Ind. Eng. Chem. Res.

2008, 47, 85558560

8555

Mathematical Model For Predicting Gel Point in the Process of Manufacturing

Alkyd Resins
M. A. B. Prashantha, J. K. Premachandra, and A. D. U. S. Amarasinghe*
Department of Chemical and Process Engineering, UniVersity of Moratuwa, Sri Lanka

A mathematical model for the prediction of gel formation in the synthesis of alkyd resins is developed. The
probability of developing linear polymer molecules is related to the average functionality, Fav. A statistical
factor is introduced to represent the probability of having free OH groups in the backbone of a linear alkyd
molecule. Factor increases from 0 to a maximum of max when the acid value decreases from AVinitial to
AVmax during the polymerization. Branch generation in alkyd molecules becomes significant only after the
acid value is reached, AVmax, and it continues until a gel is formed. At max, the average functionality (Fav(max))
and the acid value (AVmax) are calculated in terms of the number of moles of OH groups, number of moles
of COOH groups, and total number of molecules per unit mass at the beginning of polymerization. The acid
value at the gel point, AVgel, is then calculated using the values of Fav(max) and AVmax. The predicted acid
values using the new model are in good agreement with the actual data reported for polyesterification in the
synthesis of alkyd resins.
1. Introduction

P)

Control of polymerization is essential in making alkyd resins,

as gelation may occur before the required extent of polymerization is achieved. Gelation is a common problem in alkyd resin
manufacture, and it forms unwanted polymeric materials which
cannot be recycled. This results in wastes of raw materials,
processing time, and energy. Cleaning vessels also becomes a
tedious job as special chemical treatments are required. Therefore, the ability to predict the gel point of a particular polymerization system is of great importance to both research
workers and alkyd resin manufacturers.
Gelation involves aggregation of clusters in reacting polymers,
hydrogels, and colloids.1,2 It is a phase transition process occurring in connecting aggregates of monomers in branched or
unbranched chains (each monomer has only one link to each
of its nearest neighbors, except at branch points or chain ends)
or in networks (monomers are interconnected by several links).
Numerous mathematical relations have been derived in modeling
both reversible and irreversible gelation.3-10
Gelation in the synthesis of alkyd resins mainly depends on
the average functionality of reactants. W. H. Carother developed
a mathematical equation11 relating the extent of polymerization
(P), initial average functionality (F), and number-average degree
of polymerization (DP). An extension to the Carother equation
was later proposed by assuming that when a gel product was
formed the term DP reached infinity, as no further molecules
were available for the reaction to proceed. This argument led
to a simple mathematical relation given by eq 1 for predicting
the extent of polymerization up to the gel point.
P ) 2/F
(1)
Equation 1 predicts accurate results only if F is close enough
to 2, and for higher values of F, the model overestimates the
gel point. Flory suggested that Mw (weight-average molar mass)
was greater than Mn (number-average molar mass) for polydisperse (Mw * Mn) polymerization systems and therefore Mw
achieved infinity before Mn when it formed a gel.12 Florys
branching treatment led to further modification of the Carother
model as
* To whom correspondence should be addressed. Tel.: +94 11
2640337. Fax: + 94 11 2650622. E-mail: adusa2@cheng.mrt.ac.lk.

( 1 -2 F ) + ( 2r1 ) + ( FF )

(2)

The term r is the initial molar ratio of total number of COOH

groups (including from both dibasic acids and monobasic acids)
to the total number of OH groups, and F is the initial molar
ratio of COOH groups from carboxylic acids other than dibasic
acids to the total COOH groups in the reaction mixture. In
deriving this model, the extent of reaction was considered up
to the median of the molecular weight distribution curve; hence
eq 2 predicts an upper limit to the gel point. Another
mathematical relation based on the extent of reaction at infinite
molecular weight has been derived (eq 3) for predicting a lower
limit to the gel point, using further statistical analysis.11
P ) [r + rF(F - 2)]-1/2
(3)
13
Flory defined a new term, the branching coefficient (R), to
describe the incipient of the formation of an infinite network
Table 1. Actual and Predicted Gel Point Acid Values
gel point acid
values calculated
by models (mg/g)

alkyd AV final
recipes (mg/g) Carother Wiedehorn Flory Stockmayer proposed
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

