SYNTHESIS AND CHARACTERISATION OF BISPHENOL …….

205

SYNTHESIS AND CHARACTERISATION OF BISPHENOL A NOVOLAC

EPOXY RESINS FOR COATING APPLICATIONS
N. O. SHAKER
Egyptian Petroleum Research Institute, Nasr City 11727, Cairo, Egypt

Abstract
Bisphenol A novolacs were synthesized in a melting process using para formaldehyde,
and in a solution process using formalin solution and oxalic acid catalyst. 1H-NMR
investigations show a higher content of methylene bridges in the novolacs synthesized by the
melting process. These novolacs were analyzed by GPC and FT-IR spectroscopy. The
bisphenol A novolac was cured with 1,2-amino ethyl piperazine (AEP ) as a curing agent for
epoxy resins. The networks synthesized were evaluated as organic coatings for steel. The
mechanical properties of the cured epoxy resins were tested and the chemical resistances of
the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and
alkali resistance measurements. The data indicate that the cured epoxy resins have excellent
chemical resistance as organic coatings among other resins.

Introduction

Epoxy novolacs are multifunctional epoxides based on phenol formaldehyde

novolacs. Epoxy phenol novolac resins have attained commercial importance (1-3).
When cured with polyamide or aliphatic polyamines and their adducts, epoxy
novolacs show improvement over bisphenol A epoxies, but the critical performance
of each cure is limited by the performance of the curing agent. Novolac-cured
epoxies are widely employed in molding and sealing compounds for the production
of electronic devices. Commercial novolacs are used on the basis of phenol or cresol
[4-5]. Modelling reactions of epoxy-phenol systems are investigated in the literature
[6-8], while no investigations about bisphenol A novolac-cured epoxy resins have
been yet reported.

The simplest diepoxide formed is the glycidyl ether derivatives. Although these
materials are used as adhesives, they suffer from lack of flexibility, which arises
from rigid aromatic groups in the short chains. Improvements in flexibility can be
obtained by incorporation of long chain compounds into the resin before curing. The
aim of the present study is directed towards the introduction of methylene group
between aromatic groups of bisphenol A to improve both the adhesion and flexibility
properties of epoxy resins. In this respect, bisphenol A novolacs were synthesized in
a melting process using para formaldehyde, and in a solution process using a
formalin solution and oxalic acid catalyst. 1-(2-Amino ethyl) piperazine (AEP) was
selected as a suitable amine curing agent to produce organic coatings.
206 N. O. SHAKER

Experimental Materials:

Diglycidylether of bisphenol A (DGEBA) was recrystallized from acetone-

methanol mixture (20:80, v/v); m.p. 44°C [9]. 1-(2-Amino ethyl) piperazine (AEP)
was used as a hardner. High purity acetone, toluene and pyridine were used as
received. All chemicals were supplied by the Aldrich chemical company.

Techniques

Methylation of bisphenol A

Different molar ratios of bisphenol A and para formaldehyde were used for the
synthesis of the novolacs, they varied between 0.167 and 0.495 mol formaldehyde to
0.438 mol bisphenol A. The mixtures were heated to 180°C in a one-necked flask
with a reflux condenser and a drying tube filled with glass wool. After 30 min the
reflux condenser was removed and the water formed was distilled off. Then the
temperature of the reaction mixture raised up to 200°C for about 5 minutes.

For the bisphenol A novolac synthesis in solution process, 0.5 mol of bisphenol A
was refluxed with 1.5 mol of 37 % formalin solution and 1 g dehydrated oxalic for
90 min. then 100 ml water were added while stirring. After depositing, the water
layer was decanted and the residual water of the lower viscous layer was removed in
vacuo at 140°C. A colourless product was obtained in a yield of 65 %.

