Methyl methacrylate (MMA) and n-butyl acrylate
There are several studies on the degradation of homo- and (BA) monomers were purchased from Sigma-Aldrich and
copolymers of poly(alkyl acrylates) and poly(alkyl methacry- purified of inhibitor by washing with 5% NaOH solution
lates). The effect of alkyl group on the thermal, ultrasonic, and followed by washing with distilled water and distillation. The
enzymatic degradation of poly(alkyl acrylates),8-10 and thermal solvents, o-dichlorobenzene (DCB) and methanol, were pur-
and photodegradation of poly(alkyl methacrylates)11,12 have been chased from SD Fine Chemicals, distilled, and filtered through
studied. Thermal degradation of copolymers of methyl meth- a 0.2 µm nylon filter paper before use. The initiator, azobi-
acrylates with different monomers has also been reported.13-15 sisobutyronitrile (AIBN), was purchased from SD Fine Chemi-
There are several studies on the photodegradation of poly(alkyl cals and purified by precipitation in acetone. The precursor for
acrylates) and poly(alkyl methacrylates) using solid samples with the catalyst preparation, titanium isopropoxide (Ti(i-OPr)4), was
a focus on the mode of degradation and mechanism.11,16,17 The purchased from Lancaster, and the fuel glycine (H2N-
photodegradation of copolymers and blends of methyl meth- CH2-COOH) was obtained from Merck. Polystyrene standards
acrylates has also been studied.18 obtained from Polymer Laboratory were used for the calibration
The mechanical damping curves and properties of PMMABA of molecular weight.
copolymers have been studied,19 but studies on the thermal/ Polymerization. Homopolymers PMMA (Mn0 ) 120000 and
* Author to whom the correspondence should be addressed PD ) 1.6) and PBA (Mn0 ) 198200 and PD ) 1.4) and
(telephone 091-80-22932321; fax: 091-80-23600683; e-mail: giridhar@ copolymers PMMABA-6 (6% BA Mn0 ) 235000 and PD )
chemeng.iisc.ernet.in. 1.6), PMMABA-15 (15% BA Mn0 ) 215000 and PD ) 1.3),
10.1021/ie801646y CCC: $40.75  2009 American Chemical Society
Published on Web 01/13/2009
 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009 1713
PMMABA-26 (26% BA Mn0 ) 196000 and PD ) 1.5), pump and three size exclusion columns packed with cross-linked
PMMABA-42 (42% BA Mn0 ) 170000 and PD ) 1.3), poly(styrene-divinyl benzene) (Styragel HR 5E, HR 4, HR 1)
and PMMABA-68 (68% BA Mn0 ) 132430 and PD ) 1.4) (300 mm × 7.5 mm); a differential refractometer (Waters RI
were synthesized by solution polymerization technique with 2410) was used for detection, and a data acquisition system
AIBN as the initiator at 60 °C. Mn0 represents the initial stored the data. The samples collected at different time intervals
molecular weight of the polymer, and PD represents the were injected through a Rheodyne (7725i) valve with a sample
polydispersity of the polymer. Calculated amounts of MMA, loop of 50 µL. The obtained chromatogram was converted to
BA, DCB, and AIBN were placed in culture tubes, and the molecular weight distribution (MWD) using universal calibra-
mixture was flushed with N2 for 15 min. The tubes were kept tion. Tetrahydrofuran (THF) was used as the eluent at a flow
in the incubator shaker at 60 °C. The copolymers were rate of 1 mL/min.
precipitated in methanol and dried at 50 °C. Thermogravimetric Analysis. Polymer (10-15 mg) was
NMR Characterization. 1H NMR (400 MHz, Bruker) pyrolyzed in an inert atmosphere (nitrogen at 150 cm3 min-1)
spectroscopy was used to determine the composition of the in a thermogravimetric analyzer (TGA) (Perkin-Elmer, Pyris)
synthesized copolymers, using CDCl3 as a solvent and tetram- at different heating rates in the temperature range from 25 to
ethylsilane as a reference substance for resonance frequency. 750 °C.
