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A Critical Review: The Modification, Properties, and

Applications of Epoxy Resins
a
Pragyan Mohan
a
Department of Chemistry, Rama Institute of Engineering and Technology, Kampur, India
Version of record first published: 05 Feb 2013.

To cite this article: Pragyan Mohan (2013): A Critical Review: The Modification, Properties, and Applications of Epoxy Resins,
Polymer-Plastics Technology and Engineering, 52:2, 107-125

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 Polymer-Plastics Technology and Engineering, 52: 107–125, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602559.2012.727057

A Critical Review: The Modification, Properties, and

Applications of Epoxy Resins
Pragyan Mohan
Department of Chemistry, Rama Institute of Engineering and Technology, Kampur, India

ener. The prepolymer is formed by the copolymerzation of a

The article briefly reviews literature on the modification of epoxy monomer that has two nucleophlic OH groups, and the
resins and their properties, which are used for its industrial applica- other monomer has a C-O and C-Cl polar bond. The
tions. Experimental results on modified epoxy resins are collectively nucleophile attacks on the strain epoxy ring (epichloro-
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summarized, which focus on the structure, curing, and alternate hydrin) that displace chlorine by an intermolecular SN2
methods for modification of epoxy resins. The several properties such
as thermal stability, adhesive, toughness, and electrical conductivity reaction[2] having a new epoxy group, and it again reacts
have been studied during the modifications of epoxy resins, which is with nucleophile to produce secondary alcohol (Fig. 1).
useful in the field of electronic encapsulation, blending, composites, Previously, the simplest epoxy resins were prepared by
and nanocomposites, etc. The review concludes with a brief discussion the reaction of bisphenol A with excess amount of
on the most useful valuable modifications for industrial applications. epichlorohydrin in alkaline medium[3], as early as 1960.
During this reaction, the stepwise process continues until
Keywords Alternate methods of modification; Curing modifi- all the phenolic OH groups have been used in the ring
cation; Structural modification
opening reaction, leaving epoxy groups on both ends of
the polymer chains (Fig. 2).
INTRODUCTION Then, this epoxy resin prepolymer is converted into an
The successful applications of epoxy resins require the applicable form after changing it into the cross-link ther-
fundamental relationship among the structural modifica- moset form with hardener. For example, di- or tri-amine
tions and properties of epoxy resins. Over the years, this acts as a hardener, mixed with prepolymer epoxy resins
author and colleague A. K. Srivastava published an article[1] chains. The reactive epoxide rings can be opened by the
in 1997, highlighting the study of various epoxy resins and nucleophlic amino groups to cross-link polymer chains
curing agents. Further, the modification of epoxy resins together, causing the polymer to harden (Fig. 3).
and curing agents is well documented in various literature,
which describe flame resistance, adhesive property, thermal
STRUCTURE MODIFICATION WITH ENGINEERING
property and chemical stability of epoxy resins.
PROPERTY
This article presents a substantial amount of review
The outstanding property of epoxy resins (DGEBA) is
material covering up-to-date selective property investiga-
generated by its constituents[4], such as adhesive property:
tions of the modified epoxy resins during synthesis and cur-
due to presence of epoxy and hydroxyl group, the chemical
ing process, including 118 articles published by 2012. It is
resistance: due to presence of ether linkage and side by side
how it is valuable in industrial applications including trans-
toughness, rigidity: due to bisphenol A. These properties
portation, communications, construction, etc. that will be
can be studied by the analysis of epoxide equivalent weight
of value to all who are involved in the field of epoxy resins.
(EEW), hydroxyl content, chloride content, molecular
The chemistry of modified epoxy resins and its properties
weight, glass transition temperature (Tg) of epoxy resins
is not understood without having the preliminary knowl-
which are responsible for their end applications. DGEBA
edge about the formation of epoxy resins. Epoxy resins
is also known for its excellent insulating property.
represent a class of step-growth polymerization reaction
An important trend nowadays in polymer chemistry is the
of two main components: a fluid prepolymer chain with
synthesis of modified epoxy resins by using new additives or
reactive epoxide group on each end of the chain, and a hard-
compounds, which are expected to have interesting proper-
ties such as thermal stability, flame retardance, adhesiveness,
Address correspondence to Pragyan Mohan, Department of
Chemistry, Rama Institute of Engineering and Technology, Rama flexibility, toughness, anticorrosive, and antimicrobial
City, G T Road, Mandhana, Kampur 209217, India. E-mail: properties. These properties of epoxy resins are successfully
[email protected] more applicable in the industrial applications such as

