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ISSN 1995 4212, Polymer Science, Series D. Glues and Sealing Materials, 2014, Vol. 7, No. 1, pp. 61–64. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © OF Shishlov, SA Dozhdikov, VV Glukhikh, OV Stoyanov, 2013, published in Klei. Germetiki. Tekhnologii, 2013, No. 5, pp. 15–18.

Analysis of the Influence of Cardanol Content on the

Properties of Phenol–Cardanol–Formaldehyde Novolac Resins
OF Shishlova, *, SA Dozhdikova, VV Glukhikhb , and OV Stoyanovc, **
a
Uralchimplast OAO, Severoe sh. 21, Nizhny Tagil, Sverdlovsk oblast, 622012 Russia
b
Ural State Forest Engineering University, Sibirskii trakt 37, Yekaterinburg, 620100 Russia
c
Kazan State Engineering University, ul. Karla Marksa 68, Kazan, Tatarstan, 420015 Russia
*email: O.Shishlov@ucp.ru
**email: ov_stoyanov@mail.ru
Received November 27, 2012

Abstract—The influence of cardanol content on the molecular weight distribution and curing kinetics of phenol–
cardanol–formaldehyde novolac oligomers is evaluated. It is shown that, depending on the cardanol content,
the resulting oligomers can be used as components in glues and sealants of different purposes.

Keywords: cardanol, phenol–cardanol–formaldehyde resin, molecular weight distribution, glue for timber
DOI: 10.1134/S1995421214010109

INTRODUCTION formalin produced by OAO Uralkhimplast,

It is a promising trend in acquiring glue systems for
composite materials to use phenolaldehyde timber oli
gomers that contain cardanol, a renewable plant phenol
extracted from cashew nut shell liquid [1–3].
Cardanol is a combination of alkylphenols that con
sists mainly of 3 pentadecylphenol; 3 (8(Z) pentadece
nylphenol; 3 (8(Z), (11(Z) pentadecadienylphenol, and
3 (8(Z), 11(Z), 14 pentadecatrienyl)phenol [1].
Cardanol containing polymers shows strong water
and electric resistance, as well as acid and alkali resis
tance, and they resist abrasion, wear, and thermites
[3]. As a result of a carbon substituent in C15 metapo
sition, the polymers have internal plasticization and
are soluble in hydrocarbon solvents and oils [2].
Reactions of synthesis of novolac cardanol–formal
dehyde resins by condensation of cardanol with formal
dehyde at different molar ratios in presence of different
acidities generated by nonorganic and organic acids
have been studied adequately well [1–17].
At the same time, the production and use of novolac
phenol–cardanol–formaldehyde resins have been stud
ied to a lesser extent [1–3, 18–21]. Depending on car
danol content, these oligomers can be used as compo
nents in glues and sealants with different purposes.
The objective of this work is to investigate the influ
ence of cardanol content on the molecular weight
distribution and curing kinetics of phenol–cardanol–
formaldehyde novolac (two stage) oligomers.
EXPERIMENTAL
To synthesize resins and study their reactivity in the
lab, the following materials were used: (1) technical
(2) synthetic phenol under GOST (State Standard)
23519–93, (3) technical cardanol produced by South
ern Agro Phenols Ltd. (SAPL) (India) (4) oxalic acid
under GOST (State Standard) 22180–76, and
(5) hexamethylenetetramine under GOST (State Stan
dard) 1381–73.
Phenol–cardanol–formaldehyde novolac resins
(PCFNR) were synthesized using the following
procedure dure: feeding of phenol, cardanol, formalin, and
oxalic acid; 60 min condensation at 96–98°C; drying
out under atmospheric pressure after reaching 150°C;
20 min vacuum drying out at 5 kPa after reaching
184°C; and cooling down.
The resin drop temperature was measured using a
Mettler Toledo FP90 unit.
The molecular weight distribution of the obtained
resins was studied by gel penetrating chromatography
(GPC) on a Shimadzu LC 10Avp chromatograph
with 300 × 8 mm Shodex KF 803 (3 pc.) and KF 802
(3 pc.) columns and a refractometer detector (with
Aldrich tetrahydrofurane as the mobile phase).
A Mettler Toledo DSC 823e/700 differentiating
scanning calorimeter unit was used to investigate the
kinetics of curing of phenol–cardanol–formaldehyde
oligomers. Thermal currents on the DSC analyzer
(DSC measurements) were measured in closed cups
able to resist vapor pressure up to 0.2 MPa. The
dynamic DSC measurements were performed at heat
ing rates of 5, 10, and 20°C/min within 25–350°C.
The sample resin weights 4–8 mg.
The kinetic calculations were done in accordance
with already known algorithms [22, 23].

sixty one
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62 SHISHLOV et al.

Mw, g/mol Mw / Mn
5500 4.50 4.25
4.00
5000

4500 3.75
4000 3.50
3.25
3500
3.00
3000 2.75
2.50
2500
2.25
2000 2.00
1500 1.75
1.50
1000 0 10 30 4020 50 60 8070 90 100
0 10 20 40 5030 60 70 80 90 100
Cardanol content, %
Cardanol content, %

Fig. 1. Dependence of average molecular weight Mw on the Fig. 2. Dependence of Mw/Mn polydispersity on the cardanol
cardanol content in the original mixture of phenol and cardanol. content in the original mixture of phenol and cardanol.

