CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No. 3, 2008 Chemistry

Ranjana Yadav and Deepak Srivastava

STUDIES ON CARDANOL-BASED EPOXIDIZED NOVOLAC RESIN

AND ITS BLENDS
Department of Plastic Technology, H. B. Technological Institute
Kanpur – 208 002 (U.P.), India,
[email protected]
Received: May 05, 2008

Abstract. Cardanol-based novolac-type phenolic resin saturated side chain. CNSL and cardanol are used in the
was synthesized with a mole ratio 1.0:0.5 of cardanol-to- manufacture of special phenol resins for coatings, lamination
formaldehyde using a dicarboxylic acid catalyst such as and as friction materials. These polymers are synthesized
succinic acid. The cardanol-based novolac-type phenolic from CNSL or cardanol either by polycondensation with
resin may further be modified by epoxidation with electrophylic compounds such as formaldehyde,
epichlorohydrin excess at 393 K in a basic medium to furfuraldehyde or by chain polymerization through
duplicate the performance of such phenolic-type novolacs. unsaturation presented in the side chain using an acid and
Carboxyl-terminated butadiene acrylonitrile copolymer base catalyst. The cardanol based novolac type phenolic
(CTBN) has been studied by various researches with resins may further be modified by epoxidation with
diglycidyl ether of bisphenol-A (DEGBA) epoxy resin and epichlorohydrin to duplicate the performance of such
epoxidized phenolic novolac resins. The epoxidized phenolic type novolacs [1-4]. Having several outstanding
novolac resin was blended with different weight ratios of characteristics, epoxy resins show low impact resistance
carboxyl-terminated butadiene acrylonitrile copolymer in their cured state which limits the applications of epoxy
(CTBN) and cured with a stoichiometric amount of resins. To alleviate this deficiency, epoxy resins are modified
polyamine curing agent. The formation of various products by the incorporation of a reactive liquid rubber without a
during the synthesis of cardanol-based novolac resin, significant loss in other properties [5-9]. In this way, a
epoxodized novolac resin and blending of epoxidized carboxyl-terminated copolymer of butadiene and
novolac resin with CTBN has been studied by Fourier- acrylonitrile (CTBN) has been used by various researches
transform infrared (FTIR) spectroscopic analysis. Further, [10-13] with diglycidyl ether of bisphenol-A (DGEBA)
the products were confirmed by a proton nuclear epoxy resin and epoxidized phenolic novolac resins. But,
magnetic resonance (1H-NMR) spectroscopic analysis. The carboxyl-terminated polybutadiene (CTBN) is nowhere used
number average molecular weight was determined by a with cardanol based epoxy resins. Therefore, we have tried
gel permeation chromatography (GPC) analysis. The blend to produce the modified epoxy matrices, based on cardanol,
sample, having 15 wt % CTBN concentration showed by physical blending with CTBN and we have studied the
minimum cure time and most thermally stable systems. effect of CTBN addition on thermal and morphological
changes in the blends.
Key words: cardanol, formaldehyde, novolac,
epichlorohydrin, epoxy resin, butadiene acrylonitrile
copolymer , spectral methods. 2. Experimental
2.1. Materials
1. Introduction Cardanol (M/s Satya Cashsew Pvt. Ltd., Chennai),
formaldehyde (40 % solution), succinic acid, sodium
Cashew Nut Shell Liquid (CNSL), an agricultural hydroxide, epichlorohydrin (All from M/s Thomas Baker
renewable resource and the byproduct of the cashew Chemicals Ltd., Mumbai), polyamine (M/s Ciba Specialty
industry, holds a considerable promise in the different Chemicals Ltd., Mumbai) with amine value 1240–
directions because it is the source of unsaturated 1400 mgKOH/g and carboxyl-terminated butadiene –
hydrocarbon phenol, an excellent monomer for acrylonitrile copolymer (CTBN) (Hycar 1300x13) were
thermosetting polymers production. Vacuum distillation of the initial reagents. CTBN was kindly supplied by M/s
CNSL yields a pure cardanol. Cardanol is n-pentadecadienyl Emerald Performance Materials, LLC, Hong Kong having
phenol, the aliphatic side chain usually consists of mixture molecular weight M n of 3500 and acrylonitrile and
of one, two and three double bonds in a linear chain with a carboxyl contents 27 and 32 percent, respectively.
174 Ranjana Yadav et al.