11.57
9.7
5.88
5.27
4.67
7.21
2.41
1.11
0.74
10.1
9
10.2
15
15
18
18
18
29
19
20

60.34
45.76
38.65
31.67
18.54
5.84
22.04
15.84
10.18
15.6
16.4
10.2
29.75
15.39
35.12
29.1
31.17
35.02
30.79
35.02

27.74
19.27
12.43
6.6
-6.15
-16.56
9.28
0.89
-5.83
15.67
9.27
10.87
25.02
9.52
21.1
12.78
15.73
20.97
15.2
20.97

10.1021/ie8005534 CCC: $40.75 2008 American Chemical Society

Published on Web 10/16/2008

-2.92
13.47
14.86
18.45
22.22
29.54
43.77
39.81
38.55
68.49
54.59
46.6
62.35
57.87
45.43
47.54
46.82
45.46
46.95
45.46

-21.59
-12.55
-14.9
-14.52
-16.49
-12.37
10.57
3.58
0.11
37.09
21.08
31.56
34.12
23.91
15.94
10.38
12.33
15.85
11.98
15.85

18.94
16.95
13.01
10.13
3.43
-1.37
13.89
8.35
4.08
16.23
13.22
11.84
24.88
13.15
22.25
17.37
19.08
22.17
18.77
22.17

8556 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008

Figure 1. Part of an alkyd molecule with a free OH group in the backbone.

COOH groups at the gel point. The outcome of his model

consisted of three equations, as given by eqs 7, 8, and 9.
AVgel )

18700(p + f) 1.5a
- 3.5 + Fn
W
p+f

W ) aMa + pMp + fMf - 18

)(

(p + f)(Fn - 2)
1.5
-1
Fn - 2
1.5

(7)

)
(8)

Fn )
Figure 2. Variation of with acid value in the polyesterification stage of
monoglyceride mixture.

and developed a relation between the branching coefficient and

the extent of polymerization. He assumed that the term R(fb 1) is equal to unity when reaction medium becomes a gel. At
that condition R is called the critical branching coefficient
(Rc).Therefore
Rc ) 1/(fb - 1)

(4)

where fb is the functionality of branching units (molecular

species with functionality greater than 2, such as glycerol and
pentaerythritol).
Flory then related R to a probability parameter PA (probability
that an OH group had reacted) and PB (the probability that a
COOH group had reacted) as
R)

PAPBR
1 - PAPB(1 - R)

(5)

where R is the ratio of the number of OH groups (both reacted

and unreacted) in branching units to the total number of OH
groups in the reaction mixture.
Stockmayer included the effect of ring formation in his
analysis and developed another statistical relation to predict the
extent of polymerization at the gel point.14-16
Pgel2 )

( g G ) [ (f
2

- fi)Hi

(g

- gj)Hj

(6)

where fi and Hi represent the COOH group functionality and

the number of moles of i type of carboxylic acid molecules,
respectively. gj and Gj represent hydroxyl functionality and the
number of moles of j type of polyol molecules, respectively.
Wiedehorn followed a method similar to the method of Flory
but modified the critical value for branching coefficient by
considering an average of 1.5 cross-links per polymer molecule
in the reaction mixture when forming the single giant molecule.17 In his model Wiedehorn used the acid value at the gel
point (AVgel) as a measure of the number of moles of unreacted

eie - q
e

(9)