107
 108 P. MOHAN
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FIG. 1. Reaction scheme 1: Epoxide ring opening reaction mechanism.

FIG. 3. Reaction scheme 3: Cross-linking reaction.

coating materials, filler, toughening agent, encapsulation
and also in the field of composite, electrical laminates,
electronic coating, etc. 1. DGEBA [(diglycidal ether of bisphenol A) (Fig.2)].
Thermal stability is a concept used to describe the ability 2. DGEPP [Diglycidal ether of phenolphthalein (Fig. 4)].
of a moist soil to maintain a relatively constant thermal 3. DGEBF [Diglycidal ether of 9,9-bis(4-hydroxyphenyl)
resistivity when subjected to an imposed heat load, thus fluorenefFig. 4g].
preventing a power cable from exceeding its safe operating The reactivity of these three different resins toward
temperature. The effects of modifications on the thermal trimethoxy boroxine (TMB) hardener was DGEBA>
stability on the epoxy resins was studied by Lin and DGEBF > DGEPP. The order of cross-link density was
Pearce[5], who in 1979 studied the relation between cured found to be DGEBA > DGEPP > DGEBF at the same
epoxy resin structure and properties by the synthesis of curing conditions. The DGEBA-DGEBF copolymer
three different epoxy resins and copolymers: showed high heat and flame resistance due to higher aro-
matic ring content than DGEBA-DGEPP copolymer.
The FTIR data[6] suggested that possible degradation of
these three epoxy resins followed by Wieland rearrange-
ment, Claisen rearrangement, and Norrish-type reaction.
After a few years, Chen et al.[7] prepared following five
epoxy resins:
1. DGEBA (bisphenolA)
2. DGEBF (9,9-bis(4-hydroxyphenyl)fluorine)

FIG. 2. Reaction scheme 2: Epoxy resins [DGEBA ¼ diglycidalether of

bisphenol A]. FIG. 4. i. phenolphthalein; ii. 9,9-bis(4-hydroxyphenyl)fluorine.
 MODIFICATION, PROPERTIES, AND APPLICATIONS OF EPOXY RESINS 109

3. DGEFX (3,6-di hydroxyspiro-[fluorene-9,90 -xanthane]) unaffected by aniline-modified epoxy resins. The literature
4. DGEA [10,10-bis(4-hydroxyphenyl) anthrone (Fig. 5)] was further enriched by Lee and Yang[11], who synthesized
5. TGETA [9,9,10,10-tetrakis(4-hydroxyphenyl)anthracene aniline=benzyl amine-modified epoxy resins having tertiary
(Fig. 5)] amines in the middle of the polymer chain. Diethylamine was
used as curing agent to produced thermally cross-linked resins.
These were cured with the help of TMB and DDS It was concluded that electro-deposition yield and throw-
(diaminodiphenylsulfone). The glass transition tempera- ing power of the emulsion prepared from benzyl amine
ture (Tg) for the uncured and cured resins were in these modified epoxy resins were higher than those of emulsion
order TGETA > DGEFX > DGEA > DGEBF > DGEBA prepared from aniline modified epoxy resins. In another
and DGEBA < DGEBF < DGEFX < DGEA, respectively. publication Lee and Yang[12] prepared the five modified
It was further concluded that a polymer having high epoxy resins of polyether and polyester-modified epoxy
aromaticity and=or cyclic ring structures in the chain back- resin by the reaction of four different poly ethers and one
bone usually gave high heat resistance. polycaprolactonediol(PCP) with epoxy resins. The extent
Bansal and Kush[8] prepared three epoxy resins: i) of reaction of epoxy resin and polyether or polyester was
bisphenolA resins; ii) novolac resins; and, iii) furfuryl alco- evaluated by the change of epoxy equivalent weight and
the gel permeation chromatography curve of the resulting
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hol resins. These resins were cured with different hardeners;

