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Unsaturated polyester resins based on rosin maleic anhydride adduct as

corrosion protections of steel

Article  in  Reactive and Functional Polymers · July 2007

DOI: 10.1016/j.reactfunctpolym.2007.04.001

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 REACTIVE
&
FUNCTIONAL
Reactive & Functional Polymers 67 (2007) 617–626
POLYMERS
www.elsevier.com/locate/react

Unsaturated polyester resins based on rosin maleic

anhydride adduct as corrosion protections of steel
Ayman M. Atta a,*, Ibrahim F. Nassar b, Hamed M. Bedawy a
a
Egyptian Petroleum Research Institute, Nasr City 11727, Cairo, Egypt
b
Faculty of Specific Education, Ain Shams University, Cairo, Egypt

Received 10 July 2006; received in revised form 11 December 2006; accepted 2 April 2007
Available online 19 April 2007

Abstract

Unsaturated polyester resin (UP), based on 1 mol maleopimaric adduct (MPA), 1 mol maleic anhydride, 1 mol isoph-
thalic acid, 1 mol adipic acid, 1 mol propylene glycol, and 1 mol diethylene glycol, were obtained at various times during
polyesterification. They were characterized by 1H NMR and chemical titration. Increasing the reaction time to 8 h led to
an increase in (a) the number-average molar mass (Mn), (b) the glass transition temperature (Tg) and (c) the compatibility
with styrene. Several of these fractions were cured with styrene, in amount of UP/ST = 2.5 (weight of styrene, ST, and
unsaturated polyester, UP), using initiator and activator. The curing behaviors of cured UP resins with styrene were eval-
uated by DSC measurements. The prepared UP curable resins were evaluated in the field of steel coating by measuring
their mechanical properties and chemical resistance. The corrosion resistance of cured films was evaluated using salt
fog resistance test.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Unsaturated polyesters; Styrene/UP ratio; Chemical resistances; Glass transition temperature; Salt spray resistance

1. Introduction processed over a wide temperature range to form

Unsaturated polyester resins (UP) are one of the
widely used thermoset polymers in polymeric com-
posites, because of their good mechanical properties
and relatively inexpensive prices. The curing reac-
tion is a free radical polymerization of C@C double
bonds present in the UP resin and in an unsaturated
solvent which is usually styrene. With the addition
of one of the fillers and glass fibers, the resins are
*
Corresponding author. Tel.: +20 22747917; fax: +20
22747433.
E-mail address: khaled_00atta@yahoo.com (A.M. Atta).
sheet-molding compounds. They possess a wide
range of properties and are used in marine, automo-
bile, construction, sport, and furniture applications.
In these applications reinforcing glass fibers are
embedded in the unsaturated polyester matrix.
Also, other components such as fillers, additives,
and pigments may be present [1].
Rosin has been developed as a feedstock for syn-
thesis of various chemicals and intermediates for
polymers. There have been some reports regarding
the use of rosin maleic anhydride and acrylic acid
in polymer synthesis [2–4], a mixture of rosin,
maleic anhydride and acrylic acid along with some