Synthesis and Characterization of Catalyst. The solution
combustion method was used for the preparation of anatase Theoretical Model
CSN-TiO2 by using titanyl nitrate (TiO(NO3)2) as a precursor
with glycine (H2N-CH2-COOH) as a fuel. The catalyst was Photodegradation. Continuous distribution kinetics was used
characterized by using X-ray diffraction, BET surface area, to study the degradation kinetics of the polymers PMMA and
TGA/DTA, UV, and IR spectrometry. The XRD pattern of CSN- its copolymers of different compositions with BA. Reactions 1
TiO2 was recorded using a Siemens D-5005 diffractometer. For and 2 represent the polymer degradation by random scission
the CSN-TiO2 the pattern can be indexed to pure anatase phase and specific scission, respectively.23,24
of TiO2. The crystallite size was determined from XRD using kr
the Sherrer formula; the mean crystallite size is estimated to be P(x′) 98 P(x) + P(x′ - x) (1)
10 ( 2 nm, lower than the 30-35 nm for Degussa P-25. The
surface area of the catalyst, determined by using a standard BET
ks
apparatus (NOVA-1000, Quantachrome), was 246 m2/g, much P(x′) 98 Q(xs) + P(x′ - xs) (2)
higher than the 50 m2/g for Degussa P-25. The total weight
losses determined from the TGA of CSN-TiO2 and Degussa
P-25 were 15.6 and 1.4%, respectively, which indicates the P(x) represents the polymer of molecular weight x, and p(x,t)
presence of surface-bound water and hydroxyl groups for CSN- represents the instantaneous MWD of the polymer. Q(xs)
TiO2. Fourier transform infrared (FTIR) studies were carried represents a specific product with molecular weight xs in chain
out in the 400-4000 cm-1 frequency range in the transmission end scission, and q(x,t) represents the MWD of the specific
mode (Perkin-Elmer, FTIR-Spectrum-1000). The FTIR spectra product. For reactions 1 and 2, the random chain scission and
also showed higher hydroxyl content for the CSN-TiO2. Thus, specific chain scission rate coefficients are kr and ks, respectively.
CSN-TiO2 has lower size, higher surface area, and higher The distribution balance equations for the above two reactions
hydroxyl content than Degussa P-25. The XRD, TGA, UV, and are23
IR spectra of CSN-TiO2 have been reported in our earlier
∫
∂p(x,t) ∞
studies.20-22 Further details of the catalyst preparation are ) -kr(x)p(x,t) + 2 kr(x′)p(x′,t)Ω(x,x′) dx′ -
presented elsewhere.20-22 ∂t x

∫
∞
Photochemical Reactor. The photochemical reactor used in ks(x)p(x,t) + x
ks(x′)p(x′, t)Ω(x - xs,x′) dx′ (3)
these experiments consists of a jacketed quartz tube (with water
∫
circulation to maintain the temperature constant) of inner ∂q(x,t) ∞
) x ks(x′)p(x′,t)Ω(xs,x′) dx′ (4)
diameter ) 3.4 cm, outer diameter ) 4 cm, and length ) 21 ∂t
cm and a Pyrex glass reactor of inner diameter ) 5.7 cm and For random chain scission, the distribution of degraded
length ) 16 cm. A high-pressure mercury lamp of 125 W products is given by the stoichiometric kernel Ω(x,x′), and is
(Philips, India) was used as a UV light source by placing it 1/x′. For chain end scission, the stoichiometric kernels are
inside the jacketed quartz tube. The solution was taken in the represented by Dirac delta functions, Ω(x - xs,x′) ) δ(x - x′
reactor vessel and stirred with a magnetic stirrer to ensure + xs) and Ω(x,x′) ) δ(x - xs),24,25 for products having molecular
uniform mixing of the catalyst in the solution. The jacketed weights of x - xs and xs, respectively. By definition these Dirac
quartz tube was kept above 2 cm to the stirrer. The lamp emitted delta functions are symmetric and normalized to unity. The
predominantly at 365 nm, and the photon flux was 3850 µW degradation rate coefficient for random scission is assumed to