namely diethylenetriamine (DTA), dithioterephthalic acid product. Again, it was concluded that throwing power
(DTTPA), mercaptosuccinic acid (MSA), and phthalic was dependent on pH values of the resin mixture.
anhydride (PA). It was concluded that DTTPA have the Morphology and structure of organosilicon polymer-
highest thermal stability of all these curing agents. Bansal modified epoxy resins[13] was investigated by using an orga-
et al.[9] compared the thermal behavior of sulphone epoxy nosilicon polymer (denoted as ETOP) as modifier to blend
resins with DGEBA. The sulphone epoxy resins prepared with bisphenol A-type epoxy resins. It was concluded that
by epichlorohydrin and 4,40 -sulfonyldiphenol (SDP) were the cross-linked epoxy-rich phase (matrix) possessed a
thermally more stable than DGEBA. A few reports were higher glass transition temperature (Tg) than pure epoxy
also available on the synthesis of aniline-modified epoxy resins at a higher content of ETOP. This may be considered
resin[10] by the reaction of aniline and epoxy resin. as participation of epoxide groups on ETOP molecules in
The resulting modified epoxy resin was cured with the cross-link reaction of matrix and enhancing the
2-ethylhexanol-blocked toluene di-isocyanate (2-EH- cross-link density of the matrix (i.e., increasing the Tg).
blocked TDI). The cross-linked films prepared from aniline- On the other hand, a series of epoxy-bridged polyorgano-
modified epoxy resins was glossier than those prepared from siloxanes have been synthesized[14] by reacting multifunc-
commercial epoxy resins, but thermal properties were tional aminoalkoxysilanes (APTES,APMDS, APDES)with
DGEBA epoxy resin. The organic-inorganic hybrid, from
epoxy-bridged polyorganosiloxanes after the thermal curing
process, showed better thermal stability than the cured resin
network of pure epoxy-diaminopropane.
Increasing the number of publications, devoted to the
modification of epoxy resins has promoted by the syntheses
of new phasphopyrylated epoxy resins such as bis-(3-
glycidyloxy)phenylphosphine oxide (BGPPO)[15]. This
modified resins showed lower weight loss temperatures and
higher char yields than the Epon 828-based resins. The high
char yields as well as high limited oxygen index (LOI) values
of the BGPPO-based resins confirmed the effectiveness of
phosphorus-containing epoxy resins as flame retardants.
The thermal stability and flame-retardant[16] properties in
o-cresol formaldehyde novolac epoxy resins was developed
by the incorporation of organometallic compounds[2-(6-
Oxido-6H-dibenzo1,2-oxa-phosphorin-6-yl)1,4-benzenediol
(ODOPB)]. Because of the rigid, cyclic, side-chain structure
of ODOPB, the resultant phosphorus-containing epoxy
resin exhibited a higher glass-transition temperature, better
flame retardancy, higher modulus, and greater thermal
FIG. 5. i. 9,9,10,10-tetrakis(4-hydroxyphenyl)anthracene (TGETA); ii. stability than the regular bromine-containing tetrabromobi-
10,10-bis(a-hydroxyphenyl)anthrone. sphenol A epoxy resin and the linear, main-chain,
 110 P. MOHAN

