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

net/publication/242783886

Synthesis and Kinetics Study of Vinyl Ester Resin in the Presence of

Triethylamine

Article  in  Iranian Polymer Journal · November 2006

CITATIONS READS

6 1,492

3 authors, including:

Morteza Ebrahimi Reza Ghaffarian

Amirkabir University of Technology Amirkabir University of Technology
78 PUBLICATIONS   709 CITATIONS    102 PUBLICATIONS   1,038 CITATIONS   

SEE PROFILE SEE PROFILE

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

Micropump View project

encapsulation, self-healing View project

All content following this page was uploaded by Morteza Ebrahimi on 01 June 2014.

The user has requested enhancement of the downloaded file.

 Iranian Polymer Journal
15 (11), 2006, 871-878 Available online at: http://journal.ippi.ac.ir

Synthesis and Kinetics Study of Vinyl Ester

Resin in the Presence of Triethylamine
Golrokh Heidari Hamedani, Morteza Ebrahimi*,
and Seyed Reza Ghaffarian

Polymer Engineering Department, Amirkabir University of Technology,

P.O. Box: 15875-4413, Tehran, Iran

Received 12 April 2006; accepted 20 December 2006

ABSTRACT
he synthesis of an epoxy vinyl ester resin was carried out using a bisphenol-A

T based epoxy resin and methacrylic acid in the presence of triethylamine as a

catalyst. The reaction was performed in the temperature range of 90-120ºC and
epoxy to carboxyl group ratio of 1. In all conditions a conversion of more than 95%
was achieved. The reaction time (for conversions more than 95%) was different from
1.5 h at 120ºC to more than 8 h at 90ºC. The results indicated that reaction followed
a first-order kinetics. The order of reaction with respect to methacrylic acid was also
investigated by using excess method. It was found that in the reaction conditions, the
reaction rate was independent of carboxyl group concentration. The specific rate con-
stant, calculated by the regression analysis, was found to obey Arrhenius expression.
The activation energy and frequency factor were found to be 82.61 kJ/mol and
5.43×109 min-1, respectively. FTIR Analysis of vinyl ester resin revealed that addition
esterification reaction between carboxyl and epoxy groups took place and no side
reactions (i.e., etherification reaction between epoxy and hydroxyl groups) occurred
during the synthesis.

Key Words:
vinyl ester resin;
triethylamine;
esterification;
kinetics; INTRODUCTION
methacrylic acid.
Vinyl ester resins are thermosetting the rapid cure of unsaturated poly-
resins that usually consist of an ester resins which make them a
epoxy resin backbone and they are suitable product for various indus-
prepared by addition of ethyleni- trial applications such as surface
cally unsaturated acids to epoxy coatings, adhesives, printed circuit
resins in the presence of basic cata- board coatings, ultraviolet cured
lysts [1-3]. These materials were inks, composites and fibre rein-
developed in an attempt to combine forced plastics [3-7].
(*) To whom correspondence to be addressed. the chemical, mechanical and ther- Three main chemical reactions
E-mail: [email protected] mal properties of epoxy resins with that can be involved during acid-
Synthesis and Kinetics Study of Vinyl Ester Resin ... Heidari Hamedani G. et al.

epoxy reaction are as follows [8,9]: monoepoxies as a reactive diluent. Srivastava et al.
1) Addition esterification takes place between a car- [20], have studied kinetics of vinyl ester resin synthe-
boxyl group and an epoxy group: sis using bisphenol-A based epoxy resin and
O methacrylic acid in the presence of tertiary amines
OH O
(i.e., triethyl, tripropyl and tributyl amines) in the tem-
R COOH + R1 CH CH2 R1 CH CH2 O C R
perature range of 80-100ºC. Almost all previous
2) Condensation esterification takes place between a researchers have reported an overall reaction order,
carboxyl group and a hydroxyl group situated along however, reaction order with respect to each reactant
the epoxy resin chain or which is the result of the has rarely been investigated.
reaction of the epoxy group with a carboxylic acid: In the present work, we report the results of kinet-
OH R3 O ics studies of vinyl ester resin synthesis via esterifica-
R COOH + R2 CH R3 R2 CH O C R + H2O
tion of epoxy resin with methacrylic acid in the pres-
ence of triethylamine as catalyst in the temperature
3) Etherification results from reaction between an range of 90-120ºC. First we estimated an overall reac-
epoxy group and a hydroxyl group. tion order by using differential methods and then we
confirmed it by integral method. We also investigated
O OH OH R2 the reaction order with respect to acid by using an
R1 CH CH2 + R2 CH R3 R1 CH CH2 O CH R3 excess amount.