cm-2. Further details are provided elsewhere.20,21 be linearly dependent on the molecular weight of the polymer,26
Degradation Experiments. The polymer solution of con- that is, kr(x) ) krx, whereas the specific rate coefficient is
centration 2 g/L was prepared for all experiments using DCB independent of molecular weight,24 that is, ks(x) ) ks. On the
as solvent. Ninety milliliters of the solution was taken in the basis of moment analysis (see Appendix A in the Supporting
reaction vessel. Photocatalytic experiments were performed with Information for details), the variation of number-average mo-
a catalyst loading of 1 g/L. The samples were collected at lecular weight, Mn, is given by
different intervals of time and centrifuged to remove the catalyst
particles before analysis by gel permeation chromatography kkrMn0 - k2 tan (kt)
(GPC). Mn ) (5)
kkr + kr2Mn0 tan (kt)
Gel Permeation Chromatography Analysis. The GPC
consisted of a high-pressure liquid chromatography (HPLC) where k ) krksxs.
1714 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009

Thermal Degradation by Pyrolysis. The rate of degradation

of the polymer can be represented by
dc
- ) k ′cn (6)
dt
where c is mass of the polymer, k ′ is the degradation rate
coefficient and n is the apparent order of degradation. The above
equation can be represented in terms of degree of conversion
(R).27
dR
) A exp(-E/RT)(1 - R)n (7)
dt
where A is the pre-exponential factor, E is the apparent activation
energy, R is the universal gas constant, and T is the temperature
of the sample at that time.
Kissinger Method. Kissinger developed a method to estimate
the activation energy from dynamic measurements.27 In this
method, the temperature values at the maxima (Tm) of the first-
Figure 1. Fineman-Ross representation of MMA/BA composition data for
derivative weight loss curves are obtained. The maximum rate copolymers. (Inset) Dependence of instantaneous copolymer composition
occurs when d/dt (dR/dt) is zero, thus on initial comonomer composition.

d(ln(φ/T2m)) E the factor 2/3 arises from the ratio of protons of the specific
)- (8)
d(1/Tm) R identifying groups.32
The reactivity ratio of the monomer was determined from
where φ is the heating rate.27
the polymer NMR composition data by using the Fineman-Ross
The activation energy can be determined from the plot of
method.35 At low conversions, the copolymer composition is
ln(φ/T2m) against l/Tm and the order from the intercept of the
described by the copolymer equation
plot.28
Ozawa Method. Ozawa developed a method to determine
the activation energy at different conversions (R) by considering
the effect of the heating rate on thermogravimetric curves.29
d[M1]
d[M2]
) ( )(
M1 r1M1 + M2
M2 r2M2 + M1 ) (12)

This method uses the following equation for the variation of where d[M1] and d[M2] represent the compositions of monomers
conversion (R). in the copolymer and M1 and M2 represent the concentrations
of monomers in the feed and r1 and r2 are the monomer reactivity
dR E
dt
) A exp - ( )
RT
g(R) (9) ratios of MMA and BA, respectively.
In the Fineman-Ross method, the copolymer equation is
At a constant heating rate, by integrating the above equation linearized to

()
and by using Doyle’s approximation,29,30 the variation of R is
given by M1
M2 (
1-
d[M2]
d[M1]
) )
d[M2] M21
d[M1] M2 1
r - r2 (13)
log (∫0
R dR
g(R))) log
AE
R ( )
- log φ - 2.315 - 0.4567
E
RT ( ) 2

The above equation can be rewritten as

(10)
G ) r1F - r2 (14)
At fixed conversions, the plot of log φ against 1/T is linear
and the slope gives the activation energy. where G ) (x(y - 1)/y), F ) (x2/y), x ) (M1/M2), and y )
(d[M1]/d[M2]). Here x and y are ratios of monomers in the feed
Results and Discussion and in the copolymer, respectively.
