Chapter 1

1.1 GENERAL INTRODUCTION

The epoxy resin technology had its genesis in research

conducted in the United States and Europe just before the World
War-II. The first series of resins-reaction products of
epichlorohydrin and bisphenol-A was produced commercially in
1947. In ten years a production volume of some 30 million pounds
was achieved and this being tripled six years later.
In the late 1950s, a number of new epoxy resins, different in
kind from the earlier diglycidyl ethers, were introduced and by the
end of 1960 at least 25 distinct types of resins were commercially
available. At this point the term epoxy resins became generic. It is
now applied to a wide family of materials. The epoxy resins can
duplicate the performance of most other thermosetting plastics and
exceeds their performance in variety of specialized applications. In
recent polymer age, epoxy resins have gained increasing
importance due to their wide range of applications in many fields
such as coatings, electrical, electronics, casting resins, dipping
compounds, moulding powders and reinforced plastic industries
/1,2/. Because of their high strength, versatility and excellent
adhesion to variety of surfaces, epoxy resins have gained wide
acceptance by diverse users. They have revolutionized joining and
fastening technology in some industries. Epoxides are used to bond
metals, glass, ceramics, wood, many plastics, concrete and other
surfaces. A number of properties have led to rapid growth of epoxy
resins and their use in wide range of industries /3,4/.
1. Versatility: The epoxy resins are probably most versatile of
the contemporary plastics. The basic properties can be modifies in
many ways: by blending of resins types, by selection of curing
agents, and by the use of modifiers and filler.
2 Easy Cure: Epoxy resins cure quickly and easily between
temperature range from 5˚C to 150˚C, depending on the selection of
curing agent.

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3. Low Shrinkage: One of the most advantageous properties

of the epoxy resins is their low shrinkage during cure. Phenolic
casting resins, which evolved water, reveal high shrinkage, as do
the acrylic and polyester resins, which must rearrange and reorient
considerably in the liquid and semigelled phase. Epoxy resins react
with very little rearrangement and with no volatile by-products
being evolved.
4. High adhesive strength: Because of the chemical make up,
chiefly the presence of polar hydroxyl and ether groups, the epoxy
resins are excellent adhesives. The resins cure with low shrinkage,
so that the various surface contacts set up between the liquid
epoxy-resin formulation and the adherends are not disturbed
during cure. Adhesive strengths, without the need for either upon
the time or high pressures, are perhaps the best obtainable in the
contemporary plastic technology.
5. High mechanical properties: The strength of properly
formulated epoxy resins usually surpasses that of the other types
of the casting resins. This is probably in part a result of their low
shrinkage, which minimizes stresses that otherwise would weaken
mechanical structure.
6. High electrical insulation: Epoxy resins are excellent
electrical insulators.
7. Good chemical resistance: The chemical resistance of the
cured epoxy resin depends considerably on the curing agent used.
Selectively outstanding chemical resistance can be obtained by
specification of proper materials. Overall, most epoxy resins
possess extremely high resistance to caustics and good to excellent
resistance to acids.
8. Low creep: The cured epoxy resins, maintain their shape
under the prolonged stresses.
9. 100% solid: Unlike the phenolic and some other resinous
adhesives, the epoxies cure without releasing water of other

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condensation by-product. This makes it possible to bond the epoxy

resins at only contact pressure or with no pressure at all.

1.2 EPOXY RESINS

Epoxy resins comprise a group of crosslinkable materials,

which all possess the same type of reactive functional group, the
epoxy or oxirane group (I). Their chemistry and technology have
been reported in number of texts /1,6/.

The non epoxy part of the molecule may be aliphatic,

cycloaliphatic or highly aromatic hydrocarbon or it may be non-
hydrocarbon and possibly polar. It may also contain unsaturation.
The capability of the epoxy ring to react with a variety of substrates
imparts versatility to the resins. Treatment with curing agents
gives insoluble and intractable thermoset polymers. In order to
facilitate processing and modify cured resin properties, other
constituents such as fillers, solvents, diluents, plasticizers,
accelerators, etc may be included in the compositions.
To meet the different requirements of broad sweep of
applications /1, 5-16/, epoxy resins of many types are available in
combination with the variety of curing agents which contribute the
essential versatility to the epoxy system. In the following parts of
the section, commercially important epoxy resins are discussed.

1.2.1 GLYCIDYL EPOXY RESINS FROM BISPHENOLS

The first and still the most commercially important epoxy

resin is the reaction product of Bisphenol-A (BPA) and

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epichlorohydrin (ECH) in presence of sodium hydroxide.

Table 1.1 Effect of Epichlorohydrin:Bisphenol-A ratio on

resin properties
Mole ratio
η value ( n) EEW M.P. ˚C
ECH: BPA
10 :1 0.1 - 0.2 370-390 175-210 -
2 :1 ~ 0.4 450 225-290 -
1.6 : 1 1.2 700 300-375 40-50
1.57 : 1 2.0 900 450-525 65- 75
1.22 : 1 3.7 1400 870-1025 95-125
1.15 : 1 8.8 2900 1650-2050 125-135
1.11:1 12.0 3750 2400-4000 145-155

The structure of the product, diglycidyl ether of bisphenol-A

(DGEBA) is dependent upon the stoichiometry of the reactants.
Typically resins are marketed with η, in (II), in the range of 0.2 to
12. The data in Table-1.1 shows the effect of ECH:BPA ratio on
resin properties such as epoxy equivalent weight(EEW), molecular
weight ( n) etc /17/.
In addition to dominant use of bisphenol-A, several other
bisphenols have been also used to modify the properties of the
resins. There has been increasing interest in the use of bisphenol-F
/18-20/ for the synthesis of resin diglycidyl ether of bisphenol-F
(DGEBF, III) because the resulting resin has lower viscosity than
that of DGEBA resins. This is because DGEBF is the product of the
mixture of three isomers of bisphenol-F. Bisphenol-H
(hydrogenated bisphenol-A) is used to synthesize diglycidyl ether of
bisphenol-H (DGEBH, IV) /18/ which shows promising weather
resistance. Similarly, bisphenol-S (4,4,'-dihydroxy diphenyl sulfone)
is used to obtain thermally stable epoxy resin known as diglycidyl
ether of bisphenol-S (DGEBS, V) /6,21/.