Preparation of diglycidyl ether bisphenol A

In a humidity-protected 500ml glass reactor equipped with a mechanical stirrer,

dropping funnel and a condenser, the purified methylol derivative of bisphenols
(0.11 mol) were mixed with 1% of BF3.ET2O and heated at 40°C. Epichlorohydrine
was gradually added to the reaction mixture during 2 hrs. The reaction mixture was
heated at 125°C for 30 min and after cooling to 40°C, 0.22 mol of NaOH (as 50% of
aqueous solution) was added. Temperature of the reaction mixture was raised up to
80°C for 30 min. After cooling, the mixture was neutralized with 50 ml of acetic
acid (50%); and 150 ml of toluene was added and the reaction mixture was filtered
to remove sodium salts. The filtrate was washed four times with 150ml of hot water
(60-80°C), then toluene was evaporated from organic layer by rotary evaporator.

The diglycidyl ether of methylated bisphenols derived from acetone,

benzaldehyde and acetophenone derivatives were designated as DGMBA and
DGMBBA and DGMBAC, respectively. The products were obtained as viscous
products and the epoxy content (EC) was determined as reported method [10].
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 207
Physical measurements:

The prepared epoxy resins were dissolved in CDCI3 and analyzed using a Jeol
1
HNMR spectrometer model JNM-EX (270 MHz) to determine their chemical
structures. GPC analyses of the novolacs were carried out on a column set (PS 4/ps
20 HI BAR columns, Merck) with exclusion limits from 100 up to 20000 g/mol
(polystyrene in tetrahydrofuran). Tetrahydrofuran as eluent and a refractive index
detector were used. The glass transition temperatures (Tg) of the synthesized
novolacs were measured on a Perkin Elmer DSC in a temperature range of 30 to
210°C with a scanning rate of 5°C/min. The curing exotherms of the prepared epoxy
resins were measured in the presence of different weight ratios of AEP hardener as
described in previous works [11-13]. The curing exotherms were determined at two
different temperatures 40 and 60°C.

Testing of the Coatings:

It is common to use mild steel panels (15cm x 10cm) to evaluate the different
properties of coatings. The other side of panels was coated and protected against
corrosion environments by using coal tar epoxy primer.

The tested side was blasted and cleaned to apply the coating materials. Then the
panels were subjected to different testing procedure to evaluate their mechanical
properties and their durability as follows:-
• Adhesion strength (pull-off), ASTM D 4541-95
• Pencil hardness ASTM D 3363-92a
• Impact ASTM D 2794
• T- bend test ASTM D 522-93a

Chemical resistances were measured according to ASTM methods as reported in

a previous study [13].
• Hot water ASTM D 870-92,
• Acid and alkali resistances ASTM D1647-89

The acid and alkali resistances of coated panels were determined after immersion
in 10% of HCI 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 evaluated for the coated panels.
• Salt spray resistance
The coated panels were evaluated for salt-spray resistance in accordance with
ASTM B117-73. The test conditions were 35°C (±1.5°C), 95±5% relative humidity,
and 5% weigh percent of aqueous sodium chloride solution.
208 N. O. SHAKER
• Solvent resistance ASTM 02792

Results and discussion

The reaction of bisphenol A with formaldehyde in a basic medium leads to resins

of the resol type [14-16]. 1H-NMR and FT-IR-investigations on bisphenol A-
formaldehyde resins show the formation of resol resins in the presence of catalysts,
but in the absence of a catalyst novolac type resins are formed [17]. The novolac
formation by catalysis of the bisphenol A-formaldehyde reaction with oxalic acid
has already been investigated [18-19], but no information about the structure of
these novolacs was given. bisphenol A novolacs were synthesized in the absence of
solvent and catalyst to produce epoxy resins. "Bisphenol-A and para formaldehyde
were converted to the bisphenol A novolac [product (1) ]. The molar ratio between
paraformaldehyde and bisphenol A used for the syntheses of the novolacs was varied
between 0.167 and 0.495 mol para formaldehyde and 0.438 mol bisphenol A (Table
1).
OH OH OH
*