1381-5148/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2007.04.001
618 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626
other chemicals were reacted together to obtain a
polymer, or the acrylic acid modified rosin was used
and not the pure adduct of rosin acrylic acid. In
some patents [5–9] these adducts were used for the
production of alkyl and polyester resins or as a
paper sizing agent. However, there was no detailed
report about the synthesis and characterization of
the polyester and polyamides obtained from the
adducts. In this respect, we have designed both
UP resins and hardeners based on aliphatic and
cycloaliphatic systems to produce cured UP resins
that have good durability with excellent mechanical
properties. The aim of this work was to use the rosin
as potential raw materials for the production of UP
and vinyl ester resins as coatings due to its low price
and ability to modify its chemical structures. In
order to fulfill these goals, three steps were distin-
guished. We therefore report now the synthesis
and characterization of unsaturated polyester resins
obtained by the reaction of rosin maleic anhydride
adduct with maleic anhydride and ethylene or pro-
pylene glycol. On the other hand, curing measure-
ments and evaluation of the prepared UP resins
using styrene and different weight ratios of vinyl
ester resins derived from rosin as corrosion protec-
tion for steel are another goals of the present works.
2. Experimental
2.1. Materials
All materials were used without further purifica-
tion. Rosin with acid number 183 mg KOH g 1 was
used. Acrylopimaric acid (APA) and maleopimaric
acid (MPA) adducts were synthesized and purified
according to the known method [10,11]. Diacrylate
and dimethacrylate vinyl ester resins based on rosin
acid MPA were prepared as reported in previous
work [12]. The diacrylate and dimethacrylate resins
were designated as AEMPAE and MEAMPAE,
respectively. Maleic anhydride (MA), acrylic acid
(AA), ethylene glycol (EG), triphenyl phosphite,
epichorohydrine (EC), styrene (ST), P-toluenesulf-
onic acid monohydrate (PTSA) and organic sol-
vents were analytical grade products and were
analytical grade products (Aldrich Chemical Co.).
Methyl ethyl ketone peroxide (MEKP) and cobalt
octoate (Co) were used as initiator and accelerator,
respectively. MEKP was supplied as a 50% paste in
dimethyl phthalate. The Co was a 10% solution in
styrene (ST).
2.2. Technique
2.2.1. Synthesis of unsaturated polyester of rosin
The unsaturated polyester (UP) having different
chemical structure was obtained. MA was added
at the ratio of OH/COOH 1.1/1 (mol/mol). The
UP resins were prepared by reacting 1.1 mol of gly-
cols, such as EG, PG with 0.35 mol of MPA,
0.35 mol of MA and 0.35 mol of saturated aromatic
and aliphatic acids, such as adipic acid and phthalic
anhydride. The polyesterification reactions were
carried out under a slow stream of dry nitrogen
gas. The reactants were heated from room tempera-
ture to 180 °C in about 1.5 h. The temperature was
then persevered at 180 °C for about 3 h and finally
raised to 200 °C and maintained till the expected
water quantity was removed. The extent of reaction
was followed by monitoring the water volume as a
cool under nitrogen to 60 °C or just below. About
1000 ppm of hydroquinone is added as inhibitor
to avoid the polymerization of the product.
The unsaturated polyester resin (UP) was dis-
solved in adequate amount of CH2Cl2 and then an
equal volume of distilled water was added to reac-
tion products. The mixture was shacked by means
of a flask shaker for half an hour and it was then left
to separate. The organic layer was separated and the
solvent was evaporated by means of a rotary evap-
orator. The purified samples were placed in a vac-
uum oven and weighed at intervals of time until
constant weight was attained for the sample. The
polyester was viscous liquids having dark yellow
to pale brownish color.
2.3. Measurements
The hydroxyl and acid values of the synthesized
resins were determined by the conventional acetic
anhydride/pyridine method as reported in the previ-
ous work [10,11].
Infrared spectra of the prepared compounds were
recorded in polymer/KBr pellets using Mattson-
Infinity series FTIR Bench Top 961.
1
H NMR spectra of prepared resins and polyam-
ide hardeners were recorded on a 270 MHz spec-
trometer W-P-270 & Y Bruker. The solutions for
1
H NMR analysis were prepared by dissolving the
prepared compounds in CDCl3.
Transition temperature of epoxy binders was
measured with DuPont 2100 differential scanning
calorimeter at heating rate of 10 °C/min. Dynamic
curing was performed in DSC to observe the curing
 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626
behavior of epoxy binders. Dynamic curing was per-
