See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/227327777

Synthesis and characterization of oligosalicylaldehyde-based epoxy resins

Article  in  Chemical Papers- Slovak Academy of Sciences · February 2006

DOI: 10.2478/s11696-006-0012-1

CITATIONS READS

13 7,669

4 authors, including:

Ertugrul Sahmetlioglu Yavuz Sürme

Erciyes Üniversitesi Ömer Halisdemir University
53 PUBLICATIONS   949 CITATIONS    28 PUBLICATIONS   321 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Renewable Silicon-Containing Polymers View project

All content following this page was uploaded by Ertugrul Sahmetlioglu on 22 May 2014.

The user has requested enhancement of the downloaded file.

 Synthesis and Characterization of Oligosalicylaldehyde-Based
Epoxy Resins

E. SAHMETLİOGLU*, H. MART, H. YURUK, and Y. SURME

Department of Chemistry, Faculty of Arts and Sciences, Nigde University, Nigde 51100, Turkey
e-mail: sahmetlioglu@yahoo.com

Received 17 January 2005; Revised 10 May 2005; Accepted 16 May 2005

In memory of Professor Dr. Adalet R. Vilayetoğlu

The synthesis of a new epoxy resin of oligosalicylaldehyde by the reaction with epichlorohydrin
is reported. New resin’s epoxy value and chlorine content were determined and found to be 25 %
and 1 %, respectively. The characterization of the new resin was instrumented by FTIR, 1 H NMR,
scanning electron microscopy, and thermal gravimetric analyses. TGA results showed that the cured
epoxy resin has a good resistance to thermal decomposition. The mass losses of cured epoxy resin
were found to be 5 %, 10 %, 50 % at 175 ◦C, 240 ◦C, and 400 ◦C, respectively. On the curing procedure
the resin was cured with polyethylenepolyamine at 25 ◦C for 8 h and 100 ◦C for 1.5 h. The FTIR
spectrum of new epoxy resin gave the peak of oxirane ring at ν̃ = 918 cm−1 .

Epoxy resins belong to the most important ther-
mosetting polymers [1—3]. These polymers have bril-
liant characteristics such as heat, moisture and chem-
ical resistance, toughness, electrical and mechanical
resistance and good adhesion to many substrates [4].
The linear epoxy resins are converted into three-
dimensional cross-linked thermoset networks by cur-
ing [5]. This reaction occurs with a very complicated
process, because many reaction processes occur simul-
taneously [6]. In order to convert epoxy resins from
solid or semi-solid monomers into hard, infusible ther-
moset networks it is necessary to use cross-linking
agents. These cross-linkers or “hardeners” promote
cross-linking, or curing of the monomers [1]. After cur-
ing the polymer, it is characterized by high chemi-
cal and corrosion resistance and good mechanical and
thermal properties. These cured polymers are appli-
cable to surface coatings, painting materials, compos-
ites, laminates, encapsulates for semiconductors, and
insulating materials for electrical devices [7]. Recently
much attention has been paid to modifications of the
backbone of epoxy resins in attempts to enhance the
thermal and physical properties [8]. In some precon-
centration and separation studies of trace elements,
epoxy resins have been used as chelating adsorbents
[9—11].
Oligophenols and their derivatives have been used
in various fields because of their electron structure
properties. They have useful properties such as para-
magnetism, semiconductivity, and electrochemical cell
resistance to high energy [12, 13]. Oligoaminophe-
nols actively enter into reaction with the oxirane ring
of epichlorohydrin and epoxy resins forming ther-
mostable polyepoxides and epoxy copolymers [14].
Considering this, oligophenols together with epoxy
resins were used for bonding in preparation of glassy
plastics and foil dielectrics for the manufacture of mul-
tilayer printed circuit equipment.
In this study, a novel epoxy oligosalicylaldehyde-
based oligophenol was synthesized by the reaction of
oligosalicylaldehyde with epichlorohydrin and charac-
terized by FTIR, 1 H NMR, TGA, and SEM. Its epoxy
value [15], chlorine and hydroxyl contents [2] were de-
termined by the standard analytical methods.
EXPERIMENTAL
Salicylaldehyde (SA), epichlorohydrin (Sigma-
Aldrich), methanol, benzene, acetone, toluene, 1,4-
dioxane, carbon tetrachloride, dimethylformamide,
hydrochloric acid, nitric acid, sodium hydroxide,
potassium hydroxide, sulfuric acid, sodium hypochlo-
ride (Merck) were used. All reagents were of an-
alytical grade and used as received. Commercial
polyethylenepolyamine (Yickvic Hk) was used with-
out purification.
The infrared spectra were recorded on a Jasco FT-
IR 300 E spectrophotometer. The FTIR spectra were

*The author to whom the correspondence should be addressed.