phosphorus-containing epoxy resin. The main advantage of with DGEBA was investigated. The mechanical properties
ODOPB was that there no fumes or toxic gas emitted during of DGEBA modified with BMPE were improved without
the curing process. sacrificing thermal resistance.
Epoxy resins containing both phosphorous and silicon In another publication Yu et al.[25] studied the properties
were prepared[17] via fusion of phosphorous diol and a sili- of liquid crystalline epoxy resin (LCE) blend systems. With
con diol with a bisphenolA-type epoxy resins. The modified the addition of LCE resin, the blends showed that both
epoxy resins were exhibit tailored glass transition tempera- curing rate and glass transition temperature increased.
tures (159–77
C), good thermal stability ( >320
C), and The phase structures of the blends changed from homogen-
high char yields at 700
C under air atmosphere. The high ous to liquid crystalline phase when the content of LCE
char yield was demonstrated to come from the synergistic was increased. At the same time, the mechanical properties
effect of phosphorous and silicon, where phosphorous were also improved and thermal expansion coefficients
enrichesd char formation and silicon protected the char were lowed down. There was an interesting work, in which
from thermal degradation. Moreover, high flame retar- the thermal stability of epoxy resins was improved by the
dancy of the epoxy resins was found by the high LOI (limit- use of the recycling poly(ethylene terephthalate ¼ PET)
ing oxygen index) value of 42.5. waste[26] as a nucleophile during the preparation of epoxy
Hirose et al.[18] synthesized and studied the thermal resins in 2009. It was found that modification of epoxy
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properties of ester epoxy resins prepared by ester -car- resins improved tensile and flexural strengths, hardness
boxylic acid derivative (AL-polyacid, ALPA) of alcoholysis along with thermal stability due to longer alkyl fragments.
lignin(AL). The DSC data indicated that Tg increased with The incorporation of alkyl ether chains from PET glycoly-
increasing ALPA contents suggesting that lignin acted as a sis increased water absorption and chemical stability
hard segment in epoxy resin networks. Thermal degradati- against 10% HNO3, 75% H2SO4, and ethyl acetate.
on temperatures of epoxy resins slightly decreased with Three kinds of polyfunctional polyols with hydroxyl
increasing ALPA content. Zhao et al.[19] was used polydi- values of 180–320 mg=g were prepared[27] by the reaction
methylsiloxane (PDMS) as a modifier of DGEBA and ana- of hydrogenated terpinene-maleic ester type epoxy resin with
lysed thermal and mechanical behavior. They investigated secondary amines (diethylamine, N-methylethanolamine
that PDMS with low molecular weight could be dispersed and diethanolamine). The results showed that the epoxy-
in the DGEBA matrix more evenly. urethane polymers, with glass-transition temperatures
Results indicated that the block copolymer has good (Tgs) in the range 5 to 37
C, had good thermally resistant
compatibilizing effect and higher impact strength. Mean- properties, and the temperatures at 5% weight loss were in
while, Mohan and Srivastava[20,21] investigated the effect the range 235–280
C .
of saturated and unsaturated acid on the characteristic For the electronic encapsulation, the polymers should
properties of epoxy resins by the use of formic acid, acetic have reactive flame-retardant additive properties. However,
acid, propionic acid, benzoic acid, cinnamic acid, the common epoxy resins system cannot satisfy the flame-
andacrylic acid. The epoxide equivalent weight increased resistance requirements. Introducing the imide group[28]
although chlorine content, hydroxyl content decreased in has been improved flame resistance but it’s reactivity was
the presence of acids. The degradation of the chlorine low. Wang and Shieh[29] worked on this field and prepared
content value was due to the formation of a poly(allyol an epoxy resinsc ontaining phosphosus, which had flame-
chloride) during resinification. retardant effectiveness, was used in the electronic encapsula-
Recently, Bayramoglu et al.[22] used adipic acid as a tion. These phosphorous containing DOPO epoxy resins
modifier of methacrylated bisphenol A-based epoxy resins f6-H-dibenz[c,e][1,2]-oxaphosphorin-6-[2,5-bis (oxiranyl-
in 2007. The result indicated that the tensile properties methoxy) phenyl]-6-oxideg was synthesized and cured.
and thermal stabilities of modified epoxy mainly depend The phosphorus-containing epoxy resin showed lower
on the adipic acid content. The best results were obtained weight loss temperature and higher char yield than that
with 5 wt% adipic acid modification. An attempt to of bisphenolA-based epoxy resin due to the rigid struc-
improved the thermal and aging characteristics of epoxy ture of DOPO and the pendant P group thus showed
resins[23] was done by blending with either epoxy phenolic better flame retardancy, higher glass transition tempera-
novolac(EPN) or epoxy cresol novolac (ECN) with bisphe- ture, and thermal stability. High limiting oxygen index
nol A epoxy resins. It was concluded that novolac prepared (LOI) value and UL-94 V-0 rating could be achieved with
by p-cresol was a better modifier than that based on phosphorus content and no fume and toxic gas emission
phenol-based novolac. were observed. The high char yields and LOI values as
A liquid crystalline epoxy resins[24], 1,10 -bis [4-(2,3- well as excellent UL-94 vertical burn test results of
epoxypropoxyphenyleneinino methyl)]-2,20 -dimethylbiphe- DOPO epoxy resin indicated the flame-retardant effec-
nylene (BMPE) was synthesized and the effect of BMPE tiveness so it has been used in an electronic encapsulat-
content on mechanical and thermal properties of its blends ing application.
 MODIFICATION, PROPERTIES, AND APPLICATIONS OF EPOXY RESINS 111