formed at a heating rate of 20 °C/min.
2.4. Testing of the coatings
It is common to use mild steel panels (15 cm 
10 cm) to evaluate the different properties of coat-
ings. The panels are prepared according to British
standard specification 1449. The other side of panels
is coated and protected against corrosion environ-
ments by using coal tar epoxy primer.
Chemical resistance of organic coatings was eval-
uated from hot water resistance, solvent resistance
and salt spray resistance according to ASTM of
organic coatings. The coated panels were evaluated
for salt-spray resistance in accordance with ASTM
B117. The results of the salt-spray tests were evalu-
ated by two methods. One method was to measure
the area of disbonding around the scribed X. The
other method was to evaluate the disbonded area
in the lower half of the test panel in accordance with
ASTM D1654 rating system.
The acid and alkali resistances of coated panels
were determined after immersion in 10% of HCl
and 5% of NaOH aqueous solutions using distilled
water. The duration of the test was 90 days at
38 °C. The degree of adhesion and visual inspection
of blister and cracks were tested for the coated
panels.
3. Results and discussion
Using the rosin offers the possibility of a lower
cost source for production of curable resins. The
present study was intended to evaluate the mechan-
ical characterization of UP and vinyl ester resins
from rosin maleic anhydride adduct. In previous
publications [10–12], we have prepared UP and
VE resins from rosin. In this respect, VE resins were
prepared from rosin maleic anhydride adduct,
MPA, using EG and the reaction of its product with
epichlorohydrine, EC, to produce epoxy resin. The
epoxy resin was reacted with either acrylic or meth-
acrylic acid in presence of triphenyl phosphite to
produce vinyl ester resins having acrylate or meth-
acrylate end groups. The prepared vinyl ester resins
based on acrylic and methacrylic acid were desig-
nated as AEMPAE and MEMPAE, respectively.
On the other hand, UP was prepared from conden-
sation of MPA and MA with EG or PG by fusion
method [11,12]. The MPA adduct was purified and
condensed with maleic anhydride and ethylene gly-
619
col to produce UP. More details on methods of syn-
thesis, purification and characterization were
described in details in previous publications [11–
13]. The present work is intended to prepare UP
and vinyl ester resins from MPA to use in coating
applications. Tong et al. [13] found that unsaturated
polyesters based on bis(2-hydroxyethyl)-terephthal-
ate, maleic anhydride and ethylene glycol were not
compatible with styrene monomer. It was found
that, the replacement of the ethylene glycol by
another type of glycol enhances the compatibility
of the products with styrene monomer. In the pres-
ent study MPA and PG were incorporated in the
vinyl ester to increase the miscibility of the synthe-
sized resins with styrene monomers. Schulze et al.
[14] have reported on the modification of unsatu-
rated polyesters by poly(ethylene glycol) end groups
in order to modify its solution behavior in styrene
and to modify the mechanical properties of the
cured resin. It was found that the conversion of
the typical polar end groups to poly(ethylene glycol)
end groups improved the flexibility of the cured
material. Accordingly we presumed that the incor-
poration of rosin into the structure of the vinyl
esters will enhances their solubility in styrene mono-
mer. On the other hand, MPA and PG were used to
modify the chemical structure of the prepared UP
resins to modify both mechanical and chemical
resistances of cured resins.
3.1. Preparation of curable resins from MPA adduct
In previous article [12], vinyl ester resins based on
rosin were prepared from rosin adducts using rosin
acid as diene and maleic anhydride (MA) or acrylic
acid (AA) as dienophile. The produced adducts
maleopimaric and acrylopimaric adducts MPA
and APA were used to prepare vinyl ester resins.
The chemical structures of the resulting vinyl ester
resins were confirmed by 1H NMR analysis. The
prepared VE curable resins were evaluated in the
field of steel coating by measuring their mechanical
properties and chemical resistance. In the present
article, unsaturated polyester resins were prepared
from condensation of MPA, MA, PTH and AD
as dibasic acid with EG and PG as glycol. The
unsaturated polyesters under investigation are com-
posed mainly of three categories being, saturated
dibasic acids, unsaturated dibasic acids and glycols.
The resin is then diluted with vinyl or divinyl mono-
mers. The possible combinations of unsaturated
polyester and vinyl monomer permit a wide range
620 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626