2.2. Synthesis of cardanol- based novolac- mixture of ethyl acetate – benzene (60:40). The purified
type phenolic resin resin was analyzed by infra-red (IR) spectroscopic, nuclear
magnetic resonance ( 1H-NMR) spectroscopic, mass
Novolac resin with mole ratio 1:0.5 of cardanol spectroscopic and gel permeation chromatographic (GPC)
(C) to formaldehyde (F) was prepared using bicarboxylic analysis.
acid, viz., succinic acid, as a catalyst by a method similar
to that adopted by Knop and Schieb [14] for a phenol 2.3. Epoxidation of cardanol-based
based novolac. The catalyst (1 % based on cardanol) was,
novolac-type phenolic resin
first, dissolved in methanol at 333 K. Half of a catalyst
solution was added to cardanol (about 30 g), charged in a The cardanol-based novolac-type phenolic resin was
three-necked round bottom flask fitted with a Leibig’s epoxidized by a method similar to that given in [16].
condenser and mechanical stirrer. The remaining half of Approximately 1.0 mole of a novolac resin was taken in a
the methanolic solution of the catalyst was added to the 500 ml three-necked round-bottomed flask and 10 moles
formaldehyde (40 %) and this was added to the cardanol of epichlorohydrin were added to it while stirring. Then
dropwise within one hour, once the temperature of the 40 % sodium hydroxide solution was added dropwise to
reaction kettle was maintained at 393 K. The initial pH of the above mixture for a period of 5 h at 393 K. The reaction
the reaction mixture was 6.0 reduced to a value of 4.8 mixture was then subjected to distillation under vacuum
after 5 h of reaction at 393 K. Free-formaldehyde and for removal of unreacted epichlorohydrin. The resulting
free-phenol contents were checked after every 45 min to viscous product was stored for a further analysis.
see the completion of the methylolation reaction [15]. The
reaction product was cooled and dried under vacuum at 2.4. Preparation of blends of epoxidized
333 K overnight before purification by column novolac resin and carboxyl-terminated
chromatography. A resin solution prepared with n-hexane,
charged to the silica gel column chromatographic
butadiene acrylonitrile copolymer (CTBN)
purification, was adopted mainly to remove unreacted The epoxy resin was mixed physically with varying
components, impurities etc., from the methylolated concentration of CTBN ranging between 0–20 wt % with
cardanol. Purification was effected using the elutent an interval of 5 wt % (Table 1).
Table 1
Sample designations
No. Epoxy, wt % CTBN, wt % Sample code
Cardanol-based epoxidized novolac resin (prepared from novolac resin CF52)
1. 95 5 ECF521
2. 90 10 ECF522
3. 85 15 ECF523
4. 80 20 ECF524

2.5. Fourier-transform infra-red (FTIR) column oven and L-7490 R.I. Detector) was used for
spectroscopic analysis and Nuclear determination of the average number molecular weight of
magnetic resonance (1H-NMR) the synthesized cardanol-based novolac resin. A small
quantity of the resin was dissolved in THF; which acted
spectroscopic analysis both as a mobile and stationary phase and was injected
Fourier-transform infra-red (FTIR) spectra of the into the instrument. Mass spectra of the prepared samples
prepared samples were recorded on a Perkin-Elmer (Model were recorded on Micromass TofSpec2e MALDI TOF
843) infra-red spectrophotometer, using KBr pellet, in the mass spectrophotometer.
wave length range of 500–4000 cm–1. 1H-NMR spectra of
cardanol-based novolac and epoxidized novolac resins were 2.7. Differential scanning calorimetric
recorded on Bruker DRX – 300 NMR spectrophotometer (DSC) analysis
in the temperature range of 183 to 353 K.
Cure temperature of the prepared samples were
2.6. Gel permeation chromatographic (GPC) measured by taking very little quantity of blend samples
into a shallow aluminum pan sealed by an aluminum cover
analysis and mass spectroscopic analysis of differential scanning calorimetry (DSC) (TA,
Gel permeation chromatograph (GPC) (Instrument Instrument, USA; Model DSC Q20). It was placed in a
procured from E Merck consisting of a pump, L-7350 sample cell of the instrument. The starting temperature,
 Studies on Cardanol-Based Epoxidized Novolac Resin and its Blends 175