Figure 1 shows the Fineman-Ross plot for calculating the
Characterization of Copolymers. 1H NMR (400 MHz, monomer reactivity ratios, which are r1 (MMA) ) 2.98 and r2
Bruker) spectroscopy was used to determine the composition (BA) ) 0.31. These are comparable to the values reported in
of the copolymers. The MMA monomer shows a singlet peak the literature:32 r1 (MMA) ) 2.17 and r2 (BA) ) 0.44. The
corresponding to methoxy of the ester linkage (-OCH3) at δ product of reactivity ratios is approximately equal to one,
3.8. The BA shows a triplet peak corresponding to the indicating the prepared copolymers are random copolymers. The
ethyleneoxy of the ester linkage (-OCH2) at δ 4.2.31-33 These monomer reactivity of MMA is much higher than that of BA,
peaks were identified in all copolymers, and the monomer which can be seen from the inset of Figure 1.
compositions of the copolymers were found from the integrated Photocatalytic Degradation. The photodegradation of PMMA,
peak areas, according to the following equation34 PBA, and the copolymers of MMA and BA was studied with
and without catalyst. The photocatalytic degradation was carried
2am out in the presence of two different catalysts, Degussa P-25
3ab and CSN-TiO2. The photocatalytic degradation of these poly-
ym ) (11) mers occurred by both random and chain end scission, which
2am
1+ can be observed from the GPC chromatogram. In the chro-
3ab
matogram, the first peak represents the random product distribu-
where ym is the mole fraction of MMA in the copolymer, am is tion due to random chain scission and the second peak represents
the methoxy peak area, ab is the ethyleneoxy peak area, and the formation of a specific product distribution of average
 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009 1715

Figure 3. Variation of (a) random degradation rate coefficients and (b) chain
Figure 2. Variation of Mn of copolymer as a function of time for (a) 6 mol end degradation rate coefficients with mole percentage of BA in the
% BA and (b) 68 mol% of BA: (9) UV without catalyst; (b) UV + P-25; copolymer: (9) UV without catalyst; (b) UV + P-25; (2) UV + CSN-
(2) UV + CSN-TiO2. Solid lines are model fits based on eq 5. TiO2.

molecular weight 200 due to chain end scission. The end radical main chain by a hydroxyl radical or reaction with oxygen to
is responsible for the degradation of polymer by chain end form peroxide radical followed by β-scission.24 It was deter-
scission, which gives monomer or low molecular weight specific mined that only 1% of the hydroxyl radicals formed are involved
products. The analysis of the second peak indicates that these directly in main-chain scission, whereas the remaining partici-
are oligomers of MMA. A representative MWD is shown in pate in hydrogen abstraction and other radical reactions.37 The
Figure S1 of the Supporting Information. The variation of reduced band gap and increase in the number of hydroxyl groups
number-average molecular weight with time for the copolymers on the surface are the important factors for the higher activity
PMMABA-6 and PMMABA-68 is shown in Figure 2 (see also of CSN-TiO2 compared to P-25. The degradation rate coef-
Figure S2 of the Supporting Information for other compositions). ficients for both random and specific chain end scission decrease
The lines are model prediction based on eq 5. In the photodeg- with increasing mole percentage of BA in the copolymer. The
radation of PBA, the effect of specific chain scission is random degradation rate coefficients decrease exponentially and
negligible, which was observed from the absence of specific the specific chain end degradation rate coefficients decrease
products in the GPC chromatogram. The photodegradability of linearly with mole percentage of BA in the copolymer, as shown
PBA is very much less compared to all other copolymers, and in Figure 3.