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O CH3
O C O
CH3
O
DGEBH (IV)

1.2.2 FLEXIBLE EPOXY RESINS

Though the epoxy resin (DGEBA) is widely used in many

applications /22/, the cured product shows lower flexibility, lower
strength and elongation. In order to overcome these disadvantages
various types of approaches have been adopted by the industries.
One of these approaches is the incorporation of aliphatic epoxy
resin to the conventional resin system, which provides lower
viscosity in order to improve handling characteristics /17/, as well
as flexibility to the cured system by virtue of increasing the
distance between the cross-linked points. /23/
Aliphatic epoxy resins give soft composition when they are
used alone. Usually they are used in blends with other epoxide
resins. Compared with unmodified rigid resins, the bleds have
greater toughness and elongation at break /4/.

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Some of the commercial aliphatic epoxy resins are given

below.

1.2.3 MULTIFUNCTIONAL EPOXY RESINS

1.2.3.1 Trifunctional Epoxy resins

High temperature applications can be improved by the use of
higher functionality resins, which increases crosslink densities and
improves thermal and chemical resistance.
Epoxy resin (VII) based on tris (hydroxyl phenyl) methane is
one of the important epoxy resins used in high performance
applications. This resin shows excellent physical and electrical
properties, moisture resistance, formulation stability, reactivity and
retention of properties at elevated temperatures /24-25/. The
semisolid epoxy resin is useful for high performance composites,
adhesives where requirements include toughness, and long-term
high temperature oxidative resistance while the solid resins fits
into the semiconductor moulding powder industries, where the

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requirements include purity, formulation stability, fast reactivity

and electrical properties over a broad temperature range.

The important trifunctional epoxy resins is triglycidyl

isocyanurate (TGIC, VIII), the reaction product of cyanuric acid
with epichlorohydrin, marketed as PT 810 by CIBA-GEIGY /17/. It
is a crystalline compound, melting in the range 85-110 OC, with
an epoxy equivalent weight 108. Miscibility with organic compound
is limited. Because of good weather ability, PT810 is used in
outdoor powder coatings, CIBA-GEIGY also markets the triglycidyl
ether of p-aminophenol, TGEPAP (IX) which was developed by
union carbide under the designation 0500 and 0510 /17/.

Recently a trifunctional epoxy resin(X) based on 5-amino-1-

napthol /26/, is also reported when cured with nadic methyl
anhydride, shows heat distortion temperature 195 OC, flexural
strength 16.3 kg/mm2 and water absorptivity 0.25%.

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O
O

N
O
O
TG of 5-amino-1-napthol (X)

1.2.3.2 Tetra functional Epoxy resins

In the recent years, intensive research and development

efforts have gone into the improvement of resin systems as matrix
materials for advanced composite to respond the more and more
stringent demands for structural components. This led the
development of tetra functional epoxy resins from various diamines
and tetraphenols. Because of their multifunctionality, they possess
good adhesive properties, higher mechanical properties, good
chemical and environmental stability.
Glycidylation of the tetrakis(4-hydroxy phenyl) ethane(XI)
yields the tetraglycidyl ether of polyphenol with a theoretical
functionality of 4, softening point of 80 OC and epoxy-equivalent
weight 185-208 /27/. The resin is commercialized and marketed
as Araldite 0163 and Epon 1031 by CIBA-GEIGY and Shell
Chemical respectively.
Araldite MY-720 (XII) is another tetrafunctional epoxy resin,
which is marketed by CIBA GEIGY. It is a reaction product of
diamino diphenyl methane (DDM) and epichlorohydrin in excess
the epoxy-equivalent weight is 177-133 and viscosity range is from
5000 to 25000 m Pas. The other data related to this resin is also
reported in the literature /28-31/.
Recently tetra-N-glycidyl epoxy resin from m-xylene
diaminine (XIII) is commercialized /32, 33/. The resin has low
viscosity, curability at low temperatures, excellent adhesion,
electrical insulating properties and moisture resistance.

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1.2.3.3 Epoxy Novolac Resins

The novolac-based epoxy resins are polyglycidyl ether of

novolac resins. The epoxy novolac resins are synthesized by
reacting novolac resins with epichlorohydrin in presence of sodium
hydroxide. Following is the general structure of epoxy novolac resin
(XIV).

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The number of glycidyl groups per molecule per resin is

dependent upon the number of phenolic hydroxyls in the starting
novolac, the extent to which they are reacted, and the extent to
which lowest molecular weight species are polymerized during
synthesis. A wide variety of novolacs are known, based on different
phenols. The epoxies generated have functionalities that vary
between 2.5 and 6, which allows for a high degree of cross-linking
during cure for the development of higher heat and chemical
resistance polymer than the bisphenol-A based epoxy resins.
Presence of four carbon atoms in the alkyl groups on phenol yields
resins soluble in paraffin hydrocarbon /34/. Novolac resins based
on chlorophenols may be used to impart flame retardant property
to the cured products /35/.
Epoxy novolac resin based on naphthol-aldehyde oligomer
imparts better properties compared to phenol-formaldehyde
novolac and bisphenol-A based epoxy resins. The structure of some
epoxy novolac resins are shown below.
(1)

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(2)

(3)

Because of their excellent heat resistance, low water

absorption, novolac based epoxy resins have found their
applications /36, 37/ in structural laminates, electrical laminates,
high temperature adhesives, electrical encapsulations and
compression molding.