*
OH OH OH y

Product (1)
The molar mass of the novolacs synthesized (Mn) rises with increasing
concentration of paraformaldehyde in the reaction mixture. The glass transition
temperatures of the novolacs (Tg) do not significantly depend on the molar ratio of
the reacting components, but the specific heat capacities (H) determined in the glass
transition state decreased with increasing paraformaldehyde content in the reaction
mixture (Table 1). The oligomer distribution of the novolacs was estimated by GPC.
The GPC-chromatogram of two examples of the novolacs synthesized are given in
Figure (1). It can be seen that the novolacs contain a relatively high concentration of
unreacted bisphenol A. From the literature the possibility of a quantitative
determination of the low-molecular-weight oligomers in phenol or p-cresol-
formaldehyde resins [20-21] and of the phenol content [22] is known. A calibration
with model substances is a prerequisite. Therefore, only the area-% of the bisphenol
A peaks in the GPC- chromatograms as a measure for the bisphenol A content were
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 209

determined and related to the reaction conditions. The dependence of this bisphenol
A peak area-% on the molar ratio of the reacting components shows that the content
of unreacted bisphenol A decreases if more para formaldehyde is used in the
synthesis (Figure 2). Increasing the mole ratio of para formaldehyde during
synthesis of the novolacs leads to a product of higher molecular mass (Table 1). The
concentration of the methylene bridges in the novolacs synthesized was estimated
from 1H-NMR spectra. In this respect, 1HNMR spectrum of BP-10 is represented in
Figure 3. The ratio between the peaks at chemical shift 2.2 and 0.8 ppm which
represent methylene and methyl groups, respectively was used to determine the
methylene content. The concentration of the methylene bridges in the novolacs
synthesized was estimated from 1H-NMR spectra. Figure 4 shows the ratio of the
methylene and methyl protons determined from the integrals of the 1H-NMR spectra
versus the formaldehyde: bisphenol A ratio. The content of methylene bridges
increases up to a ratio of formaldehyde to bisphenol A of 0.8. FT-IR spectra of the
novolacs (Figure 5) show a band between 850 and 900 cm –1, which is not present in
the spectra of bisphenol A (Figure 5 a). This band is attributed to tri- or tetra-
substituted aromatics. Further, the hydroxylic band between 3200 and 3500 cm –1 is
broader in the novolac spectra than in those of bisphenol A. This means even
stronger hydrogen bridges in the novolacs than in bisphenol A attributed to
methylene bridges in the ortho position to the hydroxylic group in the bisphenol A
structure, which is already known for other phenolic resins [23-24].

The other way of novolac preparation is the synthesis using formalin solution,
bisphenol A and oxalic acid catalyst [18-19] as described above. The amounts of
formaldehyde used as 37% formalin solution and bisphenol A used in the synthesis
are 3 and 1 mol, respectively. The methylene bridge concentration of this novolac
determined from the 1H-NMR spectrum is lower compared with the novolacs
synthesized in a melting process though the formaldehyde excess is higher in the
solution process. Using a formaldehyde content of 3.77 mol relative to 1 mol
bisphenol A, the methylene bridge concentration can be increased, but high contents
of hydroxymethyl groups and oxymethylene bridges were determined as 1.89
refeering to one mol of bis phenol A. Therefore synthesized, novolacs from solution
process were used for the synthesis of the diglycidylether of bisphenol A [product
(2)] and designated as BPFE.
210 N. O. SHAKER
O
O
CH2 CH CH O
2 OH OCH2-CH CH2
HOCH2

CH2OH
y
CH2 CH CH O OH OCH2 CH CH2
2

O O

Product (2)

Synthesis of Novolac BP-A epoxy resin:

Epoxy resins are prepared by the reaction of compounds containing an active

hydrogen group with epichlorohydrine (EC) followed by dehydrohalogenation in
presence of NaOH. The most commonly used epoxy resins are those derived from
bisphenol-A by reaction with EC. The results of characterization of glycidyl ether
derivatives of methylated bisphenol A include epoxy functionality, epoxy equivalent
weight, EEW, and reaction yields are given in Table (2). It was observed that the
epoxy functionality of the prepared resins was varied from 2 to 4.8. On the other
hand the (Mn) determined from GPC analyses indicate that the prepared epoxy resin
have low molecular weights.