where a is the number of moles of phthalic anhydride, p is the

number of moles of polyols, f is the number of moles of oil, Fn
is the number-average functionality of mixed polyols prior to
esterification, and Ma, Mp, and Mf are molar masses of dibasic
acid, polyol, and oil, respectively. W is the weight of the reaction
mixture at the gel point after losing water, e is the number of
moles of polyols, ie is the average hydroxyl functionality of
polyol, and q is the number of moles of monobasic acid.
These models are useful not only in controlling a polymerization process without a gel formation but also in selecting a
correct formulation. The objectives of the present study were
to develop a new mathematical model for predicting the gel
point by considering the probability of forming a highly
branched molecule from linear polymer molecules during the
polymerization process and to compare its accuracy with the
existing models.
2. Basis for Mathematical Model
2.1. Basic Assumptions. The new model is based on the
assumption that incipient branching occurs at the unreacted OH
groups in branching units (monomers having more than two
functional groups) which are in the polymer backbone. Further,
ring formation reactions are assumed to be negligible during
the polyesterification. The following steps were assumed in the
development of the alkyd molecule from a linear structure to a
highly branched three-dimensional structure and finally to a
single giant three-dimensional molecule at the gel point.
2.1.1. Growth of Polymer Molecule. At the beginning of
polyesterification, dibasic acid or its anhydride reacts with
various types of monoglycerides, dipentaerythritide, and branching units, and a linear alkyd molecule is formed. As the polymer
molecule grows, the probability of the availability of free OH
groups in the polymer backbone increases and the acid value
of the polymerization mixture decreases. Figure 1 shows a part
of an alkyd molecule with a free OH group in the polymer
backbone. The steric hindrances may prevent these free OH
groups in the polymer backbone from taking part in branching.

Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008 8557

K ) initial number of moles of OH groups in branching units

which contribute to placing them in segmental positions of
polymer backbones expressed as a fraction of the initial number
of moles of OH groups in total
L ) initial number of moles of OH groups which can generate
branches as a fraction of the initial number of moles of OH
groups in total
R ) probability of the availability of linear polymer molecules
in the reaction mixture.
3.1.1. Probability Factor J. The probability factor J is
expressed as
Figure 3. Comparison of the Wiedehorn model and the proposed model
with actual data.

As a result, the average functionality of polymer molecules

exceeds the value 2 with further continuation of the polymerization reaction.
2.1.2. Branching. With the increase in the extent of polymerization, the concentration of free OH groups in monomers
and oligomers continuously decreases while the concentration
of free OH groups in the polymer backbone increases. Consequently, after a certain extent of reaction (or below a certain
acid value), the probability of the presence of free OH groups
becomes greater in polymer backbones than in monomers and
oligomers, and the branching becomes significant.
2.1.3. Gel Formation. When the branching becomes significant, the probability of the presence of free OH groups in
the polymer backbone starts to decrease while the acid value
further decreases due to the overall reduction in free OH groups.
At this stage of polymerization, the probability of the existence
of linear polymer molecules significantly decreases and finally
a highly branched single giant molecule is formed. At this
moment, the reaction medium becomes a solid lump and the
corresponding acid value is called the gel point acid value.
2.2. Probability Factor . A probability factor is introduced to represent the probability of having free OH groups in
the backbone of a linear alkyd molecule, which increases from
0 to a maximum (max) while the acid value decreases from
AVini to AVmax during the early stage of polyesterification
(Figure 2). AVmax corresponds to the acid value at which the
branching becomes significant, and when the acid value further
decreases with the increase in the extent of polymerization,
starts to decrease. As a result, for a given there are two
corresponding acid values, as shown in Figure 2. At the higher
acid value the reaction mixture has a lower amount of branched
polymer molecules, and at the lower acid value the reaction
mixture has a higher amount of branched polymer molecules.
As the reaction further continues, the acid value approaches
AVgel, at which a three-dimensional highly branched gel product
is formed.
3. Model Development
3.1. Mathematical Expression for . The probability factor
is expressed as a product of four other probability factors: J,
K, L, and R. The factors K and L are constants which depend
on the characteristics of the alkyd recipe, while J and R are
dependent on the extent of polymerization.
)JKLR
(10)
where
J ) number of moles of reacted OH groups at a given acid
value as a fraction of the initial number of moles of OH groups
in total

J)

NOH - nOH
NOH

(11)

where NOH is the initial number of moles of OH groups per

gram and nOH is the number of moles of OH groups per gram
at any moment of polyesterification. Since the stoichiometry
between COOH and OH groups is 1:1, the number of moles of
reacted OH groups at a given acid value is equal to the number
of moles of reacted COOH groups at the same acid value, and
is expressed as
NOH - nOH ) NCOOH - nCOOH

(12)

and eq 11 can be modified as

J)