programmed rate and final temperature were taken at a

heating rate of 283 K/min. OH

2.8. Thermogravimetric analysis

The thermal stability of the blend samples was (CH2)7(CH=CH)a(CH2)bCH3
determined by a comparison of the onset degradation
temperature (up to 5 % weight loss) of the cured samples where, a = 1; b = 5
with that of thermogravimetric analyzer (TGA) of TA Inst-
ruments (Model Q50 TGA) at a heating rate of 283 K/min Scheme 1
in the nitrogen atmosphere from ambient to 923 K.
periodic withdrawal of reaction mixture to analyze
formaldehyde using hydroxylamine hydrochloride [17].
2.9. Morphology The final pH of the reaction mixture was found to be 4.8.
The morphological changes due to addition of The decrease of pH in the methylolated cardanol might be
CTBN into the epoxy matrix were studied by JOEL ascribed to the formation of monohydroxyl substituted
scanning electron microscope (SEM) (Model JSM 5800). cardanol [18].
The rubber domains distributed in the matrix and interaction
of these domains with the epoxy matrix specimen surface 3.2. FTIR and 1H-NMR spectroscopic
could be observed by SEM. For this, the fractured samples analysis of cardanol-based novolac-type
were coated with a thin layer of gold-palladium alloy by
sputtering to provide conductive surfaces phenolic resin
Cardanol is a monoene meta-substituted phenol. On
the basis of FTIR, NMR and mass spectroscopic analysis
3. Results and Discussion and gel permeation chromatography (GPC) analysis elucidated
the structure of cardanol. Therefore, the empirical formula
3.1. Synthesis of cardanol-formaldehyde can be taken as C21H34O [19, 20] and the structure of cardanol
novolac type phenolic resin may be proposed as shown in Scheme 1.
The methylolation of cardanol was carried out with A shift of the peak from 1075 to 1102 and
formaldehyde in the presence of dicarboxylic acid, viz., appearance of the peak near 1708 cm–1 (Fig. 1) was
succinic acid. The initial pH of the reaction mixture found observed in a methylolated cardanol due to the C=O
to be 6.0. The formylation reaction was carried out with stretching from CH2OH. It has also been found that the
0.5 mole ratio of cardanol-to-formaldehyde. Therefore, intensity of peaks at 1594 cm–1 (C=C, str), 3009 cm–1
under these experimental conditions the complete (C–H str of alkene) and 779 cm–1 (C–H out-of-plane
formylation might be expected to yield resin with a high deformation) remained almost unaffected which indicated
ortho-ortho linkages for the phenolic novolac resin. The that the polymerization has taken place through substitution
completion of the methylolation reaction was checked by of CH2OH and not through the double bonds in the side

Fig. 1. FTIR spectrum of novolac resin CF52

176 Ranjana Yadav et al.

Fig. 2. 1H-NMR spectrum of novolac resin CF52.

