Progress in Organic Coatings 74 (2012) 608–614

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Synthesis and characterization of water borne intumescent fire retardant varnish

based on phosphate resin acid cold cured amino resin
Zhiling Ma ∗ , Jiangjiang Wang, Shu Chen, Xiaoying Li, Haiyun Ma
College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China

a r t i c l e i n f o a b s t r a c t

Article history: In this research, a water borne intumescent fire retardant varnish based on phosphate resin acid (PRA)
Received 31 July 2011 cold cured amino resin was synthesized. Infrared (IR) spectrum proved that PRA was from 1,4-butanediol
Received in revised form 14 February 2012 diglycidyl ether (BDE) and epoxy resin E-51 (E-51) via the reaction between epoxy group and P O H
Accepted 17 February 2012
of phosphate ester acid of N-butyl alcohol (BA) and pentaerythritol (PT). The introduction of BDE and
Available online 14 March 2012
E-51 improved water resistance and flexibility of painted film. The fire retardancy test demonstrated
that a higher phosphorus content is beneficial to the intrinsic fire retardancy of painted films, but the
Keywords:
high quality char formation is another key of fire retardancy of painted films. The TG and DTA proved:
Intumescent fire retardant coating
Phosphate resin acid cold cured amino
E-51 and PT are true carbon source that is beneficial to form a high quality charred layer, but their high
varnish combustion heat is detrimental to the intrinsic fire retardancy of painted film material. BDE is beneficial
Water borne to increase the intrinsic fire retardancy of painted film material, but detrimental to form a high quality
Ambient temperature curing charred layer. The conclusion also is showed directly by the scanning emission microscopy (SEM). To
Paint film achieve high performance painted film, all the components need to be balanced perfectly.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction According to the fire retardant mechanism, fire retardant coat-

Varnish is very important to protect the wooden furniture with
pretty patterns. However, the commonly used varnish itself and the
solvents are highly flammable. Moreover, the solvent can also cause
the environment pollution. Water borne fire retardant varnish can
not only protect wooden furniture against the fire but also goes with
the concept of low carbon (LC) [1,2]. Undoubtedly, it is an expected
ideal decoration material.
Traditionally, fire retardant can be divided into two types: the
additive type and reactive type. The additive type fire retardant
dominates the market because of its low price, high availability and
wide application. However, to achieve sufficient fire retardancy, a
high loading of additive type fire retardant is required. This not only
covers the pretty patterns of wooden, but also generally results in
the detrimental influence on the physical and mechanical proper-
ties of the coating [3–5]. The reactive type fire retardant is mainly
used to bond the fire retardant segments to the polymer backbone
[6]. Therefore, the reactive type fire retardant can make the polymer
into an intrinsic fire retarded material. Comparing with the addi-
tive type fire retardant, reactive type fire retardant is promising and
becoming a trend for the fire retarded painted films [7,8].
∗ Corresponding author.
E-mail address: zhilingma838838@163.com (Z. Ma).
ing can be classified into intumescent and non-intumescent. Some
non-intumescent fire retarded systems such as halogen contain-
ing fire retardant system may produce large amounts of smoke
and toxic gases when burning, and thus some of them have been
banned by the European Commission [9]. As to the halogen free
products, intumescent materials can form, by heating, a swelled
charred layer of cellular foam on the surface to provide resistance
to both heat and mass transfer, giving good heat insulation. They
are expected to be used in coatings and have attracted more and
more attention from many researchers [7,10,11]. Generally speak-
ing, an intumescent system consists of three main substances:
an acid source (e.g., phosphorus containing substance), a carbon
source (e.g., polybasic alcohol), and a gas source (e.g., nitrogen
containing substance) [12,13]. Intumescent fire retardant varnish
is prepared by combining the three main substances of intumes-
cent fire retardant (IFR) in the chemical structure of the painted
film. The most representative approach to prepare water borne
fire retardant varnish is to suggest two packs cross linking sys-
tems consisting of phosphate ester acid (PEA) and amino resin with
reactive groups. In this approach, after water evaporation, films
that consisting of phosphate/amino resin hybrid with interpene-
trating network (IPN)-like structure are formed [14]. These hybrid
films provided not only better hardness, gloss, weather ability and
chemical resistance via amino resins but also excellent fire retar-
dancy and toughness due to the organophosphorus compounds.
The main concern associated with these compounds is the synthesis

