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, 85
, 90
, 95
,
and 100
, 85
, 90
, 95
, and 100
C in the presence of
tertiary amines. Figures 1, 2, and 3 show the esteri-
cation of bisphenol-A epoxy resin with methacrylic
acid in the presence of triethyl amine (V
1
), tripropyl
amine (V
2
), andtributyl amine (V
3
), respectively. It is
apparent from the gures that acid value decreases
2 VOL. 24, NO. 1
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
FIGURE 1. Acid value versus reaction time for V
1
.
FIGURE 2. Acid value versus reaction time for V
2
.
ADVANCES IN POLYMER TECHNOLOGY 3
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
FIGURE 3. Acid value versus reaction time for V
3
.
with increase in reaction time and is not linear in the
initial stages of the reaction. This is because of a high
concentration of the reactive sites and the greater
possibilityof associationof acidandepoxide groups.
The linearity of the plots in the higher conversion re-
gion(>74%) reveals that the reactivityof a functional
group is independent of molecular size, which is a
characteristic of polyesterication reactions.
22
The number average values for degree of poly-
merization (X
n
) of V
1
, V
2
, and V
3
prepared at 80
,
85
, 90
, 95
, and 100
C 85
C 90
C 95
C 100
C
Time (min) p X
n
p X
n
p X
n
p X
n
p X
n
30 0.09 1.09 0.12 1.13 0.15 1.17 0.18 1.21 0.23 1.28
60 0.20 1.23 0.25 1.31 0.32 1.44 0.39 1.59 0.46 1.78
90 0.27 1.34 0.35 1.50 0.42 1.66 0.53 2.01 0.62 2.42
120 0.37 1.54 0.47 1.80 0.55 2.09 0.65 2.60 0.72 3.17
150 0.41 1.63 0.52 1.97 0.64 2.54 0.73 3.22 0.80 4.13
180 0.45 1.74 0.62 2.42 0.70 2.97 0.81 4.32 0.87 5.76
210 0.54 2.04 0.67 2.74 0.76 3.58 0.87 5.76
240 0.61 2.38 0.70 2.97 0.80 4.13
270 0.65 2.60 0.75 3.45 0.84 4.87
300 0.69 2.89 0.79 3.97 0.87 5.76
330 0.72 3.17 0.82 4.52 0.90 6.79
360 0.75 3.45 0.86 5.45
390 0.78 3.80 0.89 6.33
420 0.80 4.13
450 0.82 4.52
480 0.84 4.87
510 0.87 5.76
540 0.89 6.33
TABLE II
Extent of Reaction ( p) and Degree of Polymerization (X
n
) with Time for V
2
80
C 85
C 90
C 95
C 100
C
Time (min) p X
n
p X
n
p X
n
p X
n
p X
n
30 0.07 1.07 0.10 1.10 0.12 1.13 0.16 1.18 0.20 1.23
60 0.14 1.15 0.20 1.23 0.22 1.26 0.33 1.45 0.38 1.56
90 0.25 1.31 0.28 1.36 0.36 1.52 0.46 1.78 0.55 2.09
120 0.29 1.38 0.37 1.54 0.43 1.69 0.54 2.04 0.63 2.47
150 0.36 1.52 0.42 1.66 0.50 1.90 0.63 2.47 0.72 3.17
180 0.40 1.61 0.48 1.83 0.56 2.13 0.68 2.79 0.80 4.13
210 0.46 1.78 0.54 2.04 0.62 2.42 0.77 3.73 0.85 5.14
240 0.50 1.90 0.58 2.22 0.69 2.89 0.81 4.32 0.89 6.33
270 0.54 2.04 0.63 2.47 0.71 3.06 0.85 5.14
300 0.57 2.18 0.67 2.74 0.76 3.58 0.89 6.33
330 0.60 2.32 0.70 2.97 0.78 3.80
360 0.63 2.47 0.73 3.22 0.81 4.32
390 0.68 2.79 0.77 3.73 0.84 4.87
420 0.69 2.89 0.80 4.13 0.87 5.76
450 0.71 3.06 0.82 4.52
480 0.74 3.33 0.84 4.87
510 0.76 3.58 0.87 5.76
540 0.78 3.80
570 0.80 4.13
600 0.84 4.87
630 0.87 5.76
ADVANCES IN POLYMER TECHNOLOGY 5
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
TABLE III
Extent of Reaction ( p) and Degree of Polymerization (X
n
) with Time for V
3
85
C 90
C 95
C 100
C
Time (min) p X
n
p X
n
p X
n
p X
n
30 0.09 1.09 0.11 1.11 0.14 1.15 0.16 1.18
60 0.15 1.17 0.20 1.23 0.27 1.34 0.30 1.36
90 0.22 1.26 0.29 1.38 0.38 1.56 0.45 1.74
120 0.28 1.36 0.37 1.54 0.48 1.83 0.57 2.18
150 0.34 1.47 0.44 1.71 0.56 2.13 0.65 2.60
180 0.39 1.59 0.50 1.90 0.62 2.42 0.70 2.97
210 0.45 1.74 0.56 2.13 0.68 2.79 0.78 3.80
240 0.48 1.83 0.61 2.38 0.72 3.17 0.82 4.52
270 0.53 2.01 0.66 2.68 0.77 3.73 0.85 5.14
300 0.56 2.13 0.70 2.97 0.80 4.13 0.89 6.33
330 0.60 2.32 0.73 3.22 0.83 4.63
360 0.63 2.47 0.77 3.73 0.87 5.76
390 0.65 2.60 0.79 3.97 0.89 6.33
420 0.67 2.74 0.81 4.32
450 0.71 3.06 0.83 4.63
480 0.73 3.22 0.86 5.43
510 0.75 3.45 0.88 5.97
540 0.77 3.73
570 0.80 4.13
600 0.82 4.52
630 0.84 4.57
FIGURE 4. FTIR spectrum of synthesized V
1
, V
2
, and V
3
.