the homopolymer, PMMA, and degrades predominantly by Thermal Degradation. The thermal degradation of the
random scission.36 copolymers was studied at four different heating rates of 5, 10,
The rate coefficients for both random chain and chain end 15, and 20 °C min-1 using thermogravimetric analysis (TGA)
scission of these polymers are obtained by fitting the experi- in a nitrogen flow environment. The normalized weight loss
mental data with the model (based on eq 5). The values of the and differential fractional weight loss profiles for homopolymers
degradation rate coefficients obtained from the model indicated PMMA and PBA and PMMABA copolymers at a heating rate
that the degradation of the polymer by random scission is of 10 °C min-1 are shown in Figure 4. The variation of
enhanced nearly 1.4-1.7 times in the presence of P-25 and temperature with mole percentage of BA in the copolymer
2.4-3.5 times in the presence of CSN-TiO2 compared to the (PMMABA) at different conversions is shown in Figure S3 of
noncatalytic process. In the case of specific chain end scission, the Supporting Information for the heating rate 10 °C min-1.
the polymer degradation is enhanced by 1.2-1.5 times in the The degradation temperature increases linearly with mole
presence of P-25 and by 1.7-2.4 times in the presence of CSN- percentage of BA in the copolymer, indicating the increase in
TiO2 compared to the noncatalytic process. The photodegrada- thermal stability of the copolymer with mole percentage of BA.
tion is mainly photooxidative, where both chain scission and Similar profiles were observed for heating rates 5, 15, and 20
random scission are initiated by hydrogen abstraction from the °C min-1.
1716 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009

Figure 4. (a) Normalized weight loss and (b) differential fractional weight
loss profiles for PMMABA copolymers of different compositions at a Figure 6. Ozawa plots to determine the activation energy of PMMABA-6
heating rate of 10 °C min-1. (a) at low conversions from 0.1 to 0.2 and (b) at high conversions from 0.8
to 0.9.

Figure 5. Variation of activation energy (E) and order (n) with mole
percentage of BA. Figure 7. Variation of activation energy (E) with mole percentage of BA:
conversions from (b) 0.1 to 0.2 and from (9) 0.8 to 0.9. (Inset) Variation
The activation energies determined by using the Kissinger of difference between activation energies at high and low conversions.
method (using eq 8) are obtained from Figure S4 of the
Supporting Information. The solid lines are based on linear The Ozawa method is used to determine the activation energy
regression to obtain the activation energies. The variation of of the copolymer at different conversions. Figure 6 shows
the activation energy and the order of reaction for different Ozawa plots for the copolymer of 6 mol % of BA at low and
compositions of PMMABA copolymer obtained from the high conversions. Ozawa plots for the remaining compositions
Kissinger method are shown in Figure 5. This indicates that are shown in Figure S5 of the Supporting Information. The
the activation energy does not vary linearly with mole percentage variation of activation energy with mole percentage of BA in
of BA. The order of the degradation reaction decreases with the copolymer at low and high conversions is shown in Figure
mole percentage of BA in the copolymer. This may be due to 7. Figure 7 clearly indicates that there is a maximum for the
the change of degradation reaction from a two-step mechanism activation energy with mole percentage of BA in the copolymer,
(both random and chain end scission) to a one-step mechanism which can be attributed to new initiation, transfer, and termina-
(predominantly random scission). tion reactions involved at high acrylate content.38
 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009 1717
The change of activation energy with conversion indicates the different compositions (the numbers on the lines indicate mole
existence of multiple degradation mechanisms.39 The thermal percentage of BA in the copolymer). Figure S5 shows the Ozawa
degradation of PMMA occurs by both random and specific end plots for PMMABA copolymers for (a) 0 mol % of BA
initiation,40 and thermal degradation of PBA occurs predominantly (PMMA) conversions from 0.1 to 0.2, (b) 0 mol % of BA
by random scission.41 Because the homopolymers degrade by (PMMA) conversions from 0.8 to 0.9, (c) 15 mol % of BA
different mechanisms, the degradation mechanism of the copolymer conversions from 0.1 to 0.2, (d) 15 mol % of BA conversions
will change depending on the composition of the copolymer. To from 0.8 to 0.9, (e) 26 mol % of BA conversions from 0.1 to
differentiate between the multiple degradation mechanisms, one 0.2, (f) 26 mol % of BA conversions from 0.8 to 0.9, (g) 42
can analyze the differences between the activation energies at mol % of BA conversions from 0.1 to 0.2, (h) 42 mol % of BA
various conversions. The inset of Figure 7 shows the decrease of conversions from 0.8 to 0.9, (i) 68 mol % of BA conversions
difference between the activation energies at high and low from 0.1 to 0.2, (j) 68 mol % of BA conversions from 0.8 to
conversions with mole percentage of BA. With increasing BA 0.9, (k) 100 mol % of BA (PBA) conversions from 0.1 to 0.2,
content in the copolymer, the contribution of chain end scission and (l) 100 mol % of BA (PBA) conversions from 0.8 to 0.9.