chain. The band at 3395 for the sample CF52, may appear This ion acted as a hydroxy alkylating agent by
due to the presence of hydroxyl groups in the methylolated reacting with a cardanol via electrophylic aromatic
cardanol. Small peaks near 946 and 973 cm–1 indicated substitution. A pair of electrons from the benzene ring
the substitution in benzene nuclei. The small peaks near attacked electrophylic element forming an intermediate
913 and 697 cm–1 might appear due to three adjacent followed by deprotonation and regained the aromaticity
hydrogen atoms in the benzene nuclei. The peak of the ring. The reaction is shown in Scheme 3.
appearance near 722 cm–1 (Fig. 1) indicated the ortho- The methylol group of the hydroxy methylolated
and para-substitution in the benzene nuclei. The preceding cardanol was unstable under acidic condition and might
spectral data were found to be identical with those given loose water readily to form a benzylic carbonium ion as
in literature [21, 22]. shown in Scheme 4.
In the 1H-NMR spectra CF52 (Fig. 2) novolac resin, The products formed in Scheme 4 reacted with
the peak near 6.6–6.8 δ might appear due to the aryl protons another cardanol molecule to form a methylene bridge in
of the benzene nuclei. The peaks around the region of 7.1– another electrophylic aromatic substitution. This process
7.3 δ appeared due to the phenolic hydroxyl in the novolac repeated until all formaldehyde was exhausted. The related
resin. The peak at 5.3 δ might be attributed to the methylene reaction may be shown in Scheme 5.
protons whereas the peaks between 0.8–2.8 δ appeared
due to the presence of long alkyl aliphatic side-chain, CH2 = O + H2O HO CH2 OH
originally observed in cardanol. The terminal methyl group
of the alkyl side chain may also be seen as a small peak at
0.8 δ. The peak at 3.7 δ indicated the presence of methylene +
protons of C6H5–CH2–C6H5 for the bridge between the H
phenyl rings [23]. All these spectral data indicated that the +
condensation of methyolated cardanol has been completed CH2 - OH + H2O
under experimental conditions and was fully consisted of
the proposed structure (Scheme 6) resulting due to reaction Scheme 2
mechanism shown in Schemes 2-5.
On the basis of the preceding discussions, the
3.3. Molecular weight of cardanol-based
following reaction mechanism, similar to that proposed novolac-type phenolic resin by gel
by Kuriakose and Manjooran [24], may be proposed. The permeation chromatographic (GPC)
mechanism of formation of novolac oligomers, in acidic technique and mass spectroscopic analysis
media, using excess of cardanol over formaldehyde might
proceed in four steps. First, a methylene glycol was The average number molecular weight (Mn) of CF52
protonated by an acid from the reaction medium, which calculated from the number of phenolic units (p) in the
then released water to form a hydroxyl methylene novolac resins (proposed structure in Scheme 6), which
carbonium ion as shown in Scheme 2. was determined from the ratio of aromatic–methylene
 Studies on Cardanol-Based Epoxidized Novolac Resin and its Blends 177