of properties to be obtained. The selected resins

were designated as MPAUP1, MPAUP2,
MPAUP3, MPAUP4, MPAUP5 and MPAUP6
for which EG, EG–PTH, EG–AD, PG, PG–PTH
and PG–AD were used as glycols and saturated dia-
cid. The molecular weights of the prepared UP resin
were determined using end group analysis as
described in Section 2. Since methods of end group
analysis count the number of molecules in a given
weight of sample, they yield the number average
molecular weight for polydisperse materials. The
resultant molecular weights are listed in Table 1 in
conjunction with the acid number of the prepared
polyesters. End group in condensation polymers
usually involves chemical methods of analysis for
functional groups. Carboxyl and hydroxyl groups Fig. 1. IR spectrum of MPAUP1.
in polyester are usually titrated with a titrable
reagent. The degree of polymerization of the pre-
pared UP were calculated from molecular weight
of UP resins, which was calculated from hydroxyl
number and acid value, and are listed in Table 1.
Careful inspection of data indicates that the degree
of polymerization was increased with using PTH
and EG as glycol. On the other hand, the degree
of polymerization was decreased with using AD
and PG as glycol. This observation indicates that
the degree of polymerization values was reduced
with decreasing the molecular weight of the used
dibasic acid. This observation runs in harmony well
with the conclusion drawn in the work based on
polycondensation of saturated dibasic acid with
EG [13].
The chemical structure of the prepared UP was
elucidated by IR and 1H NMR analyses. In this
respect, the IR spectrum of MPAUP1 was selected
and is represented in Fig. 1. While 1H NMR spec-
trum of MPAUP6 was selected as representative Fig. 2. 1H NMR spectrum of MPAUP6.
samples and is given in Fig. 2. The characteristic
bands in the IR spectra of UP are observed at
3450 cm 1 as sharp strong band (cOH end group), 1730 cm 1 as sharp strong band (cC@O in COO ester
group), 1470 cm 1 as sharp medium band (double
bond in hydrophenanthrene moiety) and
Table 1 1110 cm 1 as broad strong band (cCAO of ester
Molecular weight of the produced UP and their hydroxyl
numbers and carboxylic values
group). The disappearance of the bands characteris-
tic of cyclic anhydride group of MPA at 1780 and
Designation OH number COOH value Mn g/mol n
mg KOH g 1 mg KOH g 1
1850 cm 1 (cC@O of cyclic anhydride group) and
the appearance of bands at 1735 cm 1 (cC@0 sym
MPAUP1 10.1 17.6 4050 7
MPAUP2 12 7.5 5753 7
in ester), 1710 cm 1 (cC@0, sym of COOH) indicate
MPAUP3 8.5 10 6064 8 that the esterification of MPA was completed by
MPAUP4 17 13 3740 6 reaction of carboxylic group OH group of EG or
MPAUP5 10.8 12.8 4754 5 PG. The IR spectra of all UP based on PTH show
MPAUP6 13.1 8.5 5194 7 bands at 1580 and 1555 cm 1 correspond to aro-
 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626 621

