ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
http://www.e-journals.net 2010, 7(3), 1101-1107
Study of Non-Isothermal Decomposition and
Kinetic Analysis of 2,4-Dihydroxybenzoic Acid-
Melamine-Formaldehyde Copolymer
S. S. BUTOLIYA*, W. B. GURNULE and A. B. ZADE
Department of Chemistry, Laxminarayan Institute of Technology,
R.T.M. Nagpur University, Nagpur-440010, India.
Department of Chemistry, Kamla Nehru College,
Sakkardara Square Nagpur-440009, India.
[email protected]
Received 27 February 2010; Accepted 20 April 2010
Abstract: A copolymer (2,4-DHBAMF) synthesized by the condensation of
2,4-dihydroxybenzoic acid and melamine with formaldehyde in the presence of
acid catalyst using varied molar proportions of the reactants. A composition of
the copolymer has been determined by elemental analysis. The number average
molecular weight has been determined by conductometric titration in non-
aqueous medium. The copolymer has been characterized by UV-Visible, IR and
1
H NMR spectral analysis. Thermogravimetric analysis was carried out to study
the decomposition and various kinetic parameters. Freeman Carroll and Sharp
Wentworth methods have been applied for the calculation of kinetic parameters
while the data from Freeman Carroll method have been used to determine
various thermodynamic parameters such as order of reaction, energy of
activation, frequency factor, entropy change, free energy change and apparent
entropy change. The results indicate that given copolymer have potential as
matrix resin for long term applications at temperature up to 350 oC.
Keywords: Copolymer, Thermogravimetry, Degradation, Kinetics, Activation energy.
Introduction
The thermal degradation study of polymers has become a subject of recent interest. It is very
important property of polymer, which decides the thermal stability and processability of the
polymer. The study of thermal behavior of polymers in air at different temperature provides
important information about its practical applicability.
Shah et al1 synthesized the terpolymer from salicylic acid - formaldehyde - resorcinol.
The terpolymer was characterized by FTIR and elemental analysis. The thermal analysis
(TGA) was performed at the heating rate of 10 0C/min. in nitrogen atmosphere. Bonde and
1102 S. S. BUTOLIYA et al.
coworkers2 synthesized and characterized polymeric chelates of azelaoyl bis-p-chlorophenyl
urea with Mn+2, Co+2, Ni+2, Cu+2 and Zn+2 ion. Thermal data have been analyzed by
Freeman-Carroll and Sharp-Wentworth methods.
Thermal analysis (TA) is a typical analytical technique to describe the relationship between
physicochemical changes and temperature3-6. In order to synthesize polymers having numerous
practical applications, there is a need to investigate the effect of heat on the polymers in order to
establish their thermal stability. Singru et al7 synthesized copolymers by the condensation of
p-cresol and melamine with formaldehyde in the presence of an acid catalyst and using varied
molar proportion of the reacting monomers. Thermal studies of the resins were carried out to
determine their mode of decomposition, the activation energy (Ea), order of reaction (n),
frequency factor (Z), entropy change (S), free energy change (F) and apparent entropy
change (S*). Thermal decomposition curves were discussed with careful attention of minute
details. The Freeman-Carroll and Sharp-Wentworth methods have been used to calculate thermal
activation energy and thermal stability. In an earlier communication a large number of copolymers
were synthesized from substituted phenols and acids with formaldehyde8-10. However, no work has
been carried out on the synthesis, characterization and thermal degradation studies of the
copolymer from 2,4-dihydroxybenzoic acid, melamine and formaldehyde.
Experimental
2,4-Dihydroxybenzoic acid, melamine and formaldehyde (37%) were purchased from the
market and are from Merck, India. Solvent like N, N-dimethyl formamide and dimethyl
sulphoxide were used after distillation. All other chemicals used were of chemically pure grade.
Preparation of 2,4-DHBAMF copolymer
The 2,4-DHBAMF copolymer was prepared by condensing 2,4-dihydroxybenzoic acid (1.54 g,
0.1 mol) and melamine (1.26 g, 0.1 mol) with formaldehyde (11.1 mL, 0.3 mol) with the molar
ratios of 1:1:3 in the presence of 2 M HCl as a catalyst (Scheme 1).
Scheme 1. Synthesis of 2,4-DHBAMF copolymer.
Study of Non-Isothermal Decomposition 1103
The mixture was heated at 126 2 0C in an oil bath for 5 h. The solid product obtained was
immediately removed from the flask as soon as the reaction period was over. It was repeatedly
washed with hot water to remove unreacted monomers. The air dried copolymer was extracted
with ether to remove excess of 2,4-dihydroxybenzoic acid - formaldehyde copolymer, which
might be present along with 2,4-DHBAMF copolymer. It was further purified by dissolving in
8% NaOH solution and filtered. It was then precipitated by drop wise addition of 1:1 (v/v) conc.