0300-9440/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2012.02.009
 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614
and acidity of PEA. Several approaches have been proposed for the
preparation of PEA. One approach is to synthesize PEA from alcohol
and POCl3 , by controlling the proportion of alcohol and POCl3 . As a
result, the main product could be phosphate diester acid or phos-
phate monoester acid that need two steps to generate, and HCl is
produced as a by product [15]. Another approach is to synthesize
PEA from P2 O5 and alcohol, in which the formation of phosphate
acid, phosphate monoester acid, phosphate diester acid and phos-
phate triester occurs at the same time. To achieve sufficient fire
retardancy, excessive PEA curing agent is normally required. How-
ever, excessive PEA will make the curing speed too fast to control.
Triethanolamine was used as the neutralizing agent to decrease
the curing speed. Nevertheless, triethanolamine reacted with PEA
and formed a water soluble salt [16]. So the introduction of tri-
ethanolamine into the system weakens the water resistance of the
coating.
The purpose of this study is to investigate a novel method to
synthesis a phosphate resin acid (PRA, an epoxy resin/phosphate
ester acid hybrid material) that can be used as curing agent at
ambient temperature to cure water borne amino resins forming
an intumescent fireproofing transparent film.
2. Experimental
2.1. Materials
Phosphorus pentoxide (P2 O5 , commercial grade) supplied by
Xiang-Fan Gaolong Phosphorus Chemical Co., Ltd. Epoxy resin E-51
(E-51, commercial grade) supplied by Shijiazhuang Kingdar Special
Coatings Co., Ltd. 1,4-Butanediol diglycidyl ether (BDE, commercial
grade) supplied by An-Hui Xinyuan Chemical Co., Ltd. Pentaerythri-
tol (PT, commercial grade) supplied by Jiang-Su Ruiyang Chemical
Co., Ltd. Melamine (M, commercial grade) supplied by Ji-Nan Taixin
Fine Chemical Co., Ltd. N-butyl alcohol (BA), Formaldehyde (F), Urea
(U), Magnesium carbonate (MgCO3 ) and Phthalic anhydride (PA)
were all analytically grade regent.
2.2. Synthesis of curing agent
PEA was prepared according to the following procedures. The
mixture of PT and BA was added into a four necked glass flask
equipped with a stirrer, a thermometer and a reflux condenser. The
P2 O5 was added in batches at 80–100 ◦ C, and then the temperature
was gradually increased to 140 ◦ C. The reaction lasted for about 4 h
until the acid value stopped decreasing. The PEA was ready for use.
PRA1–PRA3 were prepared by dropping the mixture of E-51 and
BDE into the above PEA system at 50 ◦ C. Then the reaction was con-
tinued for about 4 h. The water was added when the acid value
stops decreasing, and the stirring was continued for 30 min. The
solids content and acid value were tested respectively. The prod-
ucts were ready to be used. The specific components of products
are presented in Table 1.
2.3. Synthesis of melamine urea formaldehyde resin (MUF)
MUF was prepared according to the following procedure. A
500 ml four necked glass flask was equipped with a stirrer, a
thermometer, a reflux condenser and a dropping funnel; 0.17 g
magnesium carbonate and 150 ml formaldehyde were added and