matic cC@C stretching vibrations. The 1H NMR peratures of the heated resins from 25 to 285 °C fol-
spectra of UP, show signals at d 6.8 and 2.5 ppm lowed by cooling to 25 °C are reported as Tg2. The
which assigned to unsaturation system of change in Tg value was determined as the differences
MA(C@C), and –OH of terminal alcoholic glycol, between Tg1 and Tg2. DSC thermograms of
respectively. The signals at 2.18–2.98 ppm are MPAUP1 was selected as representative cured
assigned to (–CH2 ester). These bands were UP/styrene resins and plotted in Fig. 3. The glass
observed in all spectra of MPAUP1 and MPAUP2, transition of these UP resin systems were measured
The band at 0.9 ppm for MPAUP3 spectrum, –CH3 by DSC as indicated in Table 2. The initial scan was
of propylene glycol, indicates that the glycol used in performed to 150 °C and the Tg was taken as the
MPAUP3 is propylene glycol. The spectra of UP onset of the baseline change. The second scan was
containing PTH show a complicated aromatic pro- conducted to 280 °C and was used to check for pos-
ton signals multiplet at 7.8 ppm. sible increases in Tg. Using this method, we were
able to determine that the glass transition tempera-
3.2. Curing DSC measurements tures of the resin systems before and after Post-cure.
It was observed that the data of Tg of the UP resins
Several methods based on data of dynamic also increased during post-cure. This phenomenon
mechanical analysis (DMA) [15,16] rheological was observed and has attributed it to an increase
measurement, near infrared analysis [17] and ther- in molecular weight due to uncontrolled chain
mal differential scanning calorimetry (DSC) were
used to study the curing kinetic mechanisms. The
reactivity of resins to be cured, and the properties Table 2
DSC thermal characteristics of cured UP resins with styrene
of the end products, affects the choice of curing sys-
tem. The type and concentration of curing agents Designation Tg1 (°C)a Tg2 (°C)b DTg (°C)
may be able to control the length of cross-links MPAUP1 85.21 94.18 8.97
(cross-link density), and consequently the mechani- MPAUP2 115.5 130.3 14.8
MPAUP3 108 146 38
cal properties of the cured resins. In the present
MPAUP4 80.12 86.62 6.5
work we have used DSC measurements to evaluate MPAUP5 100.93 108.24 7.31
the curing exotherms of the prepared UP resins with MPAUP6 95.3 110.3 15
styrene as curing agents. In this respect, the cured a
Glass transition temperature of the first run (from 25 to
UP resin samples were heated and scanned from 150 °C).
25 to 150 °C and then immediately cooled at b
Glass transition temperature of the second run (from 25 to
25 °C. Tg values are reported as Tg1. While the tem- 285 °C).

Fig. 3. DSC thermal characteristics of cured MPAUP1.

622 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626
extension, and to the removal of solvent [18]. Tg of
the polymer is important for the intended applica-
tion. This transition temperature is defined as being
the temperature or range of temperature at which
the polymer passes from a hard and often brittle
stage (glass) to a resistant stage of the rubber type.
The applicable Tg values were determined from
the points of intersection of the extrapolated base-
line at the low temperature end and the tangents
to the curve at the inflection point and determine
the applicable exothermic heats of reaction (D H).
Careful inspection of Tg data of the prepared UP
resins reveals that the cured resins have low values
than 100 °C except UP resins based on PTH. This
can be referred to introducing of PTH groups will
induce some rigidity in the resin backbone. The Tg
of polymeric system has multifunctional dependence
on the micro-structural characteristics of high
molecular weight macromolecules [18,19]. The
higher Tg values are related to strong dipolar inter-
action between side substituents of the polymeric
chain. While, the glass transition temperature of
low molecular weight compounds depends on the