NCOOH - nCOOH
NOH

(13)

where NCOOH is the initial number of moles of COOH groups

per gram and nCOOH is the number of moles of COOH groups
per gram at any moment of polyesterification.
3.1.2. Probability Factor K. Two of the OH groups in a
branching unit are always used in forming a linear molecule.
Therefore K can be expressed as
K)

2(Ngly + Npen)
NOH

(14)

where Ngly is the initial number of moles of free glycerol per

gram and Npen is the initial number of moles of free pentaerythritol per gram.
3.1.3. Probability Factor L. Since glycerol contributes one
OH group and pentaerythritol contributes two OH groups for
branching, the factor L can be expressed as
L)

Ngly + 2Npen
NOH

(15)

3.1.4. Probability Factor R. The average functionality at

any moment is defined as the ratio of the total number of moles
of OH and COOH groups to the total number of moles of all
the molecules, and can be expressed as
Fav )

nOH + nCOOH
n

(16)

The average functionality (Fav) of molecules in a mixture of

dicarboxylic acid and dihydroxy derivatives like monoglycerides
is exactly 2; hence such a mixture forms entirely linear alkyd
molecules without forming a gel. On the other hand, polyols
having more than two OH groups react with dicarboxylic acid
to form linear polymer molecules consisting of unreacted OH
groups. In such a system Fav is greater than 2 and branching
occurs due to the presence of these free OH groups in polymer
backbones. Hence the probability of generating a linear polymer
molecule in a polyesterification system is assumed to be 2/Fav.
Therefore, the probability factor R is expressed as

8558 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008

R)

2
2n
)
Fav nOH + nCOOH

(17)

moles of COOH groups per gram of the reaction mixture at a

given acid value (AVx) is given by

The total number of molecules in the polyesterification

mixture at any moment of polyesterification, n, is given by
n ) N - (nest + 1) + 1

(18)

where nest is the number of moles of ester bonds per gram of

the reaction mixture at any moment of the polyesterification,
and is given by
nest ) NCOOH - nCOOH

(19)

Substitution of eqs 12, 18, and 19 in eqs 16 and 17 gives the

alternative forms of these equations as
(NOH - NCOOH) + 2nCOOH
Fav )
N - NCOOH + nCOOH
R)

2(N - NCOOH + nCOOH)

NOH - NCOOH + 2nCOOH

2(N - NCOOH + nCOOH)

NCOOH - nCOOH
KL
NOH
NOH - NCOOH + 2nCOOH

(22)

nCOOH(max) )
Substituting for nCOOH(max)
AVmax )

AVmax

5.61 104
and rearranging eq 27 yields

(29)

AVmax )

5.61 104
[(NCOOH - NOH) +
2
(NCOOH + NOH)[(NCOOH + NOH) - 2N] ] (31)

Further, the average functionality Fav(max) at ) max can

be obtained from eq 20 as
Fav(max) )

(24)

Note that varies only with Q as N, NOH, and NCOOH are

characteristic constants for a given alkyd recipe. At ) max
the branching becomes significant and, therefore, by equating
the first derivative of to 0, the corresponding Qmax can be
found:
Qmax )
+(NCOOH + NOH) ( (NCOOH + NOH)[(NCOOH + NOH) - 2N]
(25)
2
Since Q ) NCOOH - nCOOH, Qmax can be expressed as
Qmax ) NCOOH - nCOOH(max)

Hence the acid value at ) max, AVmax, can be calculated

from

Since the acid value is always positive, the negative result of

eq 30 is ignored and the equation becomes

3.2. Significance of max. As explained in section 2.2, the

probability factor varies with the extent of polymerization,
which is a direct function of the acid value (see Figure 2). Note
that the term NCOOH - nCOOH in eq 23 is a measure of the
number of ester bonds formed at any moment (see eq 19). By
assigning Q and C for the terms NCOOH - nCOOH and 2KL/NOH,
respectively, eq 23 can be modified as
C(-Q2 + NQ)
NOH + NCOOH - 2Q

(28)

(21)

(2KL/NOH)[NCOOH - nCOOH][N - (NCOOH - nCOOH)]

NOH + NCOOH - 2(NCOOH - nCOOH)
(23)