heated to 65 ◦ C, then added the mixture of 34 g melamine and 15 g
urea. The reaction was continued at 80 ◦ C for 20 min. Then 0.20 g
phthalic anhydride and 156 ml BA were added, the reaction was
continued at 80 ◦ C for 1 h. After the pH value was adjusted to 8,
the solid content was adjusted by distilling part of water and BA at
609
50–60 ◦ C under reduced pressure. Then the MUF was obtained and
ready to be used.
2.4. IR analysis
FTIR analysis was performed on a THZ1-Nicolet-380 FTIR instru-
ment (Thermo Fisher Scientific) using a KBr disc, 500–4000 cm−1 .
2.5. Fire retardancy
A variety of fire retardancy evaluations of the painted films were
carried out as following. The data recorded was reproducible to
within ±10%. The data presented in figure and table is averages of
at least five experiments.
The varnishes are obtained by mixing curing agent and MUF
together with the solids content ratio 1:1.
2.5.1. The limited oxygen index (LOI)
The samples were coated on the glass fiber that acted as sup-
ports, with dimensions of 140 mm × 52 mm, and the ratio of the wet
coating was 250 ± 5 g/m2 . LOI value was measured by JF-3 oxygen
index meter according to the testing standard of Textiles-Burning
behavior (GB/T 5454-1997).
2.5.2. Cabinet method
The cabinet method tests were carried out according to GB
12441-2005 on a fire resistant paint tester (small room mode,
Guangzhou Sunho Fire test technology Co., Ltd.). The char index
and weight loss were determined.
2.5.3. Big panel method
The fire retardancy of the painted films was studied by simu-
lating big panel method. The five layers birch plywood panels with
dimensions of 200 mm × 200 mm, and the ratio of the wet coat-
ing was 400 ± 8 g/m2 . Center the panel, face down, on the supports
with the distance between the burner and the panel is 70 mm.
The thermocouple was fixed perpendicularly on the back of the
panel and kept in line with the flame center of gas lamp, and ignite
by means of a flame approximately 750 ◦ C. Then the temperature
changes versus time were recorded to draw the temperature–time
curve. The photographs of char residue fracture were obtained by
an IXUS220HS Canon camera.
2.6. Thermal analysis
The data of TG and DTA of the painted films was obtained using a
DTU-1A thermo gravimetric analyzer (Beijing Thermal Equipment
Factory, China). The samples were examined under air flow at a
heating rate of 10 ◦ C/min from room temperature to 800 ◦ C. The
masses of sample PEA/MUF, PRA1/MUF, PRA2/MUF and PRA3/MUF
were 5.9, 5.6, 6.1 and 6.3 mg, respectively. With the high purity
zinc as the standard, the relative value of heat release in different
temperature ranges were calculated by integral method and shown
in Table 4. Hi1 , Hi2 and Hi are the heat release of per gram sample in
200–400 ◦ C, 400–650 ◦ C and 200–650 ◦ C, respectively, i = PEA/MUF,
PRA1/MUF, PRA2/MUF and PRA3/MUF.
Hi1 Hi2
Ri1 = Ri2 =
Hi Hi
2.7. Measurements of mechanical properties of painted films
A variety of physical and mechanical evaluations of the painted
films were carried out according to Chinese National Standard.
The methods include evaluation of film drying time (GB/T 1728-
89), adhesion strength “the cross hatch test” (GB/T 9286-1998),
610 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614