intermolecular interaction of individual molecules
exclusively, being controlled by the molar volume
and dipolar connectivity, hydrogen bonds, and
Van der Waals interactions between molecules. This
was observed in the UP resins based on AD that
posses lower Tg values. This was refereed to the
introduction of AD as aliphatic group will intro-
duce some flexibility as well as PG in the structure
of UP resins. On the other hand, almost UP resins
have high Tg2 values more than 100 °C which indi-
cate that the probability for formation of highly
cross-linked polymers was increased with increasing
the temperature. Increasing Tg2 above 100 °C indi-
cates that polystyrene, PS, can be obtained as
homopolymer. The probability for formation of
PS was decreased with introducing of PG in the
structure of MPAUP4. Careful inspection of data
listed in Table 2 reveals that the UP resins possess
different DTg values. It is well-known that low DTg
indicates higher curing of resins. The lower DTg val-
ues were observed when PG was incorporated with
UP instead of EG. This indicates that the reactivity
of the ST towards prepared UP resins based on PG
is much higher than UP resins based on EG at
higher temperatures. It was also observed that the
cured UP resins with PG have lower Tg2 values than
that based on EG. This can be attributed to the
higher cross-link density resulting from reaction of
UP resins based on PG with styrene curing agent
[20]. These observations agree to the results
obtained for curing exotherms of UP/styrene resins
at different temperatures. Accordingly, we can con-
cluded that the cured UP/styrene resins have high
cross-link densities when PG, MPA and AD were
incorporated in UP resins. The lower DTg values
were observed when MPA, PG were incorporated
with UP instead of EG. This indicates that the reac-
tivity of the ST towards prepared UP resins based
on MPA and PG is much higher than UP resins
based on MPA and EG at higher temperatures.
On the other hand UP resins based on MPA have
higher Tg2. This indicates that the cured UP/styrene
resins based on MPA have a tendency to form dan-
gling styrene chains which are not complete cured.
3.3. Evaluation of cured resins for coating
applications
Durability of coats may be defined as the capac-
ity of paint to endure; that is, to remain unchanged
by environment and events. Effects of environmen-
tal conditions have an enormous effect on durabil-
ity, and test methods for developing and
monitoring the performance of coating systems are
always designed to simulate conditions of usage.
They are usually designed to accelerate the degrada-
tive processes to which coatings are subjected. The
reason for this acceleration of the degradation pro-
cesses is to provide early warning of coatings failure.
There are two types of test methods to evaluate the
durability of coatings chemical resistance test and
mechanical tests. In the present work, we have dis-
cussed the chemical resistance test as described in
Section 2. In this respect, the coated panels have
subjected to chemical environments (alkali, acid,
solvent and salt spray) to study the durability of
coats. In this respect, the resistance to the corrosive
environments was assessed using the procedure out-
lined in ASTM C581-94 as explained in Section 2.
The initial appearance of the panels was affected
by the cure conditions. With exposure to the media,
the appearance of all the panels changed to show
color changes, and blistering. The observations at
3 months are summarized in Table 3. The data of
alkali-, acid-, solvent-resistance and water resistance
were determined for cured resins and are listed in
Table 3. The sign ( ) indicates failure of tests, while
(+) sign indicates the coatings pass the tests. The
failure of test indicates that the coating films losses
their adhesion with panels and show cracking and
flaking of the film. The reason for coating failure
 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626 623