1.2.4 FLAME RETARDANT EPOXY RESINS

The majority of the epoxy resin formulations are considered

to have flammability characteristics ranging from slow burning to
self-extinguishing. Flame retardancy of epoxy resin can be achieved
mainly through the addition of halogenated compounds or
phosphogenated compounds or mixture of both classes of
compounds /38-42/. The halogen or phosphorus may be
contained in the resin, in the curing agent of modifier, or in an
additive specially designed for epoxy resins.

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Flame retardant epoxy resins containing halogen, which has

been introduced directly in to the epoxy resin molecule, are now
available and growing steadily.
The structure shown in figure below is a flame retardant
epoxy resin derived from tetrahalobisphenol-A (XV).

Flame retardancy is further enhanced /43/ by adding

antimony sec-butoxide at 110˚C to the final resin. Brominated
resins are usually mixed with conventional epoxies to give 3-25%
halogen in the resin/curing agent mixture. Chlorine is less effective
than bromine, 30% chlorine is required to produce the same
relative level of retardation as 15% bromine. Antimony,
phosphorous and boron compounds are often used in conjunction
with brominated resins to reduce flammability. Approximately 5 to
6% phosphorous /44/ is required to obtain significant flame
retardation. A variety of phosphorous-halogen compositions
containing about 2% phosphorous and 6% chlorine produced self-
extinguishable epoxy resins. Direct incorporation of a flame
retarding substance into the polymer backbone during the
synthesis of epoxy resin imparts permanent fire retardancy, since
in that case there will be complete dispersal of the retarding
species throughout the polymer matrix.
Two such flame-retardant epoxy resins containing
phosphorous have following general structures /45, 46/.

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The flame retardancy of cured resin samples can be

determined mainly from the values of limiting oxygen index (LOI).
The oxygen index (OI)m is taken as the minimum percentage of
oxygen required in a nitrogen oxygen atmosphere, surrounding the
sample to maintain its combustion for at least 30 sec after ignition.
A material must be considered flammable as long as the LOI (%
oxygen) value is 26 or below /47/.
Chlorine and bromine can also be introduced in the curing
agent, e.g., chlorandic anhydride, tetrabromo and tetrachloro
phthalic anhydride.

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These flame retardant epoxy resins are nowadays used in

many applications like
(i) Structural laminates
(ii) Electrical laminates
(iii)Potting and encapsulation compounds
(iv) Adhesive and coatings.

1.2.5 COLOURED EPOXY RESINS

In past few years, coloured epoxy resins have gained

increasing importance due to their wide range of applications. For
example, coloured epoxy resins are widely used for transmittance
cables, for coloured bathtubs, for powder paints, for printing inks,
in electrical applications (Printed circuit boards), decorative sheets
etc.,/48-52/. However very few references are reported where the
colour is imparted in the resin by introducing chromophoric group
in the molecule /53, 54/.
Maslosh and co-workers developed structurally coloured
epoxy resin (XVIII) for the glass reinforced plastics and coatings
from mono and diglycidyl derivatives of -amino anthraquinone
and epichlorohydrin/53/.
Batlear et al. have synthesized coloured epoxy resins with
mol. Wt. 400-1000, which are useful as binder /54/.

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Konstantiov and co-workers have also reported coloured

epoxy resin (XVII) where the colour-forming group is attached in
the structure of resin molecule /55/.

Patel et al., synthesized and characterized colored epoxy

resin containing azo moiety by reaction between epichlorohydrin
and bis-azodiol. The cured products have good thermal stability
/56/. The photochromic properties of 1,3,3-
trimethylspiro[indoline-2,3′-[3H]naphtho[2,1-b][1,4]oxazine] doped
in PMMA and epoxy resin thin films were studied by Asiri et al.,
/57/.
There are two major classless of colourants used for
colouring of epoxy resins. They are dyes and pigments. Dyes are
soluble in the medium used and only produce colour by light
absorption. Pigments are essentially insoluble in the medium and
must be mixed in fine dispersion to provide uniform colourants.
Pigments are selected partly for their hue and shade, and
depending on the quantity present in the formulation. They can
produce colour ranging from pale pastels to deep shades with a
myriad of midtones. However, colour cannot be only the
determining factors in the pigment selection. Additional

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consideration should include dispersibility, heat stability, light

fastness, chemical resistance, opacity, and toxicity restrictions.
Achieving the optimum pigment particle size and determining
the proper dispersion process can be one of the most difficult
problems a pigment user must solve. Pigment particle size and
shape are critical to performance and acceptance of coloured resin
system. The dispersing process requires the dry powder to blend in
to the resin to “wet out” the particle and produce homogeneous
mixture.
Some pigments may darken or decompose at excessive
temperature. Light, especially daylight has destructive effect on
pigments used in epoxy resins. As a result, light fastness
requirements vary according to end-use applications.
There are less chances of above said problems with
structurally coloured epoxy resins. In coloured epoxy resins colour
forming group is attached with backbone of the resin, thus colour-
forming group is integral part of basic general structure. Coloured
epoxy resins are more beneficial than pigmented epoxy resins in
terms of dispersibility, heat stability, light fastness, chemical
resistance, opacity etc.

