Polymer Degradation and Stability 60 (1998) 67-70

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Thermal analysis of some chitosan Schiff bases

Fahd A. A. Tirkistani
Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al Mukkarmah, P.O. Box 7655,
Saudi Arabia

(Received 4 November 1996; accepted 30 December 1996)

Reactions of chitosan with aromatic aldehydes gave Schiff base polymers. The
products were characterized and identified using microanalysis and IR spectro-
scopy. Thermal analyses of the polymers showed that they are less stable than
chitosan itself. 0 1998 Elsevier Science Limited. All rights reserved

1 INTRODUCTION 2.2 Preparation of Schiff base polymers

Reactions of the amino group of chitosan with
carbonyl compounds leading to the formation of
Schiff bases have been given attention in the lit-
erature, especially after the use of chitosan to
form articles, such as membranes and fibres.’
Plisko and others2,3 used salicylaldehyde to treat
chitosan as a preliminary step towards the for-
mation of polyampholytes. Hirano and Ohe4
reported a novel, straightforward procedure for
N-acylation of chitosan by reacting with unsatu-
rated acid anhydrides which are of interest as they
affect the selective aggregation of some cancer
cells.
In this paper, the reaction of chitosan with aro-
matic aldehyde derivatives was carried out in order
to study the thermal stability of the Schiff base
polymers formed.
2 EXPERIMENTAL
2.1 Materials
Chitosan (Aldrich Chem. Co. Inc.) was used with-
out further purification.
Benzaldehyde (BA), p-anisaldehyde (ANA), p-
chlorobenzaldehyde (CBA), p-nitrobenzaldehyde
(NBA) andp-N-dimethylaminobennldehyde (DBA)
(BDH Chemical Co. Ltd) were purified using stan-
dard procedures.
67
An equimolar ratio of aromatic aldehyde to chit-
osan was fused for 0.5 h, and then 50 ml of glacial
acetic acid was added to the reaction mixture and
refluxed for 2 h. The acetic acid was removed by
distillation and the reaction mixture cooled to
room temperature, washed with diethyl ether and
ethanol to remove any excess aromatic aldehyde.
The solid products of chitosan-BA (I), chitosan-
ANA (II), chitosan_CBA (III), chitosan-NBA (IV)
and chitosan-DBA (V) were dried in a vacuum
oven for several days.
2.3 Analytical techniques
2.3.1 Infrared spectroscopy (IR)
Spectra were recorded in film form using a Pye
Unicam SP 2000 spectrophotometer and the KBr
disc technique.
Carbon, hydrogen and nitrogen contents were
measured at the Microanalytical Unit of Cairo
University.
2.3.2 D@erential scanning calorimetry (DSC)
DSC curves were obtained using the Mettler TA
3000 DSC apparatus. The samples were heated at
lO”C/min from ambient to 500°C.
2.3.3 Thermogravimetry (TG)
TG measurements were made using a Mettler 3000
thermobalance. Samples (-10 mg) were heated at
68 Fahd A. A. Tirkistani

lO”C/min in a dynamic nitrogen atmosphere

(70ml/min); the sample holder was boat-shaped,
10 mm x 5 mm x 2.5 mm deep, and the thermocouple
used to measure the temperature was placed within
1 mm of the holder.

Chltosqn
3 RESULTS AND DISCUSSION

3.1 Characterization of the polymers

All the Schiff base polymers formed are intensely

coloured, stable in air and insoluble in common
organic solvents. The IR spectrum of chitosan
(Table 1) shows a broad band at 3500cm ml due to
OH and NH2 groups. Also, the most significant
part of the spectrum is that showing the amide L- I
200
1 I

bands at 1665 and 1313 cm-‘. There are bands at 100 300 400 500

1460, 1410, 1380, 1180 and 800cm-‘, in addition Temp. ,‘C

to the usual broad band at 2900cmP1. These char-

Fig. 1. DSC curves of chitosan and Schiff base polymers
acteristic bands are in agreement with the IR spec-
trum of chitosan presented by Muzzarelli et aL5
The reaction of chitosan with aromatic aldehyde
may form two alternative products: (a) or (b) (see 100
Scheme 1).
90
CHZO” n
i- ~-’
80
&L , : ),
NH2 wt. 70
IOSS
(x) 60

50

40

30 c \ ‘L?, --. .._., _

‘.*--.. ... ..
I-
‘\
‘-..
20 .-.b

(?.,
_ 13
H
I
I I 3CH3 1 I I , 1 I
tll Cl 100 200 300 400 500 600
IV NO*
Temp. ,cC
(i; ti,$N
i
Scheme 1 Fig. 2. TG curves of chitosan and Schiff base polymers.