Table 3
Chemical resistance tests of UP cured with AEMPAE and MEMPAE at different mixing ratios
Cured network (%) Acid resistance Alkali resistance Water resistance Solvent resistance Acetone test
5 10 15 20 5 10 15 20 5 10 15 20 (5–20)a (5–20)a
MPAUP1 10 60 20 15 5 30 10 5 + + + + + +
MPAUP2 5 60 25 20 5 30 10 5 + + + + + +
MPAUP3 10 60 30 30 7 40 10 10 + + + + + +
MPAUP4 30 60 60 60 15 60 30 10 + + + + + +
MPAUP5 45 60 60 60 30 60 40 30 + + + + + +
MPAUP6 30 60 25 20 5 30 10 10 + + + + + +
MEMPAE
MPAUP1 5 30 10 5 3 20 7 4 + + + + + +
MPAUP2 4 30 10 5 3 20 7 4 + + + + + +
MPAUP3 5 50 15 10 3 30 7 7 + + + + + +
MPAUP4 20 50 40 40 7 40 20 15 + + + + + +
MPAUP5 20 50 40 40 10 40 25 20 + + + + + +
MPAUP6 15 40 20 15 2 20 7 2 + + + + + +
a
Weight percentage of AEMPAE and MEMPAE.

are legion nevertheless some reasons for failure are
readily identifiable, and attempts can be made to
compact them. The use of polar solvents such as
ketones is often used to assess the degree of cure
of a cross-linked composition for solvent resistance,
methyl isobutyl ketone or acetone is recommended.
In addition to immersion testing, solvent resistance
may be assessed by a solvent rub test. In this
respect, acetone has used to determine the degree
of curing of the present coating systems by both
immersion and rub methods. The failure of tests
was determined either by disruption or dissolution
of the coating films from panels. Generally, solvent
resistance depends primarily on polarity of cured
network resins. Non-polar polymers show solvent
resistance to water, acetone and other polar sol-
vents, whereas polymers containing sites for hydro-
gen bonding are most affected by moisture humidity
and polar solvent. Moreover, the molecular weight
and cross-link density of polymer networks are
directly related to its resistance to solvent attack.
This is due to the thermodynamic relation between
polymer network structures and solvent [21].
Cross-linking is the ultimate structural factor in pre-
venting a polymer from dissolving in a solvent.
Although this cannot eliminate the effects of polar-
ity and hydrogen bonding, it raises molecular
weight to the size of an infinite network, preventing
‘‘individual” polymer chains from dissolving in the
solvent. The higher the degree of cross-linking indi-
cates the less free volume and segmental mobility
remain available in the polymer. So that solvent
molecules can hardly penetrate the cross-linked net-
work at all. The cross-link density can be controlled
by change type of curing agents and functionality of
UP resins [22]. In this respect, it was found that the
all prepared UP resins based on MPA have good
solvent and hot water resistance with all mixing
ratios with AEMPAE and MEMPAE. This can be
attributed to increasing of cross-link density of UP
although the UP polarity is increased by increment
of UP molecular weights. The high solvent resis-
tance of the cured UP systems indicates that all
cured UP resins have high cross-link density net-
works [23].
Most conventional structural materials are sub-
ject to severe attack by many aqueous acids and
bases, most organic polymers are relatively resis-
tant to these corrosive environments. Polyesters,
polyamides, and polyurethanes may be hydrolyzed
by acid or alkaline catalysis [24]. The data of acid
and alkali resistances indicate that there is some
change on color and weight when plaques are sub-
jected to sodium hydroxide, HCl or H2SO4 during
period of 90 days. This can be referred to low
cross-linking density UP/styrene resins which
increases the exposure of polar groups of network
to environments. On the other hand incorporation
of both AEMPAE and MEMPAE as curing agent
for UP/styrene system increases acid and alkali
resistances of cured resins. This can be attributed
to high cross-link density of network decreases
their exposure to environment [23]. It was also
noticed that, the acid and alkali resistances of
cured UP resins were increased when AEMPAE
used as cross-linker instead of MEMPAE. This
624 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626