1.2.6 NON-GLYCIDYDYL EPOXY RESINS

Although the first and still most important epoxide resins are
of the glycidyl ether type, other epoxide resins have been
commercially marketed in recent years. These materials are
generally prepared by epoxidizing unsaturated compounds using
hydrogen peroxide or peracetic acid.

Such materials may be considered into following two classes

(A) and (B).

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A: Which contain a ring structure as well as epoxide group in

the molecule- The cycloaliphatic resins.
B: Which have an essentially linear structure on to which
epoxide groups are attached- The acyclic aliphatic epoxide resins.

A. Cycloaliphatic Epoxy Resins

Compared with standard diglycidyl ether resins, the liquid

cyclic aliphatic resins are paler in colour and have a much lower
viscosity. In general the cyclic aliphatic resins react more slowly
with amines, there is less difference with acid anhydrides.
Unox epoxide 201 (3,4-epoxy-6-methyl cyclohexa methyl-3,4-
epoxy-6methyl cyclohexane caboxylate, XX) and unox epoxide 206
(Vinylcyclohexanediepoxide, XXI) fall into this category. Because of
their low viscosity, the liquid cyclic aliphatic resins find use in
injection moulding and extrusion techniques as used for glass
reinforced laminates. They are also very useful diluents for the
standard glycidyl ether resins.

O CH2OCO O

CH3 H3C
Unox epoxide 201 (XX)

O
O
Unox epoxide 206 (XXI)

B. Acyclic Aliphatic Epoxy Resins

These materials differ from the previous class of resin in that

the basic structure of these molecules is long chains whereas the
cyclic aliphatics contain ring structures. These subgroups may be
distinguished as epoxidized dine polymers, epoxidized oils and poly
glycol diepoxides.

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The commercial products of these types are epoxidezed oils

/11/, epoxidized poly butadiene /58/ and polyglycoldiepoxide.

1.2.7 GLYCIDYL ESTERS

Generally, glycidyl esters are prepared by the reaction of

cycloaliphatic carboxylic acid with causic. The commercial product
of this class is diglycidyl ester of hexahydrophthalic acid (XXII) and
is marketed as CY184 (CIBA-GEIGY) and Lekutherm X-100 (Mobay
chemical Co.)

1.3 BRIEF REVIEW ON THERMALLY STABLE EPOXY RESINS

Among the different resinous materials utilized in polymeric

applications, epoxy resins have the ability to react via the epoxy
end group to generate three dimensional networks providing the
final material with rigidity, hardness and the inability to flow. Their
main problem is relatively poor thermal stability and flame
resistance which limit their applications in more demanding areas
such as aerospace and electronic industries.
Use of metal containing epoxy resins allows the possibility of
producing epoxy polymers with good mechanical properties and
high thermal stability /59-63/. On the other hand, the thermal
stability of epoxy resins can be enhanced by introducing silicon or
nitrogen compounds in resin systems.

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The aim of the work presented in the thesis is in connection

with enhancement of thermal stability of epoxy resins, hence a
literature survey regarding the various approaches adopted to
develop thermally stable epoxy resins are cited below.
Kenji, O., et al. /64/ prepared epoxy resins (XXIII) from
diphenylphosphinyl hydroquinone having good fire and heat
resistant properties. It was blended with 1,4-butanediol diglycidyl
ether and diaminodiphenyl methane to obtain product with glass
transition temperature 71˚C.

Madhu, B., et al. /65/ developed thermally stable epoxy

coatings from N-[3-(trimethoxysilyl) propyl] ethylene diamine and
copolymer of aminopropyl methyl dimethyl siloxane in finite ratio.
It was observed that the use of silicon compounds enhances the
thermal stability, chemical resistance and corrosion resistance of
the epoxy coatings.
Mija, A., et al. /66/ prepared epoxy resins bearing
azomethine groups derived from the reaction between the diglycidyl
ether of bisphenol-A and some aromatic azomethines in the
presence of n-butylamine as a catalyst. The epoxy resins
containing azomethine groups had an apparent higher thermal
stability than that of DGEBA epoxy resin.
Atta, A., et al. /67/ prepared thermally stable epoxy resins
from 5,5’-methylene-bis-salicylaldehyde and epichlorohydrin and
curing exotherms in presence of aromatic and aliphatic amines as
curing agents. The resins had excellent adhesion properties.

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Toshiharu, E., et al. /68/ prepared thermally stable epoxy

resins using the bis(3-methyl-4-phenyl)sulfone or bis(5-methyl-4-
hydroxy phenyl)sulphone. The resins were used as adhesives,
coatings etc.
Shuji, N., et al. /69/ have used (3-phenyl-4-hydroxy phenyl)
sulphone to prepare same type of epoxy resins which are useful for
potting compositions, moldings and insulators. Similarly the
various epoxy resins containing sulfone backbone are reported in
literature/70-73/.
Makoto, A., et al. /74/ prepared heat resistant triglycidyl
epoxy resins with glass transition temperature 230˚C from
aminophenols and epichlorohydrin. The resulting resins were used
to manufacture fiber reinforced plastics by filament winding
methods. Another triglycidyl epoxy resin based on 5-amino-1-
napthol was reported which when cured with nadic methyl
anhydride showed excellent thermal stability/75/.
Balabonovich, A.I., et al. /76/ studied the thermal stability
of tetrabronobisphenol A, diglycidyl ether of bisphenol A & their
mixture by curing them with 4,4’-diaminodiphenyl methane &
observed that the nonbrominated epoxy resins were more thermally
stable than brominated epoxy resins.
Becker, O., et al./77/ investigated the possibility of
improving the mechanical properties of high functionality epoxy
resins like bifunctional diglycidyl ether of bisphenol-A, trifuncitonal
triglycidyl p-aminophenyl and tetrafunctional tetraglycidyl diamino
diphenyl methane through dispersion of octadecyl ammonium ion –
modified layered silicates within the polymer matrix. They studied
the morphology of material using wide angle x-ray scattering as
well as optical and atomic force microscopy.
Jagdeesh, K. S., et al. /78/ investigated the curing behavior
of the epoxy resin N,N,N’,N’-tetraglycidyl diamino diphenyl methane
with triglycidyl p-aminophenol as a reactive diluents using 2,2’-