5.61 104

(20)

Rearranging eq 22 gives
)

AVx

5.61 104
[(NCOOH - NOH) (
2
(NCOOH + NOH)[(NCOOH + NOH) - 2N] ] (30)

Since K and L are constants for a given recipe, substituting

for J using eq 13 and R using eq 21, in eq 10 yields a
mathematical expression for as
)

nCOOH )

(26)

where nCOOH(max) is the total number of moles of COOH groups

per gram at ) max.
Substituting for Qmax in eq 25 yields
nCOOH(max) )
(NCOOH - NOH) ( (NCOOH + NOH)[(NCOOH + NOH) - 2N]
(27)
2
The acid value is the required number of moles of KOH to
neutralize the COOH groups per gram; hence the number of

(NOH - NCOOH) + 2nCOOH(max)

N - NCOOH + nCOOH(max)

(32)

Substituting for nCOOH(max) from eq 29 yields

Fav(max) )

(5.61 104)(NOH - NCOOH) + 2(AVmax)

(5.61 104)(N - NCOOH) + AVmax

(33)

3.3. Prediction of Gel Point. The polymerization reaction

forms two types of molecules: linear and branched. The
formation of linear molecules predominates at the beginning
of the reaction until the acid value decreases to AVmax, and the
branching becomes significant once AVmax is reached. If the
total number of molecules per gram at AVmax is Nmax and if all
the molecules are assumed to be taking part in the reaction at
the moment of gelation, then the number of ester bonds formed
during the period from AVmax to AVgel is Nmax - 1 and the
number of reacted functional groups is 2(Nmax - 1).
The number of functional groups reacting during the period
from AVmax to AVgel as a fraction of the total number of
functional groups available at ) max is used to denote the
extent of reaction, X, during the period from AVmax to AVgel,
and is given by
X)

2(Nmax - 1)
nOH(max) + nCOOH(max)

(34)

Since Nmax is very much greater than 1, eq 34 further simplifies

to
X)

2Nmax
nOH(max) + nCOOH(max)

(35)

Using eq 16, the average functionality at ) max can be

expressed as
Fav(max) )

nOH(max) + nCOOH(max)
Nmax

(36)

where nOH(max) and nCOOH(max) are the number of OH groups

and number of COOH groups respectively at ) max.

Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008 8559
Table 2. Average of Absolute Differences of Model Data from
Actual Data
model
average of
absolute variation

Carother Wiedehorn Flory Stockmayer proposed

13.6

5.5

25.1

11.3

4.1

Comparing eqs 35 and 36, a simple relation between the

extent of reaction during the period from AVmax to AVgel and
the average functionality at ) max can be obtained as
X)

2
Fav(max)

(37)

The extent of a polyesterification reaction is generally

expressed in terms of acid value; hence the extent of reaction
during the period from AVmax to AVgel is expressed as
X)

AVmax - AVgel
AVmax

(38)

A final equation relating the acid value at the gel point to

AVmax and Fav( max) can be obtained using eqs 37 and 38 and is
given by

AVgel ) AVmax 1 -

2
Fav(max)

functional groups such as the OH groups in glycerol have

unequal reactivity due to the effects of steric hindrance.
Stockmayer included the ring formation effects in deriving his
model. The over- and underestimations of the ring formation
effects might have caused the observed positive and negative
results of the predicted acid values. Table 2 shows that the
Wiedehorn model is in good agreement with experimental final
acid values. This suggests that his assumption for the number
of cross-links per polymer molecule, 1.5, was in close agreement
with the actual average of the number of cross-links per
molecule for synthesizing alkyd resins.
Table 2 indicates that the proposed model gave lower
deviations from actual acid values observed at the gel point for
polyesterification reactions in the synthesis of alkyd resins. A
comparison of the proposed model with the Wiedehorn model
which gave the lowest deviations from actual values is shown
in Figure 3. These results suggest that the new model is useful
in predicting the acid values at the gel point for the polyesterification reactions in synthesizing alkyd resins. However, further
study is required to examine the validity of the new model for
other polymerization reactions.
5. Conclusion

(39)