Table 1
Components of curing agent.

Curing agent Raw materials Acid no. (mg KOH/g)

PT (g) BA (ml) P2 O5 (g) E-51 (g) BDE (g)

PEA 10 26.5 35.6 0 0 597.6

PRA1 10 26.5 35.6 90.3 0 152.6
PRA2 10 26.5 35.6 54.2 23.9 279.6
PRA3 18.1 13.3 35.6 54.2 23.9 235.7

flexibility “bend” test (GB/T 1731-93). The water resistance of the 220
B
varnishes was evaluated according to water resistance test (GB/T 200
1733-1993). 180

Transmittance/%
160 1034
C
140
2.8. SEM 120
2290
100
The morphology of the char residues was observed with a 80
A

KYKY-2800B scanning electron microscope (SEM) (KYKY Technol- 60

ogy Development Ltd., China) after gold coating surface treatment. 40
The electron micrographs were taken with an acceleration voltage
20 915
of 25.0 kV.
4000 3500 3000 2500 2000 1500 1000 50 0
Wavenumbers/cm-1
3. Results and discussion
Fig. 1. The FTIR spectra of E-51, PEA and PRA1. (A) E-51; (B) PEA; and (C) PRA1.

3.1. The synthesis principle of the curing agent

The esterification reaction between P2 O5 and BA is shown in
Scheme 1. The product is a mixture of phosphate acid, phosphate
monoester acid, phosphate diester acid and phosphate triester [17],
all of which are typical acid source of IFR. But they are small
molecule compounds, and the mixture has high acid value. The
small molecule has a bad effect on the performance of the painted
film. The high acid value makes the curing process too fast to oper-
ate. Especially phosphate triester has no reactive function, so that
it could not be fixed on the painted film, and the use of such a
compound is associated with migration problems.
It is shown in Scheme 2, a macromolecular phosphate ester acid
polymer is synthesized via the reaction of PT and P2 O5 . The prod-
uct has the carbon source and acid source of IFR, and PT as a cross
linking agent can solve the migration problem. The existence of BA
makes the reaction easy to control. The specific ratio of BA and PT
is presented in Table 1 but PEA is a curing agent with high acid-
ity. It can be seen from Table 2 that, the surface drying time of
PEA/MUF is 20 min, which is too short to operate. The painted film
properties of PEA/MUF including water resistance, flexibility and
adhesion strength hardly satisfy the Technique index (GB 12441-
2005). Apparently, it is difficult to apply the varnish of PEA/MUF to
practice.
In order to reduce the acidity of the curing agent, PEA was further
modified by E-51. The epoxy groups of E-51 react with P O H of
PEA, and the phosphate resin acid (PRA) was formed (Scheme 3).
Fig. 1 shows the FTIR spectra of E-51, PEA and PRA1. As can be
seen from the spectra of PRA1, the typically vibration peak is at
915 cm−1 . This corresponds to the fact that epoxy group of E-51
disappears completely. The typically vibration peak at 2291 cm−1
and 1034 cm−1 (P O H) of PEA becomes weak. These facts above
testify the formation of the PRA.
As a curing agent, PRA1 has a lower acidity than that of PEA. And
with the linear structure and lipophilicity of E-51, the water resis-
tance and flexibility of the painted film were improved (Table 2).
Moreover, the polarity of the aliphatic hydroxyl and ether group
in the molecular of E-51 can produce electromagnetic force, so the
introduction of E-51 demonstrates an improvement of adhesion
strength. But if overdose E-51 were added, it was easy to gel during
the experiment due to the increase of the cross linking degree.
It can be seen from Table 2 that the flexibility and water resis-
tance of PRA1/MUF cannot conform to the Technique index of GB
12441-2005. In order to improve these properties of the painted
film further, E-51 was partly replaced by BDE, which has soft seg-
ment structure. As seen from PRA2/MUF in Table 2, the flexibility
and water resistance were improved. Moreover, the introduction

O O O O

ROH P 2O 5 RO P OH RO P OH RO P OR HO P OH

OH OR OR OH

Scheme 1. The esterification reaction between P2 O5 and monohydric alcohol.

O OH
O H2 H2 P
CH2OH CH 2OH C O OH
O C
C + P2O5 HO P C OH
CH 2OH CH 2OH O C C O P H2 H2
H2 H2
O C C O
O C
C C O
H2 H2

Scheme 2. The esterification reaction between P2 O5 and PT.

 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614 611

Table 2
The performance of the fire retardant varnish.

Technique index Exterior Water resistance (h) Adhesion strength Flexibility (mm) Surface drying time Hard drying time
(Grade) (min) (h)

GB 12441-2005 Uniform state ≥24 no peeling, no wrinkling 3 3 300 24

PEA/MUF Transparent 1 bubbling 3 50 20 16
PRA1/MUF Transparent 6 wrinkling 1 30 80 24
PRA2/MUF Transparent 48 transparent 1 <3 80 24
PRA3/MUF Transparent 48 transparent 1 <3 80 24

O O O

nH2C CH CH CH2 n+1HO P OH

OR

OH O OH O
O OH OH

HO CH CH2 O P O H2C CH CH CH2 O P OH

P O H2C CH
RO OR
RO

Scheme 3. Phosphate ester acid modified by epoxy.

of BDE diluted E-51, leading to the exothermal reaction easy to In a word, the specimen PRA3/MUF achieves the best fire retar-
control. dancy. To explain the results, thermal analysis of painted films and
A PRA curing agent is synthesized from P2 O5 , BA, PT, E-51 and SEM of char residues were further performed.
BDE.
3.3. Thermal analysis of painted films