6 VOL. 24, NO. 1
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
FIGURE 5. ln AV
0
/AV
t
versus reaction time for V
1
, 80
C, y = 3.9348 10
3
x (r = 0.9993); 85
C, y = 5.2918 10
3
x
(r = 0.9991); 90
C, y = 6.8548 10
3
x (r = 0.9984); 95
C, y = 9.1491 10
3
x (r = 0.9990); 100
C,
y = 11.0073 10
3
x (r = 0.9991).
forma hydroxyl group by abstracting the proton. Si-
multaneously, the carboxylate anion released by the
activated complex attacks at the terminal carbon of
the epoxy ring, forming an ester linkage with the
regeneration of catalyst.
On the basis of the mechanism proposed in
Scheme 1, the following steps may be considered for
evaluating the rate of disappearance of acid:
Acid +Cat
k
1
X (i)
k
1
(Activated acidcatalyst complex)
X +Epoxy
k
[Y] VER (ii)
According to above steps, the rate of disappearance
of acid may be obtained as
d[Acid]
dt
= k[X][Epoxy] (iii)
where,
[X] =
k
1
[Acid][Cat]
k
1
+k[Epoxy]
Therefore, the rate of disappearance of acid is ob-
tained as:
d[Acid]
dt
=
kk
1
[Acid][Cat][Epoxy]
k
1
+k[Epoxy]
(iv)
ADVANCES IN POLYMER TECHNOLOGY 7
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
FIGURE 6. ln AV
0
/AV
t
versus reaction time for V
2
, 80
C, y = 2.7800 10
3
x (r = 0.9990); 85
C, y = 3.7881 10
3
x
(r = 0.9996); 90
C, y = 4.6981 10
3
x (r = 0.9991); 95
C, y = 6.8104 10
3
x (r = 0.9988); 100
C,
y = 8.8689 10
3
x (r = 0.9995).
Since step (i) is fast and considering k
1
is
k[Epoxy], the above rate law reduces to
d[Acid]
dt
= kK
1
[Acid][Cat][Epoxy] (v)
where, K
1
= k
1
/k
1
.
It is apparent from Eq. (v) that the reaction is of
rst order with respect to acid and it is in agreement
with the experimental results.
In another possible mechanism(Scheme 2) the re-
action is initiated by dimer acidcatalyst complex.
The initiator attacks on epoxy oxygen to form the
VER with the release of the acidcatalyst complex
that canreact withanother epoxy molecule as shown
in Scheme 1.
According to the above mechanism, the following
steps may be considered for evaluating the rate of
disappearance of acid:
2Acid
k
2
k
2
[Acid]
2
(vi)
[Acid]
2
+Cat
k
3
k
3
X
1
dimer acidcatalyst complex
(vii)
Epoxy +X
1
k
4
VER +X (viii)
Since the rate of disappearance of acid may be ob-
tained as
d[Acid]
dt
= k
2
[Acid]
2
k
2
{[Acid]
2
} (ix)
8 VOL. 24, NO. 1
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
FIGURE 7. ln AV
0
/AV
t
versus reaction time for V
3
, 85
C, y = 2.7430 10
3
x (r = 0.9990); 90
C, y = 4.0757 10
3
x
(r = 0.9989); 95
C, y = 5.4797 10
3
x (r = 0.9993); 100
C, y = 7.1403 10
3
x (r = 0.9991).
By applying study state conditions with respect to
[X
1
], the value of [X
1
] may be given as
[X
1
] =
k
3
{[Acid]
2
}[Cat]
k
3
+k
4
[Epoxy]
(x)
Again,
{[Acid]
2
} = K
2
[Acid]
2
(xi)
From step (vi) where K
2
= k
2
/k
2
and therefore rate
law (ix) has been obtained as
d[Acid]
dt
=
K
2
k
3
k
4
[Acid]
2
[Epoxy][Cat]
k
3
+k
4
[Epoxy]
(xii)
Since step (vii) is fast, taking k
3
k
4
[Epoxy], the
above rate law reduces to
d[Acid]
dt
= K
2
K
3
k
4
[Acid]
2
[Epoxy][Cat] (xiii)
where K
3
= k
3
/k
3
.
The Eq. (xiii) shows that the reaction is second
order with respect to acid indicating that Scheme 2
is not in consistent to the experimental results and
the reaction proceeds only through the formation of
acidcatalyst complex.
The formation of acidcatalyst complex was elu-
cidated by IR spectra of the complex of methacrylic
acid and tertiary amines and is shown in Fig. 8. The
complexes C
1
, C
2
, and C
3
were prepared by treat-
ADVANCES IN POLYMER TECHNOLOGY 9
KINETICS AND MECHANISM OF ESTERIFICATION OF EPOXY RESIN
SCHEME 1 Mechanism of esterication of epoxy resin initiated by acid-catalyst complex.
ing the mixture of methacrylic acid and triethyl-,
tripropyl-, and tributyl-, amines, respectively in mo-
lar ratios 2:1 at 70