OH OH OH
H
Slow CH2 OH
+ +
Fast CH2OH
CH2 - OH
+ H+
C15H29 C15H29 C H +
15 29

OH OH OH
+ Slow Fast +
+ CH2 - OH + H
+
C15H29 C15H29 C15H29
H CH2OH CH2OH

Scheme 3

OH OH OH +
CH 2OH +
CH2OH2 CH 2
+
H + H 2O
+
C15H29 C15H29 C15H29

OH
OH OH

+
H C15H29 + H 2O
C15H29+ C15H29 CH 2
+
CH 2OH H2OH2C +

Scheme 4

OH OH OH
+ CH2 OH
CH2 +
+ + H
C15H29 C15H27
C15H29 C15H29

OH

OH OH +
+ H
C15H27
+ OH
C15H29 C15H29
CH2
CH2
+ C15H27
Scheme 5

[CH2] to aromatic protons,[AR], protons of the 1H-NMR of glycidyl groups per molecule in the resin depend upon
spectra as the following equation [25 ]: the number of phenolic hydroxyls in the starting novolac,
[CH2]/[AR] = (2p – 2)/(3p + 2) (1) the extent to which they were reacted and the extent to
The calculated result was Mn = 670 g/mol and p = 2.17 which the lowest molecular species were polymerized
for phenolic groups per molecule for a novolac resin CF52. during synthesis. Theoretically, all the phenolic hydroxyls
The value of molecular weight was further confirmed by might be reacted, but in practice all of them did not react
GPC trace and mass spectroscopic analysis (Figs.3 and 4). because of steric hindrance [26]. The reaction between
Finally, the structure of the cardanol-based novolac ECH and novolac resin might be thought to proceed in a
resins may be proposed as following: similar fashion as in the work given by Lee and Neville
[26]. The epoxide group of ECH reacted with phenolic
3.4. Epoxidation of novolac prepolymer hydroxyls under the alkaline medium and formed the
chlorohydrin ether which underwent dehydrochlorination
The novolac based epoxy resin was synthesized reaction and resulted in to glycidyl ether. The structure of
by the reaction with epichlorohydrin (ECH). The number the epoxy resin may be proposed as in Scheme 7.
178 Ranjana Yadav et al.

OH OH OH

NaOH
CH2 CH2 + ECH
R R R
n

O O O
O

O
O-CH2 CH CH2 O-CH2 CH CH2 CH2 CH CH2
O-CH2 CH CH2

OR CH2
CH2 CH2
R R R R
n

Where, R : C15H29
Scheme 7

The FTIR spectra of uncured cardanol-based 3.6. DSC analysis of blend samples
epoxidized novolac resins, i.e. sample ECF 52 , the
characteristic band of the oxirane ring was observed near Figs. 9 and 10 show the dynamic DSC scans of
911 and 856 cm–1, as shown in Fig. 5. The 1H-NMR cardanol-based epoxidized novolac resins without and with
spectrum (Fig. 6) further confirmed the formation of CTBN (i.e. samples ECF52 and ECF523) at a heating rate of
cardanol-based epoxidized novolac resins. The epoxide 283 K min–1. The effect of CTBN concentration on cure
equivalent weight of the prepared cardanol-based epoxidized parameters of different epoxy matrices has also been
novolac resins, i.e. sample ECF52 , was found to be compared to that of non-modified epoxy matrices in Table
305 eq/g, as determined by a titration method, whereas the 2. It is evidenced from the results that the exotherm peak
molecular mass of the sample was 791 g/mol. was shifted to lower temperatures due to enhanced reaction
rate which, finally reduced the cure time of the CTBN-
3.5 FTIR analysis of uncured and cured modified blend system (refer to Table 2). The initial addition
blend samples of CTBN in the epoxy resin decreased the cure time sharply
and this trend remained up to 15 wt % CTBN addition and
FTIR spectral analysis of uncured blend sample increased thereafter. The enhanced rate behavior could be
containing 15 wt % CTBN in epoxy resin (ECF52) is shown interpreted in terms of intermolecular transition state for
in Fig. 7. It is clear from the figure that the addition of the epoxy-amine reaction. According to this mechanism
CTBN into the neat epoxy resin shifted the peaks related [29, 30] strong hydrogen bonding species, such as acids
to the oxirane functionality from 911 and 856 cm–1 (refer
and alcohols, stabilized the transition state and strongly
to Fig. 5) to 913 and 851 cm–1, respectively (Fig. 7). A
accelerated the curing reaction. The decrease of cure time
minor change in the intensity of the peaks was also seen
in the spectrum. These observations clearly indicated that could also be explained by the fact that during the reaction
there occurred a chemical reaction between a carboxyl of CTBN with epoxy resin, some of the exothermic energy
group of CTBN and an epoxide group of the epoxy resin released during epoxy crosslinking it might have been
resulting in epoxy end-capped which would be capable of consumed by CTBN resulting in decrease of cure time [31].
reacting with the hardener (refer to Fig. 8 for the FTIR The ∆H values (Table 2) related to the cure process were
spectrum of cured product) in the same way as diepoxy determined from the area of the exotherm peak obtained
[27-28]. This was further confirmed by the appearance from DSC analysis (Figs 9. and 10) taken in a dynamic
of a new stretching peak at 1492 cm–1 due to the formation mode. In contrast, the presence of CTBN did not affect
of carboxylate anion and near 1737 cm–1 due to the significantly the heat of polymerization (∆H), indicating
formation of functional ester group and C–C multiple bond insignificant influence on the crosslinking density of the
stretching (Fig. 7). epoxy matrix [32, 30].
Studies on Cardanol-Based Epoxidized Novolac Resin and its Blends 179