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dichloro-4,4’-diaminodiphenylmethane as the curing reagent. TGA

studies showed increase in thermal stability.
Preeti, J., et al. /79/ examined the curing behavior of
diglycidyl ether of bisphenol-A (DGEBA) using multi functional
aromatic amines having phosphine oxide and amide-acid linkages
& observed that curing temperatures of DGEBA were higher with
phosphorylated amines than the conventional amine 4,4’-diamino
diphenyl sulphone. This might be due to conversion of amide-acid
linkage in amines to thermally stable imide linkage during curing
reaction.
Krzysztof, S., /80/ prepared epoxy resin that can stand as
an effective surface coating material where high performance is
needed in terms of physico-mechanical properties as well as
chemical resistance. The resins were prepared from diglycidyl ether
of bisphenol-A and mercaptan – terminated polythiourethanes as
curing agent.
Anand, M. and Srivastava A.K. /81/ compared the properties
of epoxy resins containing arsenic acrylate with that of pure epoxy
resin (DGEBA) and observed that the epoxy resin with As cured
with polyamide at 30˚C showed chemical resistance and excellent
thermal stability compared with pure DGEBA.

1.4 CURING AGENTS

Optimum performance properties are obtained by cross-

linking the epoxy resins into a three dimensional insoluble and
infusible network. The resin is treated with a curing agents or
hardener. Its choice depends on processing methods, curing
conditions and the physical and chemical properties desired.
Curing agents are either catalytic or co reactive. A catalytic
curing agent functions as an initiator for epoxy resin
homopolymerization, whereas the co-reactive curing agent acts as
a comonomer in the polymerization process.

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1.4.1 CATALYTIC CURING AGENTS

Catalytic curing agents can be used for homopolymerization,

as a supplemental curing agent with polyamines or polyamides, or
as accelerator for anhydride cured systems. The widely used
catalytic curing agents are as follows.

(1) Lewis bases

Lewis bases such as tertiary amines are used for the

homopolymerization of epoxy resins. Cure with primary or
secondary amines gives tertiary amines, which function as catalyst
for homopolymerization. Tertiary amines such as triethylamine,
benzyldimethyl amine and Dimethyl diamino phenol have found
uses in adhesive and coating applications/18/. They are also used
as accelerators for the curing of anhydride and dicyandiamide
based systems /17/. While imidazoles are used as both hardener
and accelerator /82/.

(2) Lewis Acids

The most commonly used lewis acids as catalytic curing

agents are boron trifluoride adducts. e.g. Boron trifluoride
monoethylamine (BF3NH2-C2H5). It is a crystalline material and
cures epoxy resins at 80-100˚C. It has been identified as a catalyst,
an accelerator and a crosslinking agent /83-89/.

(3) Photoinitiator

Photoinitiated cationic curing of epoxy resins is a rapidly

growing method for the application of coatings from solvent free or
high solids systems /90/. This method is used for the fabrication
of can coatings /91/ and photoresists /92/. The most efficient and

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effective Photoinitiators for the curing of epoxides are

aryldiazonium salts /93-95/, diaryiodonium salts /96/ and
triaryls ulfonium salts /97/. Upon UV irradiation,
Photoinitiators yield a Lewis acid, which cures the epoxy resins in
the conventional manner.

1.4.2 CO REACTIVE CURING AGENTS

(1) Amines

Primary and secondary amines /98/ are the most widely

used curing agents for epoxy resins. Diethylenetriamine and
triethylenetetramine are highly reactive primary aliphatic amines
with five and six active hydrogen atoms respectively available for
the cross linking. Both materials cure glycidyl ether at room
temperature. The cure time depends on the ambient temperature
and the quantity of the resin. Although these materials are widely
used in small casting and in laminates because of their high
reactivity, they have the disadvantage of high volatility, pungency
and of being skin sensitizers. Properties such as heat distortion
temperature and volume resistivity are critically dependant on the
amount of hardener used.
Cycloaliphatic amines were developed in Europe, where their
uses as epoxy curing agents were well established. Unmodified
cycloaliphatic amines require elevated temperature for curing. They
cure quickly and have excellent colour stability, low viscosity and
good chemical resistance. They are, however, more expensive than
the other types of curing agents. N-Amino ethylpiperazine(AEP),
isophoronediamine(IPD) and 1,2-diaminocyclohexane (1,2-DAC) are
the principal commercial cycloaliphatic polyamine curing agent
/17/.
A number of aromatic amines also function as crosslinking
agent /99/.By incorporating the rigid benzene ring structure into