Chem. Pap. 60 (1) 65—68 (2006) 65

c 2006 Institute of Chemistry, Slovak Academy of Sciences

recorded using KBr discs (400—4000 cm−1 ). Elemen-
tal analyses were carried out with an Erba 1106 in-
strument (for oligosalicylaldehyde). Epoxy resin was
characterized by using 1 H NMR spectra recorded with
Bruker Spectrospin Avance DPX 400 ultrashield (400
MHz) spectrometer at 25 ◦C using deuterated CHCl3
as solvent. TMS was used as internal standard. Scan-
ning electron micrograph (SEM) was obtained from
a Leon 440 scanning electron microscope. SEM was
derived from epoxy resin film by using silver adhesive
paste. TGA of epoxy resin was performed by a Du
Pont 2000 Thermal Gravimetry Analyzer. The num-
ber average molar mass (M̄N ), mass average molar
mass (M̄m ), and polydispersity index (PDI) were de-
termined by SEC (Kovo). For SEC investigations SGX
(3.3 mm i.d. × 150 mm) columns were used; eluent:
DMF (0.2 cm3 min−1 ), polystyrene standards. A re-
fractometric detector (at 25 ◦C) was used to analyze
the product.
Oligosalicylaldehyde (OSA)
OSA was synthesized through the oxidative poly-
condensation of SA with NaOCl (30 %) in aqueous so-
lution [16]. The SA (3 g; 0.025 mol) was dissolved in an
aqueous solution of KOH (10 %, 0.025 mol) and placed
into a 50 cm3 three-necked round-bottom flask. It was
fitted with a condenser, a thermometer, and a stirrer,
in addition to a funnel containing NaOCl. NaOCl was
added dropwise to this solution for about 20 min, af-
ter heating to 60 ◦C. The solution mixture was stirred
at 90 ◦C for 25 h and neutralized with 3 cm3 of HCl
(37 %) at room temperature. Then, unreacted SA was
removed by steam distillation. The crude product was
washed with water (50 cm3 ), filtered, and dried in an
oven at 105 ◦C.
Epoxy Resin
The epoxidation was carried out by refluxing OSA
and epichlorohydrin in 1 : 10 mole ratio in a three-
necked flask and sodium hydroxide was added gradu-
ally for 3.5 h. The content was dissolved in toluene and
solution was filtered in order to remove the salt. The
excess of epichlorohydrin and toluene was removed by
distillation under reduced pressure. The resulting solid
product was stored in an air-tight container.
The epoxy value (w(Ep)) of resin was determined
by analytical method [15]. This method was based on
the back titration. 0.2 g of resin was added to 30 cm3
of 0.1 M-HCl and mixed for 2 h. Then unreacted HCl
was re-titrated with phenolphthalein by standard al-
kali solution using the following formula
(V2 − V1 ) · c(NaOH) × 0.043
w(Ep) =
mass of sample
where V1 is the volume of NaOH solution used for
66
E. SAHMETLİOGLU, H. MART, H. YURUK, Y. SURME
blank and V2 is the volume of NaOH solution used
for sample.
Hydroxyl content was determined by acetylation
with acetyl chloride in pyridine. The excess of acetyl
chloride was decomposed with water and the result-
ing acetic acid, formed both in hydrolysis and in the
acetylation process, was titrated with standard alkali
using the following formula
mass of sample
w(OH) =
c(KOH) · (V1 − V2 ) × 170
where V1 is the volume of KOH solution used for blank
and V2 is the volume of KOH solution used for sample.
The chlorine content was determined by treating
the resin solution with alcoholic KOH and titrating it
against standard HCl [2].
0.0355 · c(KOH) · VKOH
w(Cl) = × 100
mass of sample
RESULTS AND DISCUSSION
The new epoxy resin was coloured in dark brown
and it was solid. Synthesis of OSA and epoxidation
with epichlorohydrin are given in Schemes 1 and 2,
respectively.
Scheme 1
FTIR (KBr; ν̃/cm−1 ): 2500—3355 (phenol—OH),
1654 (CHO), 2854—2925 (aldehyde C—H), 3030.
wi (calc. for OSA): 70.00 % C, 3.33 % H; wi (found for
OSA): 69.21 % C, 3.85 % H.
n OH
OH
KOH, NaOCl CHO
CHO
heat
n
Scheme 2
FTIR (KBr; ν̃/cm−1 ): 918 (epoxy ring), 1675 (al-
dehyde group), 2925 (aromatic proton).
The epoxy value and chlorine content of the resin
were found to be 25 % and 1 %, respectively. The
present content of hydrolysable chlorine is due to
many side reactions, such as dehydrohalogenation.
The secondary hydroxyl group content was 0.19 mol
in 100 g. The resin was soluble in acetone, dioxane,
Chem. Pap. 60 (1) 65—68 (2006)
OLIGOSALICYLALDEHYDE EPOXY RESINS
Fig. 1. FTIR spectrum of the epoxy resin.
Fig. 2. 1 H NMR spectrum of the uncured epoxy resin.
tetrahydrofuran, chloroform, and dimethylformamide,
however, insoluble in water.
In the FTIR spectra (Fig. 1) of the resins, the
bands observed at ν̃/cm−1 918 and 1675 are assigned
to the vibrations of the epoxy ring and aldehyde
groups, respectively. In addition, band at 2925 cm−1
is due to the vibration of the aromatic protons.
The singlet signal of the resin in 1 H NMR spec-
trum (Fig. 2) at δ = 10.05 is attributed to the alde-
hyde group proton. Besides, signals in the δ = 2.5—
4.5 and 7—8 range are due to epoxy ring protons and
aromatic protons, respectively. The differences of in-
tegral in aldehyde and aromatic ring protons may be
caused by the protons located in the last groups of
oligomers in the uncured resin. FTIR and 1 H NMR
spectral analyses of the resins proved that the prod-
uct was formed by the reaction between the OH group
of OSA and epichlorohydrin.
According to SEC analysis, the number average
molar mass (M̄N ), mass average molar mass (M̄m ),
and PDI values of the epoxy resins were found to be
4600 g mol−1 , 6400 g mol−1 , and 1.39, respectively.
The cured epoxy resin was soluble in inorganic acid
(nitric acid, sulfuric acid, hydrochloric acid), however,
it was insoluble for organic solvents. SEM micrograph
(Fig. 3) of cured epoxy resin was in the shape of coral
reef.
TGA of the epoxy resin (Fig. 4) cured with
polyethylenepolyamine was performed under the ni-
trogen atmosphere with a heating rate of 10 ◦C min−1
in the temperature range 30—900 ◦C in order to inves-
tigate the thermal stability. The relative mass losses
at given stages were as follows: 5 %, 30—175 ◦C; 10 %,
Chem. Pap. 60 (1) 65—68 (2006)
Fig. 3. SEM micrograph of the cured epoxy resin.
Fig. 4. TGA curve of the cured epoxy resin.
175—240 ◦C; 50 %, 330—400 ◦C. This shows that max-
imum polymer degradation occurs between 330 ◦C and
430 ◦C. However, the relative mass losses of OSA were
reported as follows: 5 %, 190 ◦C and 50 %, 435 ◦C [16].
Curing studies were performed by using polyethyl-
enepolyamine as a curing agent. The reaction occurred
between amine and epoxy ring and simultaneously be-
tween amine and aldehyde groups. Due to this double
reaction the new epoxy resin differs from other aro-
matic rings-containing epoxy resins. The cured resin
was extracted in hot tetrahydrofuran for 1 h and cross-
link ratio was found to be 80 %.
CONCLUSION
The epoxy resin was synthesized by using oligosal-
icylaldehyde and epichlorohydrin reagents. Character-
ization evidence of the resin was the peak of oxirane
ring at 918 cm−1 in FTIR spectrum. The cured epoxy
resin showed a good chemical resistance to organic sol-
vents and a weak chemical resistance against the acid
derivatives. The resin has a thermal stability up to
200 ◦C.
67