Thermoplastic polyurethane is generally used in the release) rate (G1c) and a fracture toughness (strain inten-
field of semiconductor encapsulation. The formation of an sity) factor (K1c) rate was used as a measure of toughness
interphase between hydroxyl groups of the already cured of materials[34]. Hourston et al.[35] synthesised a blend of
epoxy resin and an urethane was shown by Kieffer et al.(30). tetrafunctional epoxy resin polyetherimide (PEI).
The network density of the epoxy resin was controlled by the The material had two phase morphology and improved
functionality of the curing agent. Furthermore the depth of in fracture properties (K1c and G1c) but the morphological
interpenetration was reduced, if additional hydroxyl groups structure was not changed. The modified acrylic rubber
are present in the epoxy resin. The literature of encapsulation epoxy resin[36] was prepared by copolymerization of butyl
was further enriched by Ho and Wang[31], who synthesized acrylate (BA) with vinylbenzyl glycidyl ether (VBGE).
phenol-based and naphthol-based aralkyl epoxy resins, The modified epoxy resin had two-phase morphology in
which was semiconductor. which the rubber particles with average diameter of 2 mm
The incorporation of thermoplastic polyurethane were dispersed in the epoxy matrix. The resultant resins
particles in the synthesized epoxy resins matrix was were good interfacial adhesive between the rubber particles
achieved via epoxy ring-opening with the isocyanate and the matrix, and have increased toughness.
groups of urethane prepolymer to form an oxazolidone. Misaki et al.[37] improved the fracture properties of p,
0
They concluded that the naphthalene containing aralkyl p -diaminodiphenyl methane-cured epoxy resin and various
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epoxy resin has a low coefficient of thermal expansion, heat kinds of aromatic and aliphatic glycidyl compounds. Most
resistance, and low moisture absorption, whereas phenol of these compounds promoted the fracture toughness
aralkyl-type epoxy resins are capable of imparting low elas- although heat resistance was decreased by glycidyl com-
tic modulus and result in a low stress matrix for encapsula- pounds. The cross-linked density of resins were inversely
tion applications. Modification of the synthesized aralkyl proportional to the impact strength and fracture toughness.
epoxy resins with polysiloxane thermoplastic polyurethane Toughening of epoxy resins was improved by N-Phenylma-
has effectively reduced the stress of cured epoxy resins. leimide (PMI)-N-cyclohexylmaleimide (CMI)-styrene (St)
In the field of encapsulation, epoxy resin is a material terpolymers[38] and the epoxy resins was cured with p,p0 -
commonly used for the light-emitting diodes (LED) encap- diaminodiphenyl sulfone (DDS).
sulation. Three epoxy resins[32] were chosen in this study: (i) The 140% fracture toughness was increased by the
D.E.R.-331 was a bisphenol A type epoxy resin (ii) Eporite- addition of 10 wt% of the terpolymer (45 mol % PMI,