During the acid-epoxy reaction, the acid value and

epoxy value decrease, whilst the viscosity of the EXPERIMENTAL
epoxy vinyl ester increases. The esterification reac-
tions (1) and (2) result in a relatively small viscosity Materials
increase for a correspondingly large decrease in acid A bisphenol-A based epoxy resin (Epiran 6,
value. This is in contrast to the etherification reaction EEW=192) from Khuzestan Petrochemical Co. (Iran),
(3). In many cases it is necessary to try to keep the vis- methacrylic acid, triethylamine and hydroquinone
cosity as low as possible. In addition to the above from Merck Chemical Co., were used in this study.
reactions it is possible that unsaturated acid reacts
with a free radical mechanism thereby linking the Apparatus
acids. In the extreme case this results in gelation. In Synthesis reaction was performed in a 500 mL five-
vinyl ester resin synthesis, addition esterification (1) necked flask equipped with a stirrer, nitrogen inlet
is normally promoted by the use of suitable catalysts tube, condenser and thermometer. The reaction mix-
(such as basic catalysts) and reaction conditions. In ture was heated to desired temperature using an elec-
addition, using free radical inhibitor prevents the gela- tromantle.
tion [8-10]. Synthesized resins were characterized by using an
Several research works including Gawdzika and FTIR spectrophotometer. The acid value of the reac-
Matynia [11], Agrawal et al. [12,13] and Bajpai et al. tion mixture was evaluated according to ASTM
[14] have studied the kinetics of the reaction of car- D1636.
boxyl groups with epoxides. The kinetics of addition
esterification of cycloaliphatic epoxies with Procedure
methacrylic acid in the presence of triphenylphos- A reaction mixture consisting of 1:2 molar ratio (5:1
phine [15] and monoepoxy compounds with benzoic for the excess condition) Epiran 6 and methacrylic
acid [16], and caproic acid [17] in the presence of ter- acid with hydroquinone (200 ppm) were charged into
tiary amines has been investigated. Pal et al. [18,19] the reactor. In this situation, equimolar epoxy group to
have synthesized vinyl ester resins using bisphenol-A acid group (10:1 for the excess condition) was used.
based epoxy resin, acrylic acid and triphenylphos- The mixture was stirred and heated up to a desired
phine as catalyst, in the presence and absence of temperature followed by addition of triethylamine

872 Iranian Polymer Journal / Volume 15 Number 11 (2006)

 Heidari Hamedani G. et al. Synthesis and Kinetics Study of Vinyl Ester Resin ...

(1 phr by weight of the resin). The esterification reac-

tion was carried out at 90ºC to 120ºC (90ºC for the
excess condition), and the progress of reaction was
monitored intermittently by measuring the acid value
until the vinyl ester resin of desired acid value (<10
mg KOH/g solid) was obtained.
Concentration dependence of the reaction rate
equation was investigated by determination of acid
concentration changes. Since the acid value (AV) of
reaction mixture relates to acid groups concentration
according to eqn (1), it was used for kinetics study. Figure 1. Acid value versus reaction time.

[Acid]× 56.1 (1)

AV = As it can be observed, the band at 910 cm-1 associat-
d ed with the oxirane ring of epoxy resin (Figure 2a) is
replaced by a band at 1722 cm-1 in vinyl ester spec-
where, trum (Figure 2c), which is due to the carbonyl group
AV: acid value (mg KOH/g) of the ester formed. Another band was observed at
[Acid]: acid group concentration (mol/L) 1636 cm-1 in vinyl ester spectrum that is attributed to
d: reaction mixture density (g/mL) the acryloyl double bond which confirms formation of
The power law model was chosen for kinetics vinyl ester. The band at 3487 cm-1 in vinyl ester spec-
study and the total reaction order was estimated by trum is associated with hydroxyl group which its
differential method, which was then confirmed by absorption intensity increased compared to epoxy
integral method. resin spectrum. This is due to hydroxyl group forma-
The activation energy (Ea) and frequency factor tion during addition esterification reaction (reaction
(k0) were calculated using Arrhenius equation, based (1)). The absence of oxirane ring absorption band in
on the following equation: vinyl ester resin spectrum reveals that epoxy groups
were completely consumed in the reaction.
k = k o e − E a /RT (2) Furthermore, the lack of ether bond absorption band

where, Table 1. FTIR Absorption bands.