decreases. At high acrylate content the copolymer degrades This information is available free of charge via the Internet at
predominantly by a one-step mechanism, which can be observed http://pubs.acs.org.
from the smaller difference between the activation energies at high
and low conversions as shown in the inset of Figure 7.
Literature Cited
(1) Miller, A. Industry invests in reusing plastics. EnViron. Sci. Technol.
Conclusions 1994, 28, 16A.
The PMMABA copolymers of different compositions were (2) Penzel, E. Ullmann’s Encyclopedia of Industrial Chemistry; VCH:
New York, 1992; Vol. A21, p 157.
synthesized by using a solution polymerization technique and (3) Mark, H. F., Bikales, N. M., Overberger, Ch. G., Menges, G.,
characterized by 1H NMR spectroscopy. The reactivity ratios Kroschwitz, J. I., Eds. Encyclopedia of Polymer science and Engineering;
determined from the Fineman-Ross method indicated that the Wiley Interscience: New York, 1985; p 234.
copolymers are random. The photodegradation of these copoly- (4) Bandrup, J.; Immergut, E. H. Polymer Handbook, 2nd ed.; Wiley
Interscience: New York, 1975; Vol. 87, p 159.
mers was carried out in the presence of Degussa P-25 and CSN- (5) Cowie, J. M. G. Polymers: Chemistry and Physics of Modern
TiO2. A continuous distribution model accounting for both Materials; International Textbook Co.: Philadelphia, PA, 1973; pp 14-
random and chain end scission was used to determine the 233.
degradation rate coefficients by fitting the experimental data with (6) Gonzalez, I.; Asua, J. M.; Leiza, J. R. The role of methyl methacrylate
the model. The rate coefficients indicated that CSN-TiO2 has a on branching and gel formation in the emulsion copolymerization of BA/
MMA. Polymer 2007, 48, 2542–2547.
higher catalytic activity compared to Degussa P-25 for the (7) Kaufmann, H. S.; Falcetta, J. J. Introduction to Polymer Science
photodegradation of PMMABA copolymers. Both the random and Technology: An SPE Textbook; Wiley: New York, 1977; pp 131, 311,
and specific rate coefficients decrease with increasing mole 402.
percentage of BA in the copolymer. Therefore, it is possible to (8) Mahalik, J. P.; Madras, G. Effect of alkyl group substituents on the
thermal and enzymatic degradation of poly(n-alkyl acrylate). Ind. Eng.
predict the degradation rate coefficient of the copolymer of any Chem. Res. 2005, 44, 4171–4177.
composition. (9) Malhotra, S. L. Ultrasonic solution degradations of poly(alkyl
The thermal degradation of the copolymers was studied by methacrylates). J. Macromol. Sci. Chem. 1986, 23, 729–748.
pyrolysis using thermogravimetric analysis. Normalized weight (10) Mahalik, J. P.; Madras, G. Effect of alkyl group substituents on
loss profiles were plotted against mole percentage of BA in the the ultrasonic degradation of poly(n-alkyl acrylate). Ind. Eng. Chem. Res.