5630 was a bisphenol A type epoxy resin modified with a 5 mol % CMI, and 50 mol % St units) with Mw higher than
UV stabilizer (iii) ERL-4221 was a cyclo-aliphatic epoxy 247,000. The glass transition temperatures of the modified
resin. In this synthesis methyl hexahydrophthalic anhydride resins were equal to or higher than that of the parent epoxy
(MHHPA) and tetra-butyl ammonium bromide (TBAB) resin. The morphologies of the modified resins were depen-
was used as curing agent and a catalyst, respectively. On dent on the terpolymer molecular weight and concentration.
the bases of the thermal, environmental, and optical proper- Researchers[39] used three kind of epoxy resins to modify
ties of the cured epoxy resins, it was concluded that the toughening properties, such as DGEBA, TGPAP
Eporite-5630 was the best choice of the balance properties (triglycidyl-p-aminophenol), and TGDDM(tetra-glycidyl
for LED applications among the others. diamino diphenyl methane). They were mixed in varying
Wang et al.[33] prepared flame retardant epoxy system proportions and cured with both 3,3?-diamino diphenylsul-
from epoxy resin (diglycidyl ether of bisphenol A), low phone and 4,40 -[1,4-phenylene(1-methyl ethyl idene)]
molecular weight polyamide (cure agent, LWPA), and bis(2,6-dimethyl benzenamine). All the blends could be
ammonium polyphosphate (APP). The results of LOI and satisfactorily cured and gave homogeneous materials.
UL-94 indicate that APP had improved the flame retar- It was found that the glass transition temperature varied
dancy of LWPA-cured epoxy resins. Only 5 wt% of APP with composition, whereas values of the strain energy
could increase the LOI value of epoxy resins from 19.6 to release rate (G1c) and the stress intensity factor (K1c)
27.1, and improved the UL-94 ratings, reaching V-0 rating showed relatively small variations with the blend compo-
from no rating when the mass ratio of epoxy resin to LWPA sition. Finally, it was concluded that the toughened epoxy
is 100=40. It was interesting that LOI values of flame resins were prepared by adding a polyetherimide (PEI), in
retardant-cured epoxy resins (FR-CEP) increase with varying proportions, to the resin mixture and concluded
decreasing LWPA. that the 75=25 TGPAP=DGEBA resin mixture was the
Toughness is a good combination of strength and duc- most tough enable combination.
tility. It resists crack propogation, which is the ability of An approach to improve the toughening of epoxy resins
any material to deform plastically and to absorb energy in was done by Dai et al.[40] by blending it with HECA
the process before fracture is termed toughness. There are (hydroxyethyl cellulose acetate). HECA was totally
several approaches to enhance the toughness of epoxy resins miscible with uncured epoxy resin, but immiscible with
have been reported. A fracture energy (strain energy diamine cured epoxy resin matrix. HECA exhibited the
 112 P. MOHAN