T: temperature (K)
R: gas constant (cal/mol.K)
Relevant Wavenumber Functional
-1
spectrum (cm ) group
RESULTS AND DISCUSSION 2a 910 oxiran

Figure 1 shows the changes of reaction mixture acid 2a 1223 ø-O-C

value in relation to time at different temperatures. It is 2a, 2c 3300-3600 -OH
apparent from this figure that acid value decreases
2b 1700 C=O
with an increase in reaction time and its reduction is
faster in the initial stages of the reaction because of a 2b 810 H2C=C
higher concentration of the reactive groups, i.e. acid
2b 2400-3000 -OH
and epoxide.
FTIR Spectra of epoxy resin, methacrylic acid and 2c 1722 C=O
one of the synthesized vinyl ester resins are shown in 2c 1040-1238 ø-O-C
Figures 2a-2c and main absorption bands are present-
ed in Table 1. 2c 943, 1636 H2C=C

Iranian Polymer Journal / Volume 15 Number 11 (2006) 873

Synthesis and Kinetics Study of Vinyl Ester Resin ... Heidari Hamedani G. et al.

(a)

(b)

(c)
Figure 2. FTIR Spectra of (a) epoxy resin; (b) methacrylic acid; and (c) vinyl ester resin.

at 1120 cm-1 shows that, in the reaction conditions, to the carboxyl group in methacrylic acid, Figure 2b)
epoxy groups did not react with hydroxyl groups. in vinyl ester resin spectrum, also confirms the com-
Absence of absorption band at 1700 cm-1 (attributed pletion of acid-epoxy esterification reaction.

874 Iranian Polymer Journal / Volume 15 Number 11 (2006)

 Heidari Hamedani G. et al. Synthesis and Kinetics Study of Vinyl Ester Resin ...

To determine the kinetics parameters, the power

law model was applied. Therefore, the vinyl ester
resin synthesis reaction rate is expressed as:

− rAcid = k [Acid ] [Epoxy ]

α β
(3)

Since the synthesis of vinyl ester resin was carried out

with an equimolar concentration of acid and epoxy
groups ([Acid]=[Epoxy]), the following equation may
be considered for simplifying the rate of reaction
based on the acid concentration:

− rAcid = k [Acid ]
(α + β )
(4)
Figure 3. Ln (-rAV) versus Ln (AV).

According to eqn (1), the reaction rate in terms of acid

value (AV) may be obtained as: the reaction followed almost a first-order kinetics
(i.e., α + β = 1).
(α + β ) −1 Integral method was used to confirm the above
⎛ d ⎞
− rAV = k⎜ ⎟ AV (α + β ) (5) result. The integral form of a first-order reaction is as
⎝ 56.1 ⎠ follows:
Using differential method, total reaction order was AV0
ln = kt (12)
estimated by plotting logarithmic form of reaction rate AV
(-rAV=-dAV/dt) versus logarithmic form of acid value
(AV) based on the following equation: where,
AVo: acid value at t=0
ln( − rAV ) = lnk ′ + (α + β ) lnAV (6) AV: acid value at time 't'
where,
(α + β ) −1
Figure 4 shows plots of (Ln AVo /AVt) versus reaction
⎛ d ⎞ time using the experimental data.
k′ = k⎜ ⎟ (7)
⎝ 56.1 ⎠ The plots were linear at all temperatures with very
good correlation coefficients (r2), wherein the equa-
As it is shown in Figure 3, the plots were linear at all
tions are as follows:
temperatures with very good correlation coefficients
(r2), wherein the equations are as follows: T = 90ºC:
Ln(AVo/AVt) = 7.5×10-3 t (r2 = 0.998) (13)
T = 90ºC:
Ln(-rAV) = 0.967 Ln(AV)-4.7549 (r2 = 0.987) (8) T = 100ºC:
Ln(AVo/AVt) = 1.31×10-2 t (r2 = 0.997) (14)
T = 100C:
Ln(-rAV) = 0.9334 Ln(AV)-4.1071 (r2 = 0.994) (9) T = 110ºC:
Ln(AVo/AVt) = 3.01×10-2 t (r2 = 0.992) (15)
T = 110ºC:
Ln(-rAV) = 1.1147 Ln(AV)-4.0932 (r2 = 0.990) (10) T = 120ºC:
Ln(AVo/AVt) = 5.81×10-2 t (r2 = 0.992) (16)
T = 120ºC:
Ln(-rAV) = 0.9526 Ln(AV)-2.7045 (r2 = 0.999) (11) Above equations confirm that the reaction follows
a first-order kinetics (i.e., α + β = 1) rather than a sec-
It could be estimated from the slope of the plots, that ond-order generally observed for catalyzed esterifica-

Iranian Polymer Journal / Volume 15 Number 11 (2006) 875

Synthesis and Kinetics Study of Vinyl Ester Resin ... Heidari Hamedani G. et al.