Fig. 3. GPC trace of novolac resin

Fig. 4. MALDI-TOF mass spectrum of novolac resin CF52

Fig. 5. FT-IR spectrum of epoxidized novolac resin ECF52

180 Ranjana Yadav et al.

Fig. 6. 1H-NMR spectrum of epoxidized novolac resin ECF52

Table 2
DSC results of unmodified and CTBN-modified cardanol-based
epoxidized novolac resin cured with polyamine
∆H, J mol-1
a
Blend sample Ti, K Tonset, K TP, K Tstop, K tcure, min
ECF52 349.3 388.1 399.2 438.5 49.4 240
ECF521 343.2 382.4 398.8 438.6 53.2 223
ECF522 340.2 364.8 400.2 443.3 59.8 211
ECF523 336.5 349.3 393.3 436.0 62.9 180
ECF524 341.6 371.5 396.6 442.8 58.4 191
a
Cure time obtained by curing the sample in air oven at 393 K.
Ti – kick-off temperature, where the curing starts; Tonset – temperature where the first detectable heat is released; TP – temperature
of peak position of exotherm; Tstop – temperature of end of curing exotherm; ∆H – heat of curing; tmin – cure time in minutes.

Fig. 7. FTIR spectrum of uncured blend sample BECF523

 Studies on Cardanol-Based Epoxidized Novolac Resin and its Blends 181

Fig. 8. FTIR of cured blend sample BECF523

Table 3
Results of TG/DTG traces of unmodified and CTBN-modified cardanol-based epoxidized novolac resins
cured with polyamine
Blend First step Second step Total % CY
sample To Tmax Tf %CY To Tmax Tf %CY
ECF52 465 589 616 49.3 616 711 771 47.2 3.5
ECF521 451 592 626 62.6 626 702 787 34.4 3.2
ECF522 441 599 630 90.7 630 713 772 7.0 2.3
ECF523 449 578 628 53.8 628 711 764 42.1 4.1
ECF524 472 595 628 55.6 628 714 778 40.5 3.9

Note: To – onset temperature of degradation; Tmax – temperature of maximum rate of mass loss; Tf – extrapolated final decomposition
temperature; CY – char yield.

3.7 Thermal stability epoxy matrix respectively. SEM of CTBN modified system
showed the presence of precipitated, discrete rubber
The systems were evaluated for the thermal stability
particles, which were dispersed throughout the epoxy
in nitrogen atmosphere by thermogravimetric analysis. The
matrix, i.e. they revealed the presence of two-phase
thermogravimetric results (TG) obtained for samples ECF52
and ECF523 are shown in Figs. 11 and 12 for the evaluation morphological features. The soft elastomeric phase was
of thermal stability in the nitrogen atmosphere. The onset separated from the hard epoxy matrix during the early
temperature of degradation (To), temperature of maximum stage of the cure. The fractured surface of the most of
rate of mass loss (Tmax) and extrapolated final decomposition the rubber-toughened epoxy system has a rigid continuous
temperature (Tf) were noted from TG traces and are pre- epoxy matrix with a dispersed rubbery phase as isolated
sented in Table 3. TG analysis confirmed the occurrence of particles [37]. Some cavitations of the rubber particles
samples degradation. The degradation of the blend systems accompanied by stress whitening zones were also
was found to occur in two steps. The temperature of 5 % observed in the scan (Fig.14). This stress whitening effect
weight loss increased slightly from 567 K for pure epoxy may be related to the location deformation at the crack
(sample ECF52) resin to 573 K for the epoxy/CTBN blend tip. Furthermore, the cavitations were followed by the
(i.e. blend sample ECF523). The addition of the appropriate
onset of the shear localization process [38-40] resulting
amount of epoxy could decrease the mobility and increase the
in the observed increase of thermal properties.
stability of CTBN via the reaction between the thermal carboxyl
group of CTBN and hydroxyl group of epoxy [33-36].