can be refereed to formation of dangling chains Table 4

when MEMPAE used as cross-linker for UP resins, Salt spray resistance of cured UP styrene resins
as explained in curing exotherm measurements, Sample no. Exposure time (h) Disbonded ASTM ratinga
which increase exposure of cross-linked network area
to acidic and alkaline media. Careful inspection cm2 %
of data, Table 3, indicates that increasing MEM- MPAUP1 300 18.3 15.8 5
PAE and AEMPAE cross-linker concentrations MPAUP2 300 13 11 6
up to 10 wt% increases acid and alkali resistance MPAUP3 300 18.3 15.8 5
MPAUP4 300 18.3 15.8 5
and decreases when the concentration increases MPAUP5 300 7.1 6 7
from 15 to 20 wt%. This observation can be MPAUP6 300 13 11 6
referred to formation of high percentages of dan- a
ASTM Method, D1654-92.
gling chains when the concentrations of both
cross-linkers exceed 10 wt% which increase expo-
Table 5
sure of networks to acid and alkali solutions and
Salt spray resistance of cured UP styrene and 10 wt% of
consequently increases the hydrolysis of cured UP AEMPAE or MEMPAE resins
resins [25].
Sample no. Exposure time (h) Disbonded ASTM ratinga
area
3.4. Corrosion resistance of coating
cm2 %
MPAUP1 650 12.9 11 6
Salt spray tests are probably the most common
MPAUP2 650 7.1 6 7
tests applicable to corrosion resistance and the MPAUP3 650 7.1 6 7
most controversial. In the present work, the contin- MPAUP4 650 13 11 6
uous salt spray test was used, as described in Sec- MPAUP5 650 2.3 2 8
tion 2, to study the effect of salts on the MPAUP6 650 7.1 6 7
properties of coating films. In this respect, the MEMPAE
adhesion of substrate with coat is the main prob- MPAUP1 500 12.9 11 6
lem for coating failure. Cracking, flaking scaling MPAUP2 500 13 11 6
MPAUP3 500 12.9 11 6
or blistering due to under rusting (the latter often MPAUP4 500 13 11 6
being accompanied by brown discoloration of the MPAUP5 500 2.3 2 8
film) is due to mechanical action by the products MPAUP6 500 7.1 6 7
of corrosion. The most familiar corrosion of this a
ASTM Method, D1654-92.
type is the rusting of iron exposed to moist atmo-
sphere or water. The initial penetration of rust
through the protective coating film is based on
the coating constituents [26]. The coating constitu-
ents must be able to resist the transfer of ions
through the coating and be able to expand and
contract with the underlying surface over which it
is applied. These ions are chloride, sulfate carbon-
ate, or similar ions, which on penetrating the film
would start under film corrosion. In this respect,
the duration times of tests were determined for all
cured UP and 10 wt% of AEMPAE or MEMPAE
styrene systems and are listed in Tables 4, 5. The
panel of cured MPAUP4 after test duration was
selected and is represented in Fig. 4. The weight
percentage of 10% was selected in this test accord-
ing to previous section which indicates that per- Fig. 4. Salt spray resistance of MPAUP4 coatings.
centage is the most applicable to produce cured
resins without any deformation to mechanical dam- of coatings by using PG and PTH in the structure
age and high alkaline and acidic resistances. The of UP resins. On the other hand, incorporation of
results of salt spray indicate the strong adhesion AEMPAE vinyl ester resins instead of MEMPAE
 A.M. Atta et al. / Reactive & Functional Polymers 67 (2007) 617–626
in UP networks improves the coating performance
from 75 to 95% after 646 h of exposure to the salt
spray environment. Coating performance was con-
sistently improved for each exposure time for both
coatings. This can be attributed to relationships
between coating properties and performance. In
this respect water or dilute salt water are directed
to the coating, they are semi permeable mem-
branes, to which the principle of osmosis definitely
applies. If the steel surfaces contain chlorides, sul-
fates or other ions (on which the coating is applied)
will increase water penetration through the coating
and leads to blistering and coating failure. Strong
adhesion also prevents moisture vapor from pass-
ing through the coating and condensing in a poor
area of adhesion, leading to a blistering of coating.
This is of particular significance when it comes to
the choice of suitable coating systems. In our UP
systems, it was observed that increasing of MA
content of UP increases the adhesion of coat with
steel. This can be referred to the formation of
highly cross-linked network which prevents the
penetration of salt solution from coat to steel
[26]. The results of salt spray resistances agree with
the data reported for acid and alkali resistance.
Accordingly, the same discussion can be included
in this section. The results of salt spray results indi-
cate that the UP coatings pass 500 h without adhe-
sion failure can be used in petroleum pipeline,
tanker and marine coatings. Furthermore, cured
UP resins have excellent alkali, acid and solvent
resistance and provide a dense hard coating with
good adhesion can be used in linings for petroleum
tanks and tankers, salt barges and ships, general
chemical tankers, as well as exterior coatings for
the bottoms, boot-topping, and decks.
4. Conclusions
The following conclusions can be extracted from
the previous results:
1. Molecular weight data of UP indicate that the
degree of polymerization was increased with
using PTH and MPA as dibasic acids and EG
as glycol. On the other hand, the degree of poly-
merization was decreased with using AD and PG
as glycol.
2. DSC measurements indicate that UP resins based
on MPA, PG have lower DTg values than UP res-
ins based on EG. On the other hand UP resins
based on MPA have higher Tg2 which indicates
625
that the cured UP/styrene resins based on MPA
have a tendency to form dangling styrene chains
which are not complete cured.
3. DSC measurements indicate that the cured UP/
styrene resins have high cross-link densities
when PG and AD were incorporated in UP res-
ins. The acid and alkali resistances were
increased when PG and AD were used in prep-
aration of cross-linked networks. The acid and
alkali resistances were increased when AEM-
PAE was used as cross-linker instead of
MEMPAE.
4. Acid and alkali resistances can be referred to for-
mation of UP high cross-link density of networks
without formation of dangling chains.
5. UP and VE resins based on rosin adducts can be
used in linings for petroleum tanks, salt barges
and ships, general chemical tankers, as well as
exterior coatings for the bottoms, boot-topping,
and decks.
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