highest toughening ability when the epoxy resin was cured deterioration of the tensile properties. The impact strength
at the temperature at which the HECA existed as a liquid increased continuously and reached a maximum value.
crystalline state. The toughening ability was influenced by The higher fracture toughened epoxy resins were
the degree of substitution for acetyl of HECA, but the synthesized by the modification of epoxy resins by acrylic
impact strength of the epoxy resin blends decreased with materials[46]. The fracture toughness in modified epoxy
increasing the acetyl of HECA. resins was shown by the core=shell acrylic particles that
A more recent approach, interpenetrating network was swelled, along with the epoxy resin under exposure to
(IPN), was used to improved toughness of epoxy resins heat and gel. In this process, the epoxy resin penetrated
by Harani et al.[41] For this purpose, a PU prepolymer the surface of the shell layer and a bond was formed between
based on hydroxyl-terminated polyester has been synthe- the epoxy matrix and the core=shell acrylic particles.
sized and used as a modifier at different concentrations in They suggested that the epoxy matrix around the core=
epoxy resins to prepared IPN (Epoxy-PU). In this study, shell acrylic particles had the effect of increasing the level
the results showed that, in IPN formation, the epoxy and of energy absorption due to plastic deformation of the
the PU prepolymer reacted chemically (via grafting) and matrix and showed higher fracture toughness. Xiao
caused a drastic improvement in toughness and but not et al.[47] synthesized an epoxide-acrylate hybride oligomer
up to the satisfied level. by the reaction of DGEBA and acrylic acid. The hybride
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Again Harani et al.[42] further introduced the hydroxyl- oligomer showed some intergroup interaction in the photo-
terminated polyester resins as toughening agents for epoxy polymerization process, which include decreasing the oxy-
resin. For this purpose, the modifier that was a hydroxyl- gen inhibition to radical process. The hybride oligomer
terminated polyester resin(different concentration) was cured film showed a more uniform polymer net and higher
used at different concentrations. The results showed that glass transition temperature than that the blend of epoxy
hydroxyl-terminated polyester improved toughness and acrylate and epoxy resins.
showed better result than that of previous results. It had The literature on the toughening of epoxy resins was
been found that the mechanical properties of polymer enriched by Cao et al.[48], who improved toughening in
materials with an IPN structure were fairly superior to the epoxy resins by 4–24 phr polyester with average molecu-
those of ordinary polymers. lar weight 1.9  104 g=mol. The results showed that the
Kumar and Sivasanka[43] synthesized poly(ether impact strength and tensile strength of the modified epoxy
urethane)-based cyanate ester resin (PEUCER) with a resin were remarkably greater than those of the unmodified
biphenyl polyether. It showed better performance as a cured epoxy resin. The most suitable composition for the
toughening agent in a two-part epoxy laminate system and modified epoxy resin was the addition of 16 phr polyester,
also had better thermal stability, adhesion and flexibility. which led to 138 and 46% incremented in the impact
The toughening in the epoxy resins was successfully[44] done strength and the tensile strength, respectively. The polyester
by the introduction of hydroxyl groups in the epoxy resins dispersing in the epoxy matrix was amorphous when its
direct employment of poly(tetramethylene) glycols (PTMG) addition was less than or equal to 12 phr.
as toughener. With the incorporation of a small amount of Polysiloxanes have excellent thermal stability, moisture
PTMG, the critical fracture energy of the cured resin was resistance, good electrical properties, low stress and lower
improved greatly, while the flexural strength and the modu- Tg values. However polysiloxanes are not compatible with
lus were less influenced. epoxy resins. So, Varley[49] studied the effect of three
Several approaches have been used to improve the low-viscosity additives such as: i) epoxy-terminated
toughness of epoxy resins, including the addition of fillers, aliphatic polyester hyper branched polymer; ii) carboxy-
rubber particles, thermoplastics, and their hybrids, as well terminated butadiene rubber; and, iii) aminopropyl-
as interpenetrating polymer networks (IPNs). None of them terminated siloxane on the toughening of two epoxy resin
have been able to suitably increase resin toughness without systems. The systems used have a lower-reactive resin based
sacrificing tensile properties. Therefore, in an attempt to fill upon the diglycidyl ether of bisphenol A (DGEBA)and the
this gap, Bhuniya and Adhikari[45] in 2003 experimented amine hardener diethyltoluene diamine, while the second
with newly synthesized hydroxy-terminated silicon- epoxy resin system was based upon tetraglycidyl methylene
modified polyurethane (SiMPU) oligomers as toughening dianiline (TGDDM) and a cycloaliphatic diamine hardener.
agents for epoxy resins. The synthesized SiMPU oligomers, The results gave the information that the TGDDM-
with different concentrations, formed IPNs within the based resin systems were found not to be toughened by
epoxy resins (DGEBA). The resultant IPN products were any of the additives due to the lack of plastic deformation
cured with diaminodiphenyl sulfone, diaminodiphenyl of the highly cross-linked epoxy network, although
ether, and a Ciba-Geigy hardener under various curing con- DGEBA-based resin system was found to impart similar
ditions. The results showed that 15 phr SiMPU led to better levels of toughness improvement by both epoxy-terminated
impact strength of epoxy resins than the others without the hyperbranched polyesters and epoxy-terminated hyper-
 MODIFICATION, PROPERTIES, AND APPLICATIONS OF EPOXY RESINS 113