HCl / water with constant stirring and filtered. The process was repeated twice. The resulting
polymer sample was washed with boiling water and dried in vacuum at room temperature. The
purified copolymer was finally ground well to pass through a 300 mesh size sieve and kept in
vacuum over silica gel. The yield of copolymer found to be 82.37% (Table 1).
Table 1. Synthesis and physical data of 2,4-DHBAMF copolymer resin.
Elemental analysis, %
Reactant
Empirical formula
Empirical formula
of repeating unit
%C %H %N
Molar ratio
(2,4-DHBA), mol
Melamine (M),
Formaldehyde
2,4-Dihydroxy
weight
benzoic acid
DP Mn
(F), mol
Found
Found
Found
mol
Cal.
Cal.
Cal.
0.1 0.1 0.3 1:1:3 C13H13O4N6 317 18 5706 49.2 48.61 4.1 4.02 26.4 26.87
Characterization of copolymers
The copolymer was subjected to elemental analysis for C, H, N on a Colemann C, H, N analyzer.
The number average molecular weight ( Mn ) was determined by non-aqueous conductometric
titration in DMF using ethanolic KOH as the titrant. A plot of the specific conductance against the
milliequivalent potassium hydroxide required for neutralization of 100 g of copolymer was made.
Electronic absorption spectrum of the copolymer in DMF was recorded on Shimadzu
double beam spectrophotometer in the range of 190-700 nm. Infrared spectrum of copolymer
was recorded in nujol mull on Perkin- Elmer- spectrum RX-I spectrophotometer in the range
of 4000 - 500 cm-1. 1H NMR spectrum of all the newly prepared copolymer has been scanned
on a Bruker Advance II 400 MHz NMR spectrophotometer, DMSO-d6 was used as a solvent.
Thermal analysis
Dynamic (non-isothermal) thermogravimetric analysis of the copolymer prepared has been
carried out in air atmosphere with a heating rate 10 0C/min. in a platinum crucible.
Theoretical considerations
To provide further evidence regarding the degradation system of analyzed compounds, we
derived the TG curves by applying an analytical method proposed by Freeman- Carroll11 and
Sharp-Wentworth12.
FreemanCarroll method
The straight-line equation derived by Freeman and Carroll, which is in the form of
dw 1
log
dt = n E a . T (1)
log Wr 2.303R log Wr
1104 S. S. BUTOLIYA et al.
Where, dw/dt = rate of change of weight with time, Wr = Wc-W, Wc = wt. loss at
completion of reaction, W= total wt loss up to time t, Ea= energy of activation, n= order of
reaction.
dw 1
log
The plot between the terms dt vs. T gives a straight line from which slope
logWr logWr
we obtained energy of activation (Ea) and intercept on y-axis as order of reaction (n). The
change in entropy (S), frequency factor (z), apparent entropy (S*) can also be calculated by
further calculations.
SharpWentworth method
Using the equation derived by Sharp and Wentworth,
dC
log
dT = log A E a . 1 (2)
1 C B 2.303R T
Where, dC/dT = rate of change of fraction of weight with change in temperature, = linear
heating rate dT/dt.
dC
log
By plotting the graph between dT vs. 1 , we obtained the straight line which give
1 C T
energy of activation (Ea) from its slope.
Results and Discussion
The newly synthesized and purified 2,4-DHBAMF copolymer was found to be brownish yellow
in color. The copolymer was soluble in DMF, DMSO, THF, concentrated H2SO4 and NaOH
solution and insoluble in almost all other organic solvents. The melting point of this copolymer is
in the range of 350 0C-400 0C. This copolymer was analyzed for carbon, hydrogen, nitrogen
content. The molecular weight for 2,4-DHBAMF copolymer was found to be 5706 (Table 1).
The UV-visible spectra (Figure 1) of the 2,4-DHBAMF copolymer in pure DMSO was
recorded in the region 200 - 850 nm at a scanning rate of 100 nm min-1 and at a chart speed
of 5 cm min-1. The copolymer sample displayed two characteristic broad bands at 250 - 280
and 290 - 340 nm. These observed positions for the absorption bands indicate the presence
of a carbonyl group (ketonic) having a carbon - oxygen double bond which is in conjugation
with the aromatic nucleus13. The latter band (more intense) can be accounted for *
transition while the former bond (less intense) may be due to n* electronic transition13.
The bathochromic shift (shift towards longer wavelength) from the basic values of the C=O
group viz. 320 and 240 nm respectively, may be due to the combined effect of conjugation
and phenolic hydroxyl group (auxochromes)14.