3.8. Scanning electron microscopic analysis 4. Conclusions

Figs.13 and 14 show the SEM micrographs of DSC studies showed the exothermal heat of epoxy
fractured surface of the pure epoxy and CTBN modified crosslinking reaction due to addition of rubber into epoxy
182 Ranjana Yadav et al.

Fig. 9. DSC scan of epoxidized novolac resin ECF52.

Fig. 10. DSC scan of blend sample BECF523

Fig. 11. TGA Trace of blend sample ECF52

Studies on Cardanol-Based Epoxidized Novolac Resin and its Blends 183

Fig. 12. TGA Trace of blend sample BECF523

Fig. 13. SEM micrographs of preapared sample ECF52

Fig. 14. SEM micrographs of preapared sample BECF523

184 Ranjana Yadav et al.

matrix. The thermal stability of the cardanol based epoxy [23] Huang J., Xu M., Lin M., Lin Q., et al.: J. Appl. Polym.
resin was increased with the addition of 15 wt% CTBN in Sci., 2005, 97, 652.
the epoxy matrix. Cardanol–based epoxy network modified [24] Kuriaposa A. and Manjooran S.: Surf. Coat. Tech., 2001,
with CTBN displayed two phase separated morphology 145, 132.
[25] Lin-Gibson S., Baranauskas V., Riffle J.S. and Sorathia V.:
with dispersed rubber globules in the matrix resin. Polymer, 2000, 43, 7389.
[26] Lee H. and Neville K.: Hand book of epoxy resins,
Acknowledgements McGraw-Hill, New York 1982.
[27] Evtushenko Yu., Ivanov V. and Zaitsev B.: J. Anal. Chem.,
This work was sponsored by Council of Science 2003, 58, 347.
and Technology, UP, Lucknow. We, also, thankfully [28] Smith A.: Applied infrared spectroscopy, Wiley, NewYork 1979.
acknowledge the contributions rendered by M/s Satya [29] Horie K., Hiura H., Sawada M., Mita I. and Kambe H.: J.
Cashew Pvt. Ltd., Chennai for providing cardanol and M/ Polym. Sci. A-1, 1970, 8, 1357.
s Emerald Performance Materials, LLC, Hong Kong for [30] Ruzenberg B.: Adv. Polym. Sci., 1985, 75, 113.
providing CTBN. [31] Wise C., Cook W. and Goodwin A.: Polymer, 2000, 41,
4625.
[32] Calabrese L. and Valenza A.: Comp. Sci. Tech., 2003, 63, 851.
References [33] Cataloni A. and Bonicelli M.: Thermochimica Acta, 2005,
438, 126.
[1] Attanasi O. and Bunatti S.: La Chimica e I’Industria, 1996, [34] Gu A. and Liang G.: J. Appl. Polym. Sci., 2003, 89, 359.
78, 693. [35] Maity T., Samanta B., Dalai S. and Banthia A.: Mat. Sci.
[2] Prabhakaran K., Narayan A. and Pvithram C.: Eur. Cer. Eng: A, 2007, 464, 38.
Soc., 2001, 21, 2873. [36] Kaji M., Nakahara K. and Endo T.: J. Appl. Polym. Sci.,
[3] Pillai C., Prasad V., Sudha J., Bera S. and Menon A.: J. 1999, 74, 690.
Appl. Polym. Sci., 1990, 41, 2487. [37] Sulton J. and Garry Mc: J. Polym. Eng. Sci., 1973, 13, 29.
[4] Bhunia H., Nando G., Chakib T. et al..: Euro. Polym. J., [38] Verchere D., Sautereau H. and Pasculat J.: J. Appl. Polym.
1999, 35, 1381. Sci., 1990, 41, 467.
[5] Kinloch A. and Reiw C.: Rubber-Toughened Plastics [39] Chan L., Gillham J., Kinloch A. and Shaw S.: [in:] Riew C.