Table 2. Amount of specific rate constants.

Reaction temperature Specific rate constant

-1
(ºC) (min )

90 0.0075

100 0.0131

110 0.0301

120 0.0581

constant during the reaction time and the reaction rate

equation can be written as follows:

− rAcid = k * [Acid ]
Figure 4. Ln AVo/AVt versus reaction time. α
(17)
tion reactions [21]. The values of specific rate con-
where,
stant at different temperatures (k) are calculated from
k * = k [Epoxy ]
the slope of the plots (Figure 4) and presented in β
(18)
Table 2.
Most researchers have reported a first-order reac-
Suppose that the reaction follows zero-order kinetics
tion rate for the esterification of epoxy, although
with respect to acid; hence the reaction rate equation
Srivastava and Agrawal [15] reported a second-order
in terms of acid value may be obtained as:
reaction kinetics for this type of reaction. Somewhere
else, Srivastava et al. [20] reported a first-order kinet- ⎛ 56.1 ⎞ ∗
k ∗∗ = ⎜ ⎟k (19)
ics for the reaction of epoxy with metharylic acid in ⎝ d ⎠
the presence of tertiary amine, however, they pro-
where,
posed a second-order mechanism for the reaction, i.e.
-rA = k [Acid][Epoxy]. They stated that according to dAV
− = k ∗∗ = cte (20)
the mechanism the reaction was first-order with dt
respect to acid and emphasized that it was in agree-
Figure 5 shows the relationship of AV and reaction
ment with the experimental results, i.e. overall reac-
time in the excess condition.
tion order. We think, first of all since the carboxylic
The plot was found to be linear with a very good
and epoxide groups were not equimolar in their work,
correlation coefficient, wherein the equation is as fol-
therefore using the formula of -ln(AV/AVo)=kt for
lows:
determining the overall reaction order was not com-
pletely justified. Secondly, the comparison of the
AV= 25.062 - 0.516 t (r2 = 0.979) (21)
overall reaction order with the order of carboxylic
group needs some more experimental data.
This equation confirms that the reaction follows a
In the present work, the excess method was applied
zero-order kinetics with respect to acid and since the
to find the reaction order with respect to each reactant
overall reaction order was determined to be one (i.e.,
(i.e., α and β). For this purpose a reaction mixture
α + β = 1), it follows first-order kinetics with respect
consisting of a 5:1 molar ratio of Epiran 6 and
to epoxy.
methacrylic acid was used. The reaction temperature
of 90ºC was chosen in this condition. Figure 6 shows plots between Ln k (driven from
Since epoxy group concentration is in excess (10 Table 2) and the reciprocal of the reaction tempera-
times of acid group concentration), it is assumed to be ture. It is apparent from Figure 6 that they obey

876 Iranian Polymer Journal / Volume 15 Number 11 (2006)

 Heidari G. et al. Synthesis and Kinetics Study of Vinyl Ester Resin ...

CONCLUSION

It can be concluded from the obtained results that the

esterification reaction of a bisphenol-A based epoxy
resin with methacrylic acid in the presence of triethyl-
amine as catalyst follows a first-order kinetics. The
reaction was found to be zero-order with respect to
acid by using excess method. The amounts of Ea and
ko were calculated to be 82.61 kJ/mol and 5.434 × 109
min-1, respectively.