RESULTS AND DISCUSSION 2440 g/mol (cardanol content is 100%). This kind of
The typical phenol/formaldehyde ratio for novolac dependence can be explained by the influence of two
resins is 1/(0.75–0.85). Concurrently, low molecular oppositely directed factors on the molecular weight of
resins with Mw ÿ 2000 g/mol are obtained that are mostly the forming oligomer: the first one is a positive induc tive
linear in terms of structure, with methylene groups effect of m alkyl substituent (+I eff.) that improves the
between phenol cores [24, 25]. In this work, the phenol/ reactivity of cardanol in SE 2 reactions compared to
formaldehyde ratio is 1/0.8. If a mixture of phenol and phenol, and the second one is the steric factor of the
cardanol is used as a raw material, Mw of the novolac bulk C15 hydrocarbon substituent that, in its respect,
resins that are obtained in the specified molar range will inhibits the course of polycondensation, which speaks
be 1590–5120 g/mol (Fig. 1) and have the following the molecular mass of the resulting oligo mer. At the
chemical formula: same time, the steric factor prevails when the cardanol
content is at least 40% (see Fig. 1).
OH OH OH The dependence of polydispersity changes in the
forming oligomer (Mw/Mn) upon the cardanol content in
H2 H2 the original mixture of cardanol and phenol is sim ilar in
OLD OLD
its essence (Fig. 2).
CHEAP CHEAP CHEAP

m It follows from Fig. 3 that the drop temperature of the

R = –H
As the cardanol content increases, Mw of the form
ing oligomer rises from 1590 (cardanol content is 0%)
to the peak 5120 g/mol (cardanol content is 35%). Mw
then suddenly changed to 3040 g/mol (cardanol con
tent is 40%) and continues to fight decrease to
forming oligomers fought from 99 (cardanol content is
0%) to 89°C (cardanol content is 35%), then the
temperature changed to 64°C (cardanol content is 40%)
and continues to decline to 5°C (cardanol content is
100%). Although a consider able molecular mass growth
in this range, the gradual decrease in temperature in the
oligomers with the car danol content from 0 to 35% can
be due to the internal plasticizing effect of the C15
hydrocarbon substituent.
The sharp decline in the drop temperature of the oli
gomer the cardanol content in which is 40% can be due
to a sharp decrease in molecular mass against the
backdrop of increasing internal plasticization.
To study the influence of the cardanol content on the
reactivity of the oligomer during DSC study of curing
with hexamethylene tetramine, the ratio of 0.1 mol of
hexamethylene tetramine to 1 mol of phen nol fragment
in the oligomer was used. The influence

POLYMER SCIENCE Series D Vol. 7 No. 1 2014

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ANALYSIS OF THE INFLUENCE OF CARDANOL CONTENT
Tdrop temperature, °C
110
100
90
80
70
60
50
40
30
20
ten
0 ten 30 4020 50 60 70 80 90 100
Cardanol content, %
Fig. 3. Dependence of the drop temperature of PCFNR on the
cardanol content in the original combination of phenol and
cardanol.
of the cardanol content on the reactivity of the oligo
mer is complex and (Fig. 4) depends on two oppositely
directed factors: the first one is a positive inductive
effect of the m alkyl substituent (+I eff.) cardanol
fragments in SE 2 reactions compared to phenol
fragments, and the second one is the steric factor of
the bulk C15 hydrocarbon substitu ent that, in turn,
inhibits the course of the reaction with
hexamethylenetetramine.
In this instance, the steric factor depends on both,
the influence of the molecular weight of the oligomer
and the number of bulk C15 hydrocarbon substituents
in the structure of the oligomer. As the cardanol con
tent grows from 5 to 30%, the reactivity of oligomers
increases for +I eff. prevails over the influence of the
steric factor. The oligomer with the cardanol content of
35% has the highest molecular mass, and, in this
instance, the steric factor prevails over +I eff., that can
be seen in the decreasing reactivity of the oligomer.
With the cardanol content ranging from 40 to 80%, the
reactivity of oligomers increases, which may be due to
the decline in the influence of the steric factor that
depends on the molecular weight level, despite the
increase in the steric factor that depends on the influ
ence of bulk C15 hydrocarbon substituents. With the
cardanol content ranging from 80 to 100%, the react
tivity of oligomers declines, which may be due to the
prevalence of the influence of the steric factor, that
depends on the influence of C15 hydrocarbon substitu
ents, over the influence of +I eff.
CONCLUSIONS
The influence of cardanol content on the molecu
lar weights distribution of phenol–cardanol–formal
POLYMER SCIENCE Series D Vol. 7 No. 1 2014
63
ÿ, min
9.0 8.5
8.0 7.5
7.0 6.5
6.0 5.5
5.0 4.5
4.0 3.5 2
3.0 2.5
2.0 0
10 20
30 40 first
50 60
70 80
90 100
Cardanol content, %
Fig. 4. Dependence of the curing time of PCFNR at 140°C
during which conversion degree of (1) 50 and (2) 90% is
reached from the cardanol content in the original mixture of
phenol and cardanol.
dehyde novolac resins has been evaluated. The
dependence of the average molecular mass of oligo
mers from cardanol content has been shown.
It has been shown that the influence of the cardanol
content on the reactivity of phenol–cardanol–form
aldehyde novolac resins with hexamethylene tetra
mine during curing is complex and depends on two
different directed factors: the positive inductive effect of
the m alkyl substituent and the steric influ ence of bulk
C15 alkyl substituents.
Depending on their cardanol content, the resulting
oligomers can be used as components in glues and
sealants for different purposes.
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