3.2. Fire retardancy
The intrinsic flammable behaviors of the painted film were mea-
sured by the oxygen index value method. As can be seen from
Table 3, the LOI: PEA/MUF > PRA3/MUF > PRA2/MUF > PRA1/MUF.
The higher phosphorus content is advantageous to intrinsic fire
retardancy of painted film materials.
Fire retardancy—in paint, the ability of a paint to retard the
spread of a flame over coated substrate is usually achieved at the
sacrifice of the paint film. In fact, it is not only related to the intrin-
sic fire retardancy of painted film material, but also associated with
the property of charred layer that was formed by heating. The
charred layer provided resistance to both mass and heat transfer
and retarded the degradation of the underlying materials. The sim-
ulating big panel method and the cabinet method were used to
judge the protective ability of painted films against the fire.
The weight loss and char index obtained from the cabinet
method are given in Table 3. It is shown that PRA3/MUF has lower
weight loss and highest char index.
The temperature versus time curve obtained from the simu-
lating big panel method is given in Fig. 2. Fig. 2 shows that the
temperature of plywood increased sharply and occurred over a
very short period during the combustion. Indeed the whole sample
was burned approximately 2.3 min. After painted with the varnish,
Thermal analytical techniques are effective methods to investi-
gate the thermal degradation behavior of fire retardant materials.
Generally, the high char yield and low exothermic heat testified
that the fire retardancy was excellent. Figs. 5 and 6 and Table 4
show the thermal analysis data of painted films.
In the case of painted films, the degradation occurs in two suc-
cessive stages (Fig. 5): between 200 ◦ C and 400 ◦ C, the pyrolysis
of painted film produced a lot of combustible gas, which corre-
spond approximately to 40–50% of the mass loss, and lead to an
exothermic peak in the DTA curves. In that range of temperature,
it is generally accepted that the intumescing process develops. The
second step occurring between 400 ◦ C and 650 ◦ C, can be assigned
to the degradation of the expanded structure probably via oxidative
reactions. Some more thermal degradation products were formed
and burned and another exothermic heat peak appeared in DTA
trace in this step.
250
200
150
Temperature

the temperature rising rate decreased apparently. The temperature

rising rate: PRA3/MUF < PRA2/MUF < PRA1/MUF < PEA/MUF.
The photographs of char residue fracture of big panel method are 100 PEA/MUF
PRA1/MUF
given in Fig. 3. The visual observation showed that the charred layer PRA2/MUF
of PEA/MUF has a thin slice framework, and was so soft that it is PRA3/MUF
50 plywood
difficult to cut during the operation. The charred layer of PRA1/MUF
(Fig. 3b) was more compact than that of PEA/MUF. When touched,
it gave a feeling of hardness. PRA2/MUF presents a more intumes- 0
cent charred layer than that of PRA1/MUF, but the char was loose. 0 100 200 300 400 500 600 700 800
It can be seen obviously that the cellular foam charred layer of t/s
PRA3/MUF not only maintain the char integrity but also has a three
dimensional framework. Fig. 2. Temperature–time curve obtained from the simulating big panel method.
612 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614

Table 3
The flammability behavior of the painted films.

Method Sample PEA/MUF PRA1/MUF PRA2/MUF PRA3/MUF

Combustion behavior Intumescing Intumescing Intumescing Intumescing

After flame time (s) 5.66 40.08 17.18 26.40
After glow time (s) 0 0 0 0
Oxygen index Damaged length (mm) 12 56 46 41
IH (mm) 1 4 2 2.5
LOI 28.9 23 23.5 25
P% 10.8 4.8 5.2 5.5

Char index (cm3 ) 32 63 55 89

Cabinet
Weight loss (g) 2.7 4.7 4.9 4.7

Fig. 3. The photograph of char residue fracture of big panel method.

Table 4
Thermal analysis data of painted films.

Sample P% calcd. TG DTA

◦
On-set ( C) Char yield at (%) Heat (mJ/mg)

400 ◦ C 650 ◦ C Hi1 Ri1 Hi2 Ri2 Hi

PEA/MUF 10.8 180 53.3 22 409 0.37 685 0.63 1094

PRA1/MUF 4.8 225 65.5 29 413 0.42 565 0.58 978
PRA2/MUF 5.2 180 56.2 22 267 0.39 411 0.61 678
PRA3/MUF 5.5 205 61.6 27 336 0.30 782 0.70 1118
 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614 613

Fig. 4. SEM micrograph of char residue of painted films at 400 ◦ C.