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cross-linked network, products are obtained with significantly

higher heat distortion temperature than that are obtained with the
aliphatic amines. Typical aromatic amines used for this purpose
include 4,4’-diaminodiphenylmethane/100/ 4,4’-diaminodiphenyl-
sulfone/101/ 3-aminobenzylamine, m-phenylenediamine , 4,4’-di-
aminoazodiphenylene /17/.
Polyamides are extremely versatile curing agents. They are
the largest volume epoxy curing agents in USA covering 25% of the
total market. They are the reaction products of vegetables oil
fattyacids in any ratio. They provide good mechanical properties,
exhibit readily workable pot lives and cure under mild conditions.
They are mainly used in coating formulations.
Dicyanamide(cyanoguanidine) is widely used as curing agent
in one-pack epoxy formulations for prepregs and electrical
laminates, for epoxy powder coatings and as adhesives for high
temperature cures /102/. Its latency as a curing agent is due to its
high melting point (206˚C) and its low solubility in epoxy resins at
ambient temperature. The curing reaction of dicyanodiamide with
various epoxy resins has been extensively studied by a number of
workers /103-105/. Another type of latent catalyst, available
commercially is ketimines. They are the reaction products of
ketones and primary aliphatic amines.

(2) Diacid Anhydrides

After the amines, acid anhydride constitutes the next most

commonly used reagent for curing of epoxy resins. Numerous
structurally different anhydrides are commercially available.
Commonly used acid anhydrides include phthalic anhydride,
tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
They are low cost hardeners, which produce polyester type
structures in the cured resin. They react slowly with glycidyl epoxy
resins but react faster with cycloaliphatic epoxy resins /12/. Most

24
 Chapter 1

anhydride cures of epoxy resins involve a catalyst especially for low

temperature cures. The catalysts for epoxy –anhydride reactions
are usually either lewis acids or lewis bases and their use has been
reviewed /106/.
Epoxy-anhydride systems exhibit low viscosity and long pot
life, low exothermic heat of reaction and little shrinkage when
cured at elevated temperature. The cured systems exhibits good
mechanical and electrical properties and is used in filament-wound
epoxy pipe and electrical-casting applications. Anhydride cured
formulations exhibit better thermal stabilities then similar amine –
cured systems. Anhydrides are the principal curing agents for
cycloaliphatic and epoxidized olefin resins.

(3) Miscellaneous curing agents

In addition to amine and acid anhydrides, many other curing

agents are available. Increasing attention is being given to the cure
of epoxy resins with isocyanates and the subject has been reviewed
/107/. Mercaptans are used to improve the cure rate of the resins
/108/. The thermoset resins like novolac /109/ resolac /110/,
melamine-formaldehyde and urea-formaldehyde are also used as
curing agents to obtain combined properties of these resins with
epoxides.
In general, various types of curing agents are commercially
used for the curing of epoxy resins in various applications. Some of
them with their applications are listed in Table 1.2.

25
 Chapter 1

Table1.2 Curing agents for epoxy resins and their

applications
Type Application
Adhesives, small
NH2CH2CH2NHCH2CH2NH2 casting electrical
1
DETA encapsulation, civil
engineering
NH2(CH2)2NH(CH2)2NH(CH2)2 NH2
2 General Purpose
TETA

3 Laminates

MPD
High performance
composites and
coatings, adhesives,
4
filament winding,
DDM
electrical
encapsulation
High performance
composites and
coatings, adhesives,
5
filament winding,
DDS electrical
encapsulation

6 General Purpose

Piperidine
Adhesives

7
TEA

26
 Chapter 1

Type Application
Construction
adhesives, sealants,
8 Polyamidoamines
floring, concrete
bonding
Maintenance
coatings, castings,

9 Polyamides trade sale paints,

adhesives, marine
coatings

Casting, potting,

10 encapsulation,
filament winding
Phthalic anhydride

11 Casting

Hexahydro phthalic anhydride

Improve heat

12 deflection
temperature (HDT)
Pyromellitic dianhydride

13 High HDT

Nadic methyl anhydride

Cl O
Cl
O
14 Cl Flame retarding
Cl O

Chloroendic anhydride

27
 Chapter 1

Type Application

Electrical laminates,
powder coatings,
15 Dicyanodiamide
single-package
adhesive

16 Polycarboxylic polyesters Powder coatings

Powder coatings,

17 Isocyanates maintenance
coatings

18 Polymercaptans and polysulfides Sealants, adhesives

Stove paints, can

19
coatings, finishes

Malamine-formaldehyde resin

Fast-bake enamels,

20 stove primers, can

Urea-formaldehyde resin and drum coatings,

topcoats

Baked enamels,

21 drum and pail

coatings
Resol

Moulding

22 compounds, powder
coatings
Novolac

28
 Chapter 1

1.5 MODIFIERS

The behavior and properties of a system can be controlled by

the addition of diluents, fillers, toughening agents, etc. Most
commercial epoxy resin systems contain modifying agents.

1.5.1 DILUENTS

Diluents affect the properties of the cured resin systems and

in particular, lower the viscosity in order to improve handling
characteristics. Diluents have minor effect on the performance of
room temperature cured resins, but chemical resistance and
thermal properties are usually substantially reduced.

Table 1.3 Commercial Reactive Diluents

Name Structure

n-butyl glycidyl ether

C12-14 aliphatic
glycidyl ether

o-cresol glycidyl ether

Neopentylglycon
diglycidyl ether
Butanediol diglycidyl
ether

Diluents can be classified into reactive or nonreactive types.