These results indicate that the prepared methylated resins have polyfunctional
epoxy groups.

The chemical structure of both novolacs bisphenol A epoxy resin was confirmed
1
by HNMR analysis. In this respect, the spectrum of BPE-5 was represented in
figure (6a). The disappearance of -OH peak at 4.7 ppm in spectrum of BP, figure
(6b), and appearance of two peaks at 2.82 ppm (CH2 epoxy), 2.94 ppm (OCH2
epoxy), and 3.43 ppm (CH epoxy) indicates the formation of glycidyl ether group
[11-13].

Evaluation of the prepared resins as organic coatings:

The curing experiments, reported here, were formulated as liquid epoxy coatings
with different ratios of curing agent. In all samples 1% of (ET)3N (wt% based on
weight of epoxy binder) was added as catalyst.
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 211

The tests for measuring the mechanical properties were evaluated after 24h at
ambient temperature (25°C). The data of mechanical properties (pull-off, impact,
bending and hardens) for cured epoxy resins based on methylated bisphenol A epoxy
with curing agents are listed in Table (3). The data reported on adhesions (pull-off)
indicate that all cured epoxy resins based on novolacs bisphenol A epoxy resin have
superior adhesion properties with steel than other cured resins. This can be
attributed to the high epoxy functionality of resins and the presence of terminal
glycol groups as indicated from hydroxyl numbers of the prepared epoxy binders
based on novolacs bisphenol A. It has been demonstrated that the presence of small
controlled amounts of terminal glycol groups can have beneficial effects on
adhesion [25-26]. It was also noted that the mixing ratios between epoxy resins and
AEP hardener affected the impact of coatings films. This was observed by
deformation of coating films when the mol % of AEP hardener was increased.
Moreover, the films were deformed when mixing ratios for methylated epoxy resins
were increased while the mixing mol ratios of epoxy: hardeners were decreased to
give the best results with impact and T- bend tests. These behaviors indicate that the
ratios of cross-linking agent affect the mechanical properties of coatings and the
high cross-linking density networks decreases the mechanical properties of the
formed network. The variation of hardness results (by pencil test) from soft
(minimum cross-links) to hard coatings (maximum cross- link- density) indicate that
the best results were determined at low mixing mol ratio for epoxy: hardener
systems.

Evaluation of chemical resistance for cured resins:

There are two types of test methods to evaluate the durability of coatings,
chemical resistance test and mechanical tests. The coated panels have subjected to
chemical environments (alkali, acid, solvent and salt spray) to study the durability of
coats. The data of alkali, acid, solvent- resistance and water resistance were
determined for cured epoxy systems (based on methylated epoxy resins of bisphenol
A) and listed in Table (4). The sign (-) indicates failure of tests, while (+) sign
indicates that 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 use of polar solvents such as ketones is often used to assess the degree of
cure for a cross-linked composition for solvent resistance. 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
212 N. O. SHAKER