The lower acidity of PRA1 than that of specimen PEA, leads to
comparatively thermal stabilization of the painted films. The onset
temperature of the specimen PRA1/MUF is increased. Meanwhile,
the char yield of the specimen PRA1/MUF is much higher than
that of specimen PEA/MUF at the same temperature. As shown in
Table 4, the char yield of the specimen PEA/MUF and PRA1/MUF are
53.3 and 65.5 wt% at 400 ◦ C, 22 and 29 wt% at 650 ◦ C, respectively.
The results imply that E-51 is an essential carbon source. Never-
theless, the relative exothermic heat of the PRA1/MUF increases
in the temperature range between 200 ◦ C and 400 ◦ C. The results
indicate that the degradation products of E-51 in that temperature
range have high combustion heat, which is detrimental to retard the
spread of a flame over coated substrate. But the total heat release
of painted film PRA1/MUF at the range of 400–650 ◦ C is lower than
that of PEA/MUF. The case manifest that the introduction of E-51
could be beneficial to the formation of a thermally stable charred
layer.
In the specimen PRA2/MUF, a part of E-51 was substituted
by BDE. Compared with specimen PRA1/MUF, the onset tem-
perature and the char yield as well as the exothermic heat of
specimen PRA2/MUF decreased. Especially, in the temperature
range between 200 ◦ C and 400 ◦ C, the exothermic heat decreases
obviously. It proves that BDE is beneficial to increase the intrinsic
fire retardancy of painted film material, but detrimental to form

100
1
2
80
Residue weight (%)

3
4
60
Exo

40
1
2
20 3
4
0
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature Temperature (°C)

Fig. 5. TG curves of painted films with different curing agent. 1, PEA/MUF; 2, Fig. 6. DTA curves of painted films with different curing agent. 1, PEA/MUF; 2,
PRA1/MUF; 3, PRA2/MUF; 4, PRA3/MUF. PRA1/MUF; 3, PRA2/MUF; 4, PRA3/MUF.
614 Z. Ma et al. / Progress in Organic Coatings 74 (2012) 608–614
a high quality charred layer. The results were coincident with the
test of fire retardancy and SEM of char residues.
In the specimen PRA3, more BA was replaced by PT. The speci-
men PRA3/MUF had higher initial decomposition temperature and
char yield than those of PRA2/MUF. Particularly, the lower relative
exothermic heat and higher char yield in the temperature range of
200–400 ◦ C is very advantageous to the fire retardancy. The results
imply that PT is a true carbon source. The heat release of specimen
PRA3/MUF increased at the range of 400–650 ◦ C, which is detrimen-
tal to the intrinsic fire retardancy of painted film material especially
in the high temperature flame.
3.4. SEM
SEM is an important way to characterize the morphology
directly. Fig. 4 shows the SEM images of the char residue of painted
films at 400 ◦ C. The development of an intumescing structure can
be observed.
It can be seen from Fig. 4 that the structures of swelled shape
char residue with many small cavities which is similar to the inside
of a honeycomb are formed. The cavities most likely originate from
the small bubbles constantly formed during combustion. The intro-
duction of E-51 made the char layer of PRA1/MUF much more
compact than that of PEA/MUF. The results imply that E-51 is an
essential carbon source and tends to form a high quality charred
layer.
The visual observation of PRA2/MUF and PRA3/MUF shows
that their char residue behaviors are somewhat different from
that of PEA/MUF and PRA1/MUF. The charred layer of PRA2/MUF
maintains the char integrity of the material. The charred layer
of PRA3/MUF shows that compact cavities structure looks like a
foamed cake. It is because that the soft segment structure of BDE
improves the hydrodynamics behavior and flexibility of painted
film’s melting liquid phase. The essential carbon source of PT made
the compact cavities wall solid. Consequently, an excellent charred
layer formed. This parameter is very important when dealing with
intumescing systems since those systems mainly act in the con-
densed phase via a barrier mechanism that limits heat and mass
transfer.
4. Conclusion
A water borne intumescent fire retardant varnish based on phos-
phate resin acid (PRA) cold cured amino resin was synthesized. The
PRA curing agent is from P2 O5 , BA, PT, E-51 and BDE. Both of BDE
and E-51 decrease the acid value of curing agent via the reaction
between epoxy group of E-51 and P O H of PEA. They also improve
water resistance and flexibility of painted film. In fire retardancy:
E-51 is beneficial to form a stable charred layer, but detrimental to
retard the spread of a flame over coated substrate. BDE is beneficial
to increase the intrinsic fire retardancy of painted film material, but
detrimental to form a high quality charred layer. PT is beneficial to
form a high quality charred layer, but its high heat release is detri-
mental to the intrinsic fire retardancy of painted film material. To
achieve high performance painted film, all these components need
to be balanced perfectly. It is a very important work we will do in
the future.
Acknowledgement
The work was financially supported by Shijiazhuang Kingdar
Special Coatings Co. Ltd. (He Bei, China).
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