The former are mostly low molecular weight (130-210) glycidyl
ethers (Table 1.3) of low viscosity which reduce the cross-link
density of the system. Glycidyl esters are also commercially
available. Acrylics such as 1,6-hexanediol diacrylate and

29
 Chapter 1

trimethylolpropane triacrylate are multifunctional diluents, which

are used with primary and secondary amines /96/.
Solvents and plasticizers are nonreactive diluents, aromatic
hydrocarbons such as toluene or xylene, significantly reduce the
viscosity of liquid DGEBA resins, but this is accompanied by a 15-
25% decrease in compressive yield strength and a 10-20%
reduction in compressive modulus. If the solvent is trapped in the
cured system, solvent resistance is reduced and cracks develop if
the resin is used in heat cured coatings. Dibutyl phthalate is
widely used as non reactive diluents for liquid resins.
The use of solvents and reactive diluents in epoxy systems
has been reported in the literature /111-112/.

1.5.2 FILLERS

Fillers are used with epoxy resin systems mainly to reduce

costs /113-114/. They also reduce curing shrinkage, lower the
coefficient of expansion, reduce exotherm and may increase
thermal conductivity. Commercial fillers may be organic and
spheroidal, granular or fibrous in shape. They are chalk powder.
Silica, mica, metal oxide, phenolic micro balloons etc. They are
used in tooling, casting, molding or encapsulating epoxy systems.

1.5.3 TOUGHENING AGENTS AND FLEXIBILIZERS

Unmodified epoxy resins based on aromatic segments exhibit

brittleness and low elongation after curing with hardeners e,g.
polyamines and anhydrides. Aliphatic diepoxides diluents are used
to enhance the flexibility of the cured products. Polyaminoamide
hardeners, based on aliphatic polyamines /115/ and dimerized
fatty acids perform similarly. Liquid polysulfide polymers
possessing terminal mercaptan improve impact properties in
conjunction with polyamine hardener.

30
 Chapter 1

Liquid butadiene-acrylonitrile copolymer containing terminal

carboxyl group provides flexibilization by inclusion of rubbery
segments in the epoxy resin chain. Carboxyl-terminated
poly(butadiene-co-acrylonitrile) are also used as toughner /116/
Toughening can be attributed by the incorporation of a small
amount of elastomer as a discrete phase of microscopic particles
embedded in the continuous rigid resin matrix /117-119/.
Elastomer modified epoxy resins are used in composites and
structural adhesives /120/, coatings and electronic applications
/121/.

1.6 RANGE OF APPLICATIONS

Epoxy resins are commercially used in coating and

structural applications. Through the proper selection of resin,
modifier and curing agent, the cured epoxy resin system can be
tailored to specific performance characteristics. The choice depends
on cost, processing and performance requirements. Cured epoxy
resins exhibit excellent adhesion to a variety of substrates;
outstanding chemical and corrosion resistance; excellent electrical
insulation; high tensile, flexural and compressive strength, thermal
stability; a wide range of curing temperatures and low shrinkage
upon cure.
Because of their versatility, the epoxy resins are used in
thousands of industrial applications: Anticorrosion & antifouling
coatings /122-123/, honeycomb structure /124/, for paint brush
bristles and for concrete topping compounds /125/, body solders
and caulking compounds for the repair of plastics and metal boats,
for automotive springs and casting compounds /126/, abrasive &
water lubricated conditions for pump applications /127/,
electrochemical sensing /128/, conducting adhesives as a lead free
alternative in electronic packaging /129/, electro conductive resins
filled with graphite for casting application /130/, electronic

31
 Chapter 1

packaging /131/, potentiometric sensor for perchlorate ions

/132/, for fabrication of stamping dies, patterns tooling ; caulking
and salient compounds in building and highway construction
applications /133-135/, for cryogenic use /136/, high voltage
composite insulator /137/and in applications where high orders of
chemical resistance are required.
Other applications include potting and encapsulating
compounds /138-141/ and as impregnating resins for aerospace
applications, filament wound structure and tooling fixtures /142-
143/, adhesives for aircraft /144,145/, aerospace textile
composites /146/, composite materials in space environment for
development of a moon base /147/, in high performance vehicle
/148/
Epoxy based solutions are used as maintenance and product
finishes, marine finishes, structural steel coatings, tank coatings,
aircraft finishes, automotive primers and furniture finishes
/149,150/. They are also used in decorative floor applications; as
chemical resistant mortar and floor topping compounds
/151,152/, in printing ink, dental and surgical applications /153-
157/, for cholesterol level lowering agents /158/, for voltammetric
sensors /159/, for humidity sensors /160/, for manufacturing the
jet-printed LCD color filter /161/, in fuel cells /162/, for optical
ammonia sensor /163/, for marine primer steel coating
applications /164/ and for light weight chemical resistant foams
/113,165,166/.

1.7 BRIEF ACCOUNT ON PRESENT WORK

Epoxy resins are among the most important thermosetting

polymers in wide use as a matrix for fibre-based composites,
structural adhesives, surface coatings, etc. Most of the
commercially available epoxy resins are oligomers of DGEBA. The

32
 Chapter 1

epoxy resins are characterized by the presence of the oxirane

group.