Table 1. Microanalyses and characteristic IR bands of chitosan and Scbiff base polymers
_-.
Polymer Chemical Microanalysis, found/calcd. (%) IR (KBr) (cm-‘)
formula _~~.
C H N
~~
Chitosan CbHl ,&N 44.6j44.7 6.916.8 8.6/8.7 3500-2750 (OH, NH& 2900 (C-H aliphatic) and 1460 (C-O-C)
I C,3H&4N 62.4162.7 5.8/6.0 S.SjS.6 3750-3 100 (OH), 3000 (C-H aliphatic), 1700 (C = 0) and 1420 (C = N)
II CwH,,&N 60.5/60.2 6.016.1 5.2jS.O 3800-2950 (OH), 3000 (C-H aliphatic), 1710 (C = 0) and 1460 (C = N)
III C,3H,404NCl 55.4/550 4.814.9 5.1/4.9 37Xk-2830 (OH), 3000 (C-O aliphatic), 1680 (C=O) and 1510 (C=N)
IV CIXHI&NZ 53.5/53.1 4.714.8 9.Oj8.9 320&2500 (OH), 1700 (C = 0) and 1460 (C = N)
V CI~HZOQNZ 61.2/61.6 6.916.9 9.9/9.6 3400-3000 (OH), 1730 (C = 0) and 1430 (O-C-O)
 Thermal analysis of some chitosan Schiff bases 69

Table 2. DSC data for chitosan and Schiff base polymers

Polymer First stage Second stage Third stage Fourth stage

Peak temp. Heat flow Peak temp. Heat flow Peak temp. Heat flow Peak temp. Heat flow
(“C) (“C) (“C) (“C)
Chitosan 99 Endo 292 Endo 314 Exo 466 Exo
I 102 Endo 206 Endo 270 Exo
II 100 Endo 180 Shoulder Endo 245 Exo
III 100 Endo 200 Shoulder Endo 290 Exo
IV 103 Endo 230 Shoulder Endo 300 Exo
V 102 Endo 200 Shoulder Endo 300 Exo

Table 3. TG date for chitosan and Schiff base polymers

Polymer First stage Second stage Remaining after 500°C

T,, T,,, wt loss (%) T,, T,,, wt loss (%)

Chitosan 80 90 8 271 334 49 43

I 90 98 7 235 281 63 30
II 85 95 7 238 287 71 22
III 100 103 8 257 301 54 38
IV 98 103 7 248 295 69 24
V 100 105 7 253 300 59 34

The IR spectra of the Schiff base polymers loss of -8%. The second stage starts at 271°C and
formed show a strong absorption band at reaches a maxmium at 334°C with weight loss of
3350cm-’ for the OH groups. The band at 49%. This is similar to the results suggested by
1420 cm-’ is attributed to the u,,,~~+~&C=N) Schlotzhauer et aL7 Bihari-Varga et al.(j assigned
vibrations (Table 1). From microanalysis and IR the first degradation stage of chitosan to the loss of
spectra of formed polymers, structures (b) were a water molecule. TG for the Schiff base polymers
excluded and structures (a) are the only possible also shows two degradation stages. The first starts
structures. at -90°C with weight loss of -7% due to the loss
of water. Table 3 represents the TG data for chit-
3.2 Thermal methods of analysis osan and Schiff base polymers. The main thermal
process of the prepared polymers takes place at
3.2.1 DSC temperatures lower than the second degradation
DSC curves of chitosan and Schiff base polymers I, stage of chitosan, indicating that all the Schiff base
II, III, IV and V are shown in Fig. 1. Chitosan polymers are less stable than chitosan. It was found
exhibits two endothermic peaks at 99 and 292°C that chitosan is more stable than chitin to depoly-
and two exthothermic peaks at 314 and 466°C. This merization due to the stabilizing effect of free
is similar to the peaks suggested by Bihari-Varga et amino groups. Nagasawa et aL8 studied the rela-
aL6 The DSC curves of chitosan-aromatic aldehyde tionship between depolymerization and sulfation
polymers, as shown in Fig. 1, show an endothermic of chitin and chitosan. They used sulfuric acid at
peak at -100°C. Another endothermic peak was 0°C. On the basis of the molecular weights and the
observed for each of the polymers at 206, 180, 200, sulfur content of the reaction products, they con-
230 and 2OO”C, respectively. This endothermic peak cluded that no structural change in the mono-
was followed by an exothermic peak at 270, 245, saccharides occurred during reaction with sulfuric
290, 300 and 300°C for the Schiff base polymers I, acid, but drastic depolymerization and sulfation
II, III, IV and V, respectively. Table 2 represents the occurred immediately after dissolution in sulfuric
different heat flow values of the polymers. acid. The temperature and length of the treatment
influenced the extent of depolymerization. It seems
3.2.2 TG that the instabilities of the Schiff base polymers
TG curves of chitosan and all the prepared poly- compared with chitosan are due to the absence of
mers are shown in Fig. 2. Chitosan degrades in two the free amino group in the prepared polymers as
stages. The first stages begins at -80°C with weight they are replaced are by the aromatic aldehydes.
70 Fahd A. A. Tirkistani

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1977, p. 134. mal Anal., 1975, 7, 675.
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