2005, 44, 6572–6577.
copolymer, and the results indicate that the thermal stability of (11) Kaczmarek, H.; Kaminska, A.; Herk, A. V. Photo oxidative
the copolymers increase with mole percentage of BA in the degradation of poly(alkyl methacrylate)s. Eur. Polym. J. 2000, 36, 767–
copolymer. The Ozawa method was used to determine the 777.
activation energies at different conversions. The difference (12) Marimuthu, A.; Madras, G. Effect of alkyl group substituents on
the degradation of poly(alkyl methacrylates) in supercritical fluids. Ind. Eng.
between the activation energies at high conversion and low Chem. Res. 2007, 46, 15–21.
conversion decreases with mole percentage of BA, indicating (13) Grassie, N.; Farish, E. The thermal degradation of copolymers of
the shift of degradation reaction mechanism from a two-step styrene and methyl methacrylate. Eur. Polym. J. 1967, 3, 305–315.
process to a one-step process. (14) Grassie, N.; Farish, E. The thermal degradation of copolymers of
methyl methacrylate and acrylonitrile. Eur. Polym. J. 1967, 3, 619–625.
(15) Grassie, N.; Torrance, B. J. D. Thermal degradation of copolymers
Acknowledgment of methyl methacrylate and methyl acrylate. I. Products and general
characteristics of the reaction. J. Polym. Sci.: Part A-1 1968, 6, 3303–
G.M. thanks the Department of Science and Technology, 3314.
India, for financial support and a Swarnajayanthi Fellowship. (16) Harbron, E. J.; McCaffrey, V. P.; Xu, R.; Forbes, M. D. E.
Stereochemistry and pseudosymmetries in main chain polymeric free
radicals. J. Am. Chem. Soc. 2000, 122, 9182–9188.
Supporting Information Available: Appendix A: Derivation (17) Chiantore, O.; Trossarelli, L.; Lazzari, M. Photooxidative degrada-
of number average molecular weight, Mn (eq 5) based on tion of acrylic and methacrylic polymers. Polymer 2000, 41, 1657–1668.
moment analysis. Figure S1 shows the time evolution of the (18) Guerrero, A. R.; Ramirez, J. C. Photodegradation of poly(methyl
normalized mass distribution of the copolymer PMMABA-6 methacrylate)/bisphenol A polycarbonate blends. Polym. Bull. 1994, 33,
541–548.
with reaction (UV + CSN-TiO2) time. Figure S2 shows the
(19) Kaplan, D. S. Structure-property relationships in copolymers to
variation of Mn of copolymer with time for (a) 0 mol % of BA composites: molecular interpretation of the glass transition phenomenon.
(PMMA), (b) 15 mol % of BA, (c) 26 mol % of BA, (d) 42 J. Appl. Polym. Sci. 1976, 20, 2615–2629.
mol % of BA, and (e) 100 mol % BA (PBA). Figure S3 shows (20) Nagaveni, K.; Sivalingam, G.; Hegde, M. S.; Madras, G. Solar
the variation of temperature with mole percentage of BA in photocatalytic degradation of dyes: high activity of combustion synthesized
nano TiO2. Appl. Catal., B 2004, 48, 83–93.
PMMABA at different conversions (the numbers on the lines (21) Sivalingam, G.; Nagaveni, K.; Hegde, M. S.; Madras, G. Photo-
indicate conversions). Figure S4 shows the Kissinger plots to catalytic degradation of various dyes by combustion synthesized nano
determine the activation energies of PMMABA copolymers of anatase TiO2. Appl. Catal., B 2003, 45, 23–28.