both immersion and rub methods. The failure of tests was determined either by
disruption or dissolution of the coating films from panels. The higher the degree of
cross-linking indicates the less free volume and segmental mobility remain available
in the polymer. So that solvent molecules can hardly penetrate the cross-linked
network at all. The crosslink density can be controlled by changing the type of
curing agents and functionality of epoxy resins [27-28]. In this respect, it was found
that the all prepared epoxy resins based on methylated epoxy resins of bisphenol A
have good solvent resistance with all mixing ratios with AEP. It was also noted that
the increasing of epoxy functionality from 2 to 4.8 for methylated epoxy resins of
bisphenol A resins enhances solvent resistance for all epoxy resins / curing agents
mixing ratios. This can be attributed to increasing of crosslink density by increment
of epoxy functionalities, although the epoxy polarity is increased by increment of
epoxy functionalities. Only specific functional groups in the polymer may cause
sensitization to such reagents. The acidic hydroxyl group in phenolic resins remains
sensitive to alkali even after final cure [29]. In the present systems, the structure of
network based on methylated epoxy resins of bisphenol A as epoxy binders and AEP
as curing agent, have aliphatic ester groups, which are sensitive to both aqueous
acidic and alkaline solutions. The data of acid and alkali chemical resistance for
cured methylated epoxy resins of bisphenol A indicate that these networks posses
high resistance to alkaline and acidic aqueous solutions, although they have ester
groups. The high alkaline and acidic resistance can be referred to high crosslink
density of networks due to high epoxy functionalities. This can be attributed to high
crosslink density of network decreases their exposure to environment [30]. It was
also that chemical resistance of cured epoxy based on methylated epoxy resins of
bisphenol A fails due to at lower mixing mol ratios the decreasing of hardener
content, which decreases cross-link density of network and increase the attack of
ester groups of network to acidic and alkaline solutions. On the other hand, the
lower acid and base resistance of cured BPE-5 and BPE-7.5 can be referred to the
formation of dangling chains (bonded from end and free from another end) which
increase the attack of ester and amide groups with both acid and alkali media [11].
The data listed in Table (5), indicate that the alkali and acid resistances were
decreased when the mixing ratios between novolacs bisphenol A epoxy resin with
AEP were decreased. This can be referred to the high ability to form dangling
chains.
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 213
Testing Corrosion Resistance of Coating

The continuous salt spray test was used, as described in experimental section to
study the effect of salts on the properties of coating films. The duration times of tests
were determined for all cured epoxy systems based methylated epoxy resins of
bisphenol A and listed in Table (5). The test was stopped when the films show poor
adhesion. The results of salt spray indicate the strong adhesion of coatings by the
increase of epoxy functionalities. This was observed from the improvement in
coating performance from 75 to 95% for BPFE after 1000 h of exposure to the salt
spray environment. Coating performance was consistently improved for each
exposure time for both coatings. This can be attributed to relationships between
coating properties and performance. In this respect, the adhesion of substrate with
coat is the main problem for coating failure. Strong adhesion also prevents moisture
vapor from passing 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. It was observed also that increasing of epoxy
functionality increases the adhesion of coat with steel. This can be referred to the
curing of epoxy groups with AEP hardner produce hydroxyl groups. It has been
shown that the concentration of resultant hydroxyl group has a deleterious effect on
the adhesion of the epoxy coating to the steel metal. The high salt spray resistance of
cured epoxy resins can be attributed to the alicyclic structure of AEP that have high
resistance to osmosis and electroendosmosis by comparing to aliphatic amines [31].
Essentially four types of epoxy materials are used in petroleum pipeline, tanker and
marine coatings: the epoxy coal tar type coating, the amine catalyzed ambient
temperature cure coating, the polyamide epoxy coating, and the epoxy ester type
coating. Furthermore, an unlimited number of combinations can be formulated that
are still called epoxy. In the present system of cured epoxy polyamine resins, based
on both BPE-10 and BPE-15 have excellent alkali, acid and solvent resistance and
provide a dense hard coating with good adhesion. So from these points epoxy resins
based on novolacs bisphenol A epoxy resin 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.
214 N. O. SHAKER
Table (1): Synthesis of novolac resins from bisphenol A and paraformaldehyde at varied
paraformaldehyde content in a melting process.
Paraformaldehyde Bisphenol A Mn Tg H
Novolac
(mol) (mol) (g/mol) (oC) (JK/g)
BP-5 0.167 0.438 380 33.0 0.71
BP-7.5 0.250 0.438 590 54.3 0.55
BP-10 0.330 0.438 620 54.4 0.44
BP-15 0.495 0.438 820 59.1 0.40

Table (2): Physico-chemical Characterization of Glycidyl Ether of Novolacs bisphenol A.