Advances in Chemistry, Am. Chem. Soc., Ser 22:67, and Gillham J. (eds.), Rubber-modified epoxies: morphology,
Washington DC 1989. transitions and mechanical properties. American Chemical
[6] Kinloch A. and Young R.: Fracture behaviour of polymers, Society, Washington D.C 1984, v. ACS 208.
Appl. Sci., London 1983. [40] Sue H., Garciameitin E. and Pickelman D.: [in:] Arands C.
[7] Huang J. and Kinloch A.: Polymer, 1992, 33, 1330. (Ed.) Polymer toughening. Marcel Dekker, NewYork 1996.
[8] Huang J. and Kinloch A.: J. Mater. Sci., 1992, 27, 2763.
[9] Riew C., Rowe E. and Siebert A.: Rubber toughened ВИВЧЕННЯ ЕПОКСИДНИХ НОВОЛАЧНИХ
thermosets: ACS meeting- symposium on toughness and
brittleness of plastics, division of organic coatings and plastics
СМОЛ НА ОСНОВІ КАРДАНОЛУ
Attantic city, N.J, October 18, 1974. ТА ЇХ СУМІШЕЙ
[10] Frigone M., Masica L. and Aciermo D.: Eur. Polym. J.,
1995, 31, 1021. Анотація. Синтезовано фенольну новолачну смолу на
[11] Tripathi G. and Srivastava D.: Mat. Sci. Eng:A, 2007, 443, 262. основі карданолу з мольним співвідношенням карда-
[12] Pearson R. and Yee A.: J. Mater. Sci., 1989, 24, 2571. нол:формальдегід 1.0:0,5 з використанням як каталізатор
[13] Clayton May: Epoxy resin – Chemistry and technology, дикарбонової кислоти, зокрема янтарної. Таку смолу у
Marcel Dekker, New York 1988. подальшому модифікували надлишком епіхлоргідрином при 393
[14] Knop A. and Schieb W.: Chemistry and application of К у лужному середовищі. Вивчені у різному масовому
співвідношенні суміші дигліциділового етеру бісфенолу А і
phenolic resins, Springer Verlag, New York 1979.
полігліцидної новолачної смоли з кополімером бутадієну з
[15] Devi A., Chandra K. and Srivastaava D.: Proceedings of акрилонітрилом, що містить кінцеві карбоксильні групи
the 14th National Thermal Analysis Symposium, Vadodra, India, (БАКК). Як структуруючий агент таких сумішей використаний
2004, 22. поліамін у стехіометричній кількості стосовно епоксидних
[16] Devi A. and Srivastava D.: Mater. Sci. Eng. A, 2007, 458, 336. груп. Формування зшитих структур вищеназваних сумішей
[17] Urabanski J., Czer Winkski W., Janika K, Majewsta F. and вивчено різними методами ІЧ-спектроскопічного аналізу. .
Zowall H.: Handbook of analysis of synthetic polymers and Середньомолекулярну масу визначали гель-хроматографією.
plastics, Ellis Horward ltd., Chicketa 1977. Встановлено, що мінімальна тривалість структурування і
[18] Sperling G.: J. Am. Chem. Soc., 1954, 76, 1190. найвища термічна стабільність систем спостерігається при
[19] Sathiyalekshmi K.: Bull. Mater. Sci., 1993, 16, 137. вмісті в таких сумішах 15 % мас. БАКК.
[20] Chakrawarti P. and Mehta V.: Ind. J. Tech., 1987, 25, 109.
[21] Mythili C., Retna A. and Gopalkrishnan S.: Bull. Mater. Ключові слова: карданол, формальдегід, новолак,
Sci., 2004, 27, 235. епіхлоргідрин, епоксидна смола, бутадієн-акрилонітриловий
[22] Tyman J.: Chem. Soc. Rev., 1979, 8, 499. кополімер, спектральні методи.