REFERENCES
1. Hamerton, I., Howlin, B. J., and Jepson, P., Coord.
Chem. Rev. 224, 67 (2002).
2. Lee, H. and Neville, K. (Editors), Handbook of Epoxy
Resins. McGraw-Hill, New York, 1972.
3. Roşu, D., Mititelu, A., and Çaşcaval, C. N., Polym.
Test. 23, 209 (2004).
4. Balcerzak, E. and Janeczek, H., Polymer 45, 2483
(2004).
5. Xu, K. and Chen, M., Polymer 45, 1133 (2004).
6. Lapprand, A., Arribas, C., Salom, C., Masegosa, R. M.,
and Prolongo, M. G., J. Mater. Process. Tech. 143, 827
(2003).
7. Lubin, G. (Editor), Handbook of Composites. Van Nos-
trand Reinhold, New York, 1982.
8. Musa, G. and Mohammad, H. R., Iran. Polym. J. 5,
1026 (1996).
68
View publication stats
E. SAHMETLİOGLU, H. MART, H. YURUK, Y. SURME
9. Kurnoskin, A. V., Polymer 34, 1060 (1993).
10. Su, Z. X., Chang, X. J., Zhan, G. Y. et al., Anal. Chim.
Acta 310, 493 (1995).
11. Chang, X. J., Gong, B. L., Yang, D. et al., Anal. Lett.
30, 2611 (1997).
12. Ragimov, A. V., Mamedov, B. A., and Liogon, B. I.,
Polym. Sci. U.S.S.R. 19, 2922 (1977).
13. Ragimov, A. V., Mamedov, B. A., Ismailova, Kh. O.,
and Liogon, B. I., Polym. Sci. U.S.S.R. 27, 318 (1985).
14. Ragimov, A. V., Mamedov, B. A., and Gasanova, S.
G., Polym. Int. 43, 343 (1997).
15. Ekberov, O. H. and Basan, S., Polymer Chemistry
Lab., Cumhuriyet University Press, Sivas, 1995.
16. Kaya, I., Vilayetoğlu, A. R., and Mart, H., Polymer 42,
4859 (2001).
Chem. Pap. 60 (1) 65—68 (2006)