The values of AVmax and Fav(max) can be calculated from eqs

31 and 33, and therefore eq 39 predicts the acid value at the
gel point of a polyesterification reaction in the synthesis of alkyd
resins.
4. Comparison of the New Model with Existing Models
The experimental data published in the literature 18-21 were
used to evaluate the mathematical models available for predicting the onset of gel point in the synthesis of alkyd resins,
including the proposed model. The mathematical models used
in the analysis were the Carother model, the equation for the
lower limit gel point, the equation for the upper limit gel point,
the Flory equation, the Stockmayer equation, and the Wiedehorn
equation. The extent of polymerization of the experimental data
used in this analysis was found to be above 94%. Therefore
the actual acid values at the gel point corresponding to each of
these recipes were assumed to be just below the experimentally
observed final acid values. Table 1 shows the actual data of
both single oil systems and oil blends available in the literature
with calculated acid values at the gel point using different types
of models. Table 2 shows the average values of the absolute
differences between the calculated and actual data for each
model. The majority of the predicted values calculated using
the models of the lower limit gel point and upper limit gel point
(eqs 2 and 3) were negative. Hence the predicted data from
these two models were not included in Table 1. The models of
Carother, Flory, and Stockmayer are widely used in predicting
the gel points of polymerization reactions due to their simplicity
and applicability to a wide variety of polymers. However, the
predicted values using these models deviated considerably from
the actual values for the polyesterification reactions in the
synthesis of alkyd resins (see Table 2). The possible reasons
for these deviations are discussed below.
The Carother model was based on the assumption that Mn
reached infinity at the gel point. However, in reality, Mw reaches
infinity before Mn. Further, Carother did not consider effects
other than initial functionality, such as structural changes during
the polymerization and side reactions. Flory assumed equal
reactivity of functional groups in deriving his model. However,

The new model gave better predictions of acid values at the

gel point than the existing models for the polyesterification
reactions in the synthesis of alkyd resins. Since the new model
was developed on the basis of the availability of OH groups in
the polymer backbone during the polyesterification stage of the
manufacturing of alkyd resins, further study is required to
examine its applicability for other polymerization reactions.
Nomenclature
AVini ) initial acid value of the polyesterification of alkyd resin
AVx ) acid value at any moment
AVmax ) acid value at ) max
AVgel ) acid value at gel point
Fav ) average functionality at any moment given by ratio of total
moles of OH and COOH to total moles of molecules
Fav(max) ) average functionality at ) max
J ) fraction of reacted moles of OH groups at a given acid value
to initial moles of OH
K ) OH groups in branching units which contribute to place them
in segmental positions of polymer backbones expressed as a ratio
to initial moles of total OH groups
L ) ratio of branch generating OH groups to total moles of OH
groups
N ) total number of moles of molecules per gram of reaction
medium before starting polyesterification
NCOOH ) initial moles of COOH groups per gram
NOH ) initial moles of OH groups per gram
Ngly ) moles of free glycerol per gram of reaction medium before
starting polyesterification
Npen ) moles of free pentaerythritol per gram of reaction medium
before starting polyesterification
Noil ) initial moles of oil per gram
Nmax ) total number of molecules per gram at max
n ) total number of moles of molecules per gram of reaction
medium at any moment after starting polyesterification
nCOOH ) total moles of COOH groups per gram at any acid value
after starting polyesterification
nCOOH(max) ) total number of moles of COOH groups per gram at
max
nCOOH (max) ) total number of COOH groups per gram at max

8560 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008
nest ) number of moles of ester bonds per gram at a given acid
value after starting polyesterification
nOH ) total moles of OH groups per gram at any acid value after
starting polyesterification
nOH (max) ) total number of OH groups per gram at max
R ) probability of availability of linear polymer molecules in
reaction mixture
X ) functional groups reacted during polyesterification reaction
from AVmax to AVgel as a fraction of total number of functional
groups at max
Greek Symbols
) probability of having free OH groups in backbone of linear
alkyd molecule
max ) maximum value of for a given recipe of making alkyds

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ReceiVed for reView April 7, 2008

ReVised manuscript receiVed August 11, 2008
Accepted September 3, 2008
IE8005534