ACKNOWLEDGEMENT

Figure 5. Acid value (AV) versus reaction time (Temperature

The authors wish to thank Research and Technology
of National Petrochemical Company of Iran for finan-
= 90ºC).
cial support.
ture. It is apparent from Figure 6 that they obey
Arrhenius law. REFERENCES
The slope and intercept of the plots obtained by
regression analysis were used to calculate the energy 1. Czauderna B., Preparation of vinyl ester resins,
of activation (Ea) and frequency factor (ko). The Ger. Offen. DE3, 528, 461, 1987.
amounts of Ea and ko were found to be 82.61 kJ/mol 2. Launikitis M.B., Handbook of Composites, Luben
and 5.434 × 109 min-1, respectively. Srivastava et al. G. (Ed.), Van Nostrand, Reinhold Co., New York,
[20] found that using triethylamine catalyst in com- 38-49, 1982.
parison to tripropylamine and tributylamine, a maxi- 3. Scott T.F., Cook W.D., Forsythe J.S., Kinetics and
mum reaction rate was attained. They reported Ea and network structure of thermally cured vinyl ester
ko for triethylamine catalytic system to be 57.02 resins, Eur. Polym. J., 38, 705-716, 2002.
kJ/mol and 1.077 × 106 min-1, respectively, which are 4. Astrom B.T., Manufacturing of Polymer
less than what we have obtained in this study. Composites, Chapman and Hall, London, 86,
1997.
5. Karbhari V.M., Rivera J., Zhang J., Low-tempera-
ture hydrothermal degradation of ambient cured E-
glass/vinyl ester composites, J. Appl. Polym. Sci.,
86, 2255-2260, 2002.
6. Yebassa D., Balakrishina S., Feresenbet E.,
Raghavan D., Start P.R., Hudson S.D., Chemically
functionalized clay vinyl ester nanocomposites:
Effect of processing parameters, J. Polym. Sci.
Part A: Polym. Chem., 42, 1310-1321, 2004.
7. Abadie M.J.M., A comparative study of unsaturated
polyester resins and vinylesters, Composites, 37,
15-18, 1997.
8. Oldring P., Waterborne and solvent based epoxies
and their end user applications, John Wiley,
London, 2, 1997.
Figure 6. Plot of Ln k versus reciprocal of temperature. 9. Blank W.J., He Z.A., Picci M., Catalysis of the

Iranian Polymer Journal / Volume 15 Number 11 (2006) 877

Synthesis and Kinetics Study of Vinyl Ester Resin ... Heidari G. et al.

epoxy-carboxyl reaction, J. Coat. Technol., 74, 33-

41, 2002.
10. Oldring P., Hayward G., Resins for surface coat-
ings, Sita Technology, 2, 1987.
11. Gawdzik B., Matynia T., Synthesis and modifica-
tion of epoxy-based divinyl ester resin, J. Appl.
Polym. Sci., 81, 2062-2067, 2001.
12. Agrawal S., Srivastava D., Mishra A., Rai J.S.P.,
Decomposition behavior of vinyl ester resins pre-
pared in presence of tertiary amines, Polym. Plast.
Technol. Eng., 41, 327-340, 2002.
13. Agrawal S., Mishra A., Rai J.S.P., Effect of dilu-
ents on the decomposition behavior of vinyl ester
resin, J. Appl. Polym. Sci., 87, 1952-1956, 2003.
14. Bajpai M., Shukla V., Kumar A., Film perform-
ance and UV curing of epoxy acrylate resins,
Prog. Org. Coat., 44, 271-278, 2002.
15. Srivastava A., Agrawal S., Kinetics of esterifica-
tion of cycloaliphatic epoxies with methacrylic
acid, J. Appl. Polym. Sci., 86, 3197-3204, 2002.
16. Kakiuchi H., Tanaka Y., Study of epoxy com-
pounds.VII. Base-catalyzed reaction of substituted
phenyl glycidyl ethers with benzoic acid, J. Org.
Chem., 31, 1559-1564, 1966.
17. Matejka L., Dusek K., Specific features of the
kinetics of addition esterification of epoxide with
the carboxyl group, Polym. Bull., 15, 215-221,
1986.
18. Pal N., Srivastava A., Rai J.S.P., Synthesis of vinyl
ester resins in the presence of monoepoxides: A
kinetic study, Polym. Plast. Technol. Eng., 42,
105-122, 2003.
19. Pal N., Srivastava A., Rai J.S.P., Kinetics and
mechanism of esterification of epoxy resin in pres-
ence of triphenylphosphine, Int. J. Chem. Kinet.,
36, 280-285, 2004.
20. Srivastava A., Pal N., Agrawal S., Rai J.S.P.,
Kinetics and mechanism of esterification of epoxy
resin with methacrylic acid in the presence of ter-
tiary amines, Adv. Polym. Technol., 24, 1-13,
2005.
21. Odian G., Step Polymerizations: Principles of
Polymerization, Wiley InterScience, New York,
2nd Ed., 1981.

878 Iranian Polymer Journal / Volume 15 Number 11 (2006)

View publication stats