1718 Ind. Eng. Chem. Res., Vol. 48, No. 4, 2009

(22) Nagaveni, K.; Hegde, M. S.; Madras, G. Synthesis and structure (33) Pouchert, C. J. The Aldrich Library of NMR Spectra, 2nd ed.;
of nanocrystalline TiO2 with lower band gap showing high photocatalytic Aldrich Chemicals: Milwaukee, WI, 1983.
activity. Langmuir 2004, 20, 2900–2907. (34) Vail, N. K.; Barlow, J. W.; Beaman, J. J.; Marcus, H. L.; Bourell,
(23) Daraboina, N.; Madras, G. Thermal and photocatalytic degradation D. L. Development of a poly(methyl methacrylate-co-n-butyl methacrylate)
of poly(methyl methacrylate), poly(butyl acrylate) and their copolymers. copolymer binder system. J. Appl. Polym. Sci. 1994, 52, 789–811.
Ind. Eng. Chem. Res. 2008, 47, 6828–6834. (35) Fineman, M.; Ross, S. D. Linear method to determining monomer
(24) Kodera, Y.; McCoy, B. J. Distribution kinetics of radical mecha- reactivity ratios in copolymerization. J. Polym. Sci. 1950, 5, 259–265.
nisms: reversible polymer decomposition. AIChE J. 1997, 43, 3205–3214. (36) Marimuthu, A.; Madras, G. Photocatalytic oxidative degradation
(25) Madras, G.; McCoy, B. J. Time evolution to similarity solutions of poly(alkyl acrylates) with nano-TiO2. Ind. Eng. Chem. Res. 2008, 47,
for polymer degradation. AIChE J. 1998, 44, 647–655. 2182–2190.
(37) Grollmann, U.; Schnabel, W. Free radical-induced oxidative
(26) Madras, G.; Chung, G. Y.; Smith, J. M.; McCoy, B. J. Molecular degradation of polyacrylamide in aqueous solution. Polym. Degrad. Stab.
weight effect on the dynamics of polystyrene degradation. Ind. Eng. Chem. 1982, 4, 203–212.
Res. 1997, 36, 2019–2024. (38) Grassie, N.; Torrance, B. J. D.; Fortune, J. D. Thermal Degradation
(27) Kissinger, H. E. Reaction kinetics in differential thermal analysis. of Copolymers; Air Force Materials Laboratory: Wright Patterson, OH, 1971.
Anal. Chem. 1957, 29, 1702–1705. (39) Schmidt, V.; Soldi, V. Influence of polycaprolactone-triol addition
(28) Wang, X. S.; Li, X. G.; Yan, D. Y. Thermal decomposition kinetics on thermal stability of soy protein isolate based films. Polym. Degrad. Stab.
of thermotropic poly(oxybenzoate-co-trimethylene terephthalate). J. Appl. 2006, 91, 3124–3130.
Polym. Sci. 2000, 78, 2025–2036. (40) MacCallum, J. R. The thermal degradation of poly(methyl meth-
(29) Ozawa, T. A new method of analyzing thermogravimetric data. acrylate). Die. Makromol. Chem. 1964, 83, 137–147.
Bull. Chem. Soc. Jpn. 1965, 38, 1881–1886. (41) Haken, J. K.; Tan, L. Mechanism of thermal degradation of
(30) Doyle, C. D. Kinetic analysis of thermogavimetric data. J. Appl. poly(alkyl acrylate)s using pyrolysis gas chromatography mass spectroscopy.
Polym. Sci. 1961, 5, 285–292. J. Polym. Sci., Part A 1988, 26, 1315–1322.
(31) McManus, N. T.; Penlidis, A. NMR analysis of butyl acrylate/
methylmethacrylate/R-methyl styrene terpolymers. J. Appl. Polym. Sci. 2006, ReceiVed for reView October 29, 2008
106, 2093–2098. ReVised manuscript receiVed December 4, 2008
(32) Mishra, A.; Daswal, S. Copolymerization of n-butylacrylate with Accepted December 6, 2008
methyl methacrylate by a novel photoinitiator, 1-(bromoacetyl)pyrene. Int.
J. Chem. Kinet. 2007, 39, 261–267. IE801646Y