Epoxy Mn Yield
Oligomers EEW
Functionality (g/mol) (%)
BPE-5 295 2.0 590 73
BPE-7.5 242 2.8 680 62
BPE-10 243 3.0 730 70
BPE-15 212 4.8 1020 70
BPFE 200 4.0 800 83

Table (3): Coating tests of Glycidyl Ether of Novolacs bisphenol A Epoxy Resins Cured
with Hardner at Different Mixing Ratios
Mol ratios Pull-off Impact
Sample T-bend Hardness
of BP: EAP MPa (J/mm)
BPE-15a 1:1 10 10 + HB
BPE-15b 2:1 12 12 + H
BPE-15c 3:1 13 15 + 2H
BPE-15d 4:1 15 18 + 2H
BPE-10a 1:1 10 10 + H
BPE-10b 2:1 5 5 + HB
BPE-10c 3:1 3 1.5 + B
BPE-10d 4:1 3 1.5 + B
BPE-7.5a 1:1 13 12 - H
BPE-7.5b 2:1 15 14 - H
BPE-7.5c 3:1 18 15 + 2H
BPE-7.5d 4:1 20 20 + 2H
BPE-5a 1:1 15 12 + 2H
BPE-5b 2:1 8 8 + H
BPE-5c 3:1 5 3 - B
BPE-5d 4:1 5 3 - B
1:1 7 10 + 2H
2:1 10 15 + H
BPFE
3:1 12 20 + H
4:1 15 20 + H
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 215
Table (4): Chemical Resistance Tests of Glycidyl Ether of Novolacs bisphenol A
Epoxy Resins Cured with Different Mixing Rations
Acid Alkaline
Water Acetone
Sample no. Resistance Resistance
Resistance Rub test
(day) (day)
BPE-5a 7 7 - +
BPE-5b 30 30 + +
BPE-5c 45 45 + +
BPE-5d 50 50 + +
BPE-7.5a 14 14 + +
BPE-7.5b 45 45 + +
BPE-7.5c 60 60 + +
BPE-7.5d 90 90 + +
BPE-10a 45 45 + +
BPE-10b 60 60 + +
BPE-10c 90 90 + +
BPE-10d 90 90 + +
BPE-15a 90 90 + +
BPE-15b 90 90 + +
BPE-15c 90 90 + +
BPE-15d 90 90 + +
90 90 + +
90 90 + +
BPFE
90 90 + +
90 90 + +

Table (5): Salt Spray Resistance of Cured Glycidyl Ether of Novolacs bisphenol A
Epoxy Resins.
Exposure time Disbanded area (1) ASTM
Sample No. (h) RATING
MM2 %
BPE-5a 300 67.40 58.1 2.5
BPE-5b 400 35.90 31.0 3.0
BPE-5c 500 5.20 4.4 7.0
BPE-5d 500 13.00 11.0 6.0
BPE-7.5a 646 2.33 2.0 8.0
BPE-7.5b 646 3.38 2.9 7.7
BPE-7.5c 646 5.20 4.4 7.2
BPE-7.5d 646 12.90 11.0 6.0
BPE-10a 350 67.40 58.1 2.5
BPE-10b 450 35.90 31.0 3.0
BPE-10c 550 5.20 4.4 7.0
BPE-10d 600 13.0 11.0 6.0
BPE-15a 750 2.33 2.0 8.0
BPE-15b 750 3.38 2.9 7.7
BPE-15c 750 5.20 4.4 7.2
BPE-15d 750 12.90 11.0 6.0
1000 2.33 2.0 8.0
1000 5.20 4.4 7.2
BPFE
1000 3.38 2.9 7.7
1000 2.33 2.0 8.0
216 N. O. SHAKER
SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 217
218 N. O. SHAKER
 SYNTHESIS AND CHARACTERISATION OF BISPHENOL ……. 219

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220 N. O. SHAKER

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‫‪222‬‬ ‫‪N. O. SHAKER‬‬

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