Which is able to react with compounds possessing active

hydrogen atoms, including amines, amides or mercaptans. Various
glycidyl esters, glycidyl amine derivatives and thioethers have been
synthesized using this approach /6, 167/.
The epoxy resins most commonly used today in advanced
composite and coating applications are the o-glycidyl ethers and N-
glycidyl amines as they possess good adhesive characteristics as
well as good mechanical and physical properties with excellent
weather resistance. But now a day the thermal properties of epoxy
resins have also gained importance for the same applications.
Hence it was thought interesting to prepare thermally stable epoxy
resins. This work aims to prepare azomethine group epoxy resins
to enhance their thermal stabilities.
The curing reaction of a liquid crystalline epoxy monomer, N,
N'-bis[4-(2,3-epoxypropoxy)benzylydene]-1,4-phenylenediamine,
with an aromatic diamine, sulfanilamide was studied by Mija and
Cascaval /168/. Structurally different diepoxides, triepoxides or
tetraepoxides bearing azomethine linkages were synthesized and
characterized by Mikroyannidis /169/. Epoxy resins containing
both aromatic and aliphatic groups and derived from azomethine
bisphenols by reaction with diglycidyl ether of bisphenol A epoxy
resins in the presence of triethanolamine as catalyst were
synthesized by Mititelu et al., /170/. Thermally stable epoxy resin
containing imide and naphthyl groups was synthesized, and
characterized by Ren et al., /171/. Owing to the relatively high
thermal stability given by the presence of azomethine linkages,

33
 Chapter 1

heat-resistant epoxides were prepared by reacting hydroxy and / or

carboxy substituted azomethines or bisazomethines with
epichlorohydrin in the presence of a quaternary ammonium
bromide as catalyst /172-174/. Epoxy based on bisphenol-A are
widely used in many applications /175, 176/ but the properties of
cured epoxy resins is not in the range that required for higher
temperature applications. The higher functionality first appeared in
1950’s, where the glycidyl derivatives of aromatic polyamides
/177/ and phenol/178/ were prepared. The literature survey
showed that the reaction of epoxy ring with amine and alcohol is
well established/179/. A trifunctional epoxy resin based on 5-
amino 1-naphthol /26/ was also reported which when cured with
nadic methyl anhydride showed very good mechanical and physical
properties. Another trifunctional epoxy resin widely used in
aerospace application and adhesives was based on p-aminophenol
/180/ which showed higher crossed linked density and thermal
stability over the other types of epoxy resins. The reaction of epoxy
resin with different amino phenol may yield the thermally stable
resins. Nipons oil and fats co. Ltd. /181/ worked on synthesis and
purification of triglycidyl-p-aminophenol. The same product was
prepared by Akiyama, M. & Yao, T /182/ and used as fiber
reinforced plastics. Jagannathan, N.R. and Herring F.G. /183/ has
characterized the above said product using NMR spectroscopy.
Hence one may expect the polymers with azomethine
segments in the main chain to have a high thermal stability. The
research work described in this thesis is mainly related to the
elaborative aspects like studies on synthesis and thermal stability
of resins, their characterization by various chemical methods and
by using advanced instruments and on coating applications of the
prepared epoxy resins.

The entire work has been divided into following parts.

34
 Chapter 1

A. Synthesis and Characterization of Monomers

The various monomers (SB) used for resin preparation were

synthesized by reacting 2-hydroxy benzaldehyde with:
(1) o-amino phenol
(2) m-aminophenol
(3) p-aminophenol
which gives a condensation products known as 2,2’ –
bishydroxy diphenyl azomethine, 2,3’ – bishydroxy diphenyl
azomethine, 2,4’ – bishydroxy diphenyl azomethine respectively.
The synthesized monomers were characterized by meting point,
solubility test, viscosity, percentage yield, Nitrogen estimation and
by instrumental analysis such as infrared (IR), Nuclear magnetic
resonance (NMR) spectroscopy.

B. Synthesis & Characterization of Epoxy Resins

The epoxy resin containing schiff base in the main chain has
been synthesized by reacting above prepared monomers with
epichlordhydrine & bisphenol – A in weight proportions of 90:10,
70:30, 50:50, 30:70 and 10:90. The resins were characterized in
terms of viscosity, epoxy equivalent weight and IR spectroscopy.

C. Thermal study

It describes the thermal study of synthesized resins. The

results of the isothermal curing of resins by using diethylene
triamine (DETA) at room temperature and 4,4'-diaminodiphenyl
sulfone (DDS) at 160oC have been discussed in terms of gel point,
peak exotherm temperature and curing time. The curing kinetics of
epoxy resins using differential scanning calorimetry was studied
using TA Instruments, Differential Scanning Calorimeter on
dynamic run. The kinetic parameters such as activation energy,

35
 Chapter 1

order of reaction and the frequency factor were determined using

Borchardt-Daniels method.
The thermogravimetric study of cured epoxy resins is also
described in this chapter. The temperature characteristics such as
Ti (temperature of onset of decomposition), Tmax (temperature of
maximum rate of decomposition), T50 (half volatilization
temperature) and Tf (temperature of completion of decomposition),
integral procedural decomposition temperature (IPDT) and the
activation energy were calculated using Broido and Doyle's
methods. These parameters are discussed to established relative
thermal stability of the synthesized resin.

D. Coating Application of Resins

The prepared resins were applied on mild steel and tin

panels of required sizes as per IS specifications using DETA and
DDS as the curing agents. Following studies are incorporated in
this chapter.
The coating applications of epoxy resins were studied by
applying the resin systems on the mild steel panel having
dimensions 150 X 50 X 1.25 mm [quality as per IS:513;.1963] with
flat brush confirming to IS:384-1964. The coated mild steel panels
were tested by drying time i.e. tack free time, scratch hardness,
impact resistance, acid and alkali resistance, water and weather
resistance and solvent resistance. For the determination of
flexibility and adhesion, tinned steel panels having dimensions 150
X 50 X 0.315 mm as per Indian Standard Specification [IS: 197 -
1969] were used. The flexibility was measured using two different
size of rods viz., 114" and 118" rod by conical mandrel.

36
 Chapter 1

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