The IR-spectra of 2,4-DHBAMF copolymer resin was shown in Figure 2. A broad band
appeared in the region 3320 - 3324 cm-1 may be assigned to the stretching vibration of the
phenolic hydroxyl groups exhibiting intermolecular hydrogen bonding15. The presence of
weak peak at 2362 - 2379 cm-1 describes the -NH- in the melamine moiety may be ascribed
in the polymeric chain13,15. The sharp band displayed at 1573 - 1620 cm-1 may be due to
the stretching vibration of carbonyl group. A weak band at 1447 - 1449 cm-1 is ascribed to
aromatic ring. The sharp and weak band at 1279 to 1344 cm-1 suggests the presence of -CH2-
methylene bridges14. In the polymer chain 1, 2, 3, 4, 5- penta substitution of aromatic ring is
recognized from the bands appearing13 at 812.3 - 813.7.
Study of Non-Isothermal Decomposition 1105
Transmittance, %
Absorbance
wavelength Wavenumber cm-1
Figure 1. UV visible spactra of 2,4- Figure 2. Infrared spectra of 2,4-
DHBAMF copolymer. DHBAMF copolymer.
1
H NMR spectra of 2,4-DHBAMF copolymer resin is shown in Figure 3. There is a
weak signal appearing at 7.2 - 7.8 ppm may be due to aromatic proton. The intense singlet
signal appeared in the region 4.5 - 5.5 ppm can be assigned to phenolic proton of Ar-OH15.
The medium triplet signal appeared at 3.6 - 4.2 ppm may be due to amido protons CH2-NH-
polymer chain16. Also the medium doublet signal in the range of 1.9 to 2.5 ppm is attributed
to the protons of methylenic bridge Ar-CH2-NH- of polymeric chain15.
Chemical Shift , ppm
Figure 3. 1H NMR spectra of 2,4-DHBAMF copolymer.
TG of 2,4- DHBAMF copolymer
Thermogram of this copolymer is shown in Figure 4. Thermogram of copolymer depicts
three step decomposition in the temperature range 40 0C - 800 0C. The first step is of slow
decomposition between 40 0C to 340 0C corresponds to 36.49% loss which may attribute to
loss of side chain of aromatic nucleus and methylene bridges along with loss of water
molecule against calculated 37.31% present per repeat unit of the polymer. The second step
decomposition starts from 340 0C to 480 0C that represents degradation of aromatic ring and
amido groups attached to aromatic ring (76.06% found and 76.71% calculated). The third
step of decomposition starts from 480 0C to 800 0C corresponds to 99.01% loss of remaining
melamine moiety against calculated 100% loss (Table 2).
Thermoanalytical data
A plot of percentage mass loss versus temperature is shown in the Figure 4 for a
representative 2,4-DHBAMF copolymer. To obtain the relative thermal stability of the
copolymer, the method described by Freeman-Carroll and Sharp-Wentworth was
adopted. By using thermal decomposition data and then applying above methods the
activation energy (Ea) is calculated. The activation energy calculated by these methods is
depicted in Table 2.
1106 S. S. BUTOLIYA et al.
% Weight loss
Temperature, oC
Figure 4. Thermogram of 2,4-DHBAMF copolymer.
Table 2. Thermogravimetric data of 2,4-DHBAMF copolymer corresponding to heating rate
of 10 0C/min.
Ea
Thalf, 0C
First stage Second stage Third stage
kJ/mol.
S Z S* n
Trange1a, W1 Trange1b, e Trange1c, f
0 d 0 W 1 0 W 1 FW SW
C C C
40-340 36.49 340-480 76.06 480- 800 99.01 480 21.37 20.97 8.45 1238.7 -22.56 0.9
a
First degradation temperature range, bSecond degradation temperature range, cThird degradation
temperature range, dFirst maximum loss, eSecond maximum loss, fThird maximum loss.
The thermal stability of polymer predicted on the basis of the initial decomposition
temperature is in concurrence with that predicted from the activation energy values. By using
the data of Freeman-Carroll method various thermodynamic parameters have been calculated
(Table 2). Fairly good straight-line plots are obtained using the two methods. This is expected
since the decomposition of terpolymer is known not to obey first order kinetics perfectly7,9,17.
Conclusion
The 2, 4-DHBPOF copolymer based on the condensation polymerization of 2,4-
dihydroxybenzophenone and oxamide with formaldehyde in the presence of acid catalyst
has been prepared and proposed structure have been determined by various physicochemical
techniques. Thermoanalytical data was used to calculate activation energy by Freeman-
Carroll and Sharp Wentworth methods. The results indicate that given copolymer have
potential as matrix resin for long term applications at temperature up to 350 oC.
Acknowledgment
Authors are thankful to the Director, Laxminarayan Institute of Technology, R.T.M. Nagpur
University, Nagpur for providing laboratory facilities and also thankful to RSIC, Punjab
University, Chandigarh for carrying out spectral analysis.
Study of Non-Isothermal Decomposition 1107
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