branched polyesters rubber additive, but the siloxane hardness, adhesion, and flexibility of the film. The improve-
additive was found not to improve toughness at all for the ment in these properties indicated that the rubber-modified
DGEBA-based resin system due to the poor dispersion resin would be more durable than the epoxy based on
within the epoxy matrix. di-glycidyl ether of bis-phenol-A and other epoxies. The ther-
The literature on blending of epoxy resins was further mal stability of the cycloaliphatic-based epoxy resin was
strengthened by Gupta et al.[50], who synthesized blends increased with the addition of 15 wt% CTBN in epoxy matrix.
of epoxy resin (DGEBA) by anionically polymerized poly- The grafted silicon rubber[55] had been used to toughen
caprolactam and studied the curing reactions, kinetics, an epoxy resin, which was prepared by copolymerization
morphology, and thermal stability. The results analysis of methyl vinyl silicon rubber with vinyl acetate. The results
indicated that the initial degradation temperature (Ti), indicated that the epoxy resins had been reinforced and
activation energy (E), heat of reaction (DH), and pre- toughened obviously by the addition of g-SRs. The mechan-
exponential factor (Z) increased with increasing DGEBA ical properties of modified epoxy resins depended not only
content from 50 to 80 wt% in the reactive blends and on synthesis processes of copolymerization, but also on
increased drastically above 70 wt% DGEBA content due the amount of the g-SRs. The best combination of tensile
to the higher cross-link density. and impact strengths for the cured modified epoxy resins
The extent of curing reaction of polycaprolactam with had been reached by that modified with 15 phr g-SRs.
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DGEBA is dependent on the blend composition. Cardanol- Toughening of epoxy resins was provided by the silica
formaldehyde epoxy resins[51] were prepared by the blending nanopartical reinforcement[56] was studied by of adding 5
of DGEBA resins and cardinal-phenol formaldehyde (CPF). vol % of silica nanoparticles on an epoxy resins via a sol-gel
The CPF was the main constituent of Cashew net shell liquid process. The addition of 5 vol %. silica-nanoparticles could
(CNSL). DGEBA-CPF blend showed higher water absorp- improve the stiffness and the toughness of an epoxy resin.
tion, improve toughening with marginal improvement in It has understood that by the use of different additives
mechanical and surface hardness properties. the toughening property of epoxy resins was improved.
Epoxy asphalts[52] were prepared by mixing of modified These results gave an idea to the researchers, that how
asphalt fstyrene-butadiene-styrene (SBS)g with epoxy resin. can they not use the epoxy resins for improving the tough-
The effects of epoxy resin contents, ratio of curing agent to ness of the other polymers. Thus Shulin et al.[57] used the
epoxy resin and curing temperature on properties of epoxy epoxy resins to improve the toughening properties of
asphalt were investigated. Results indicated that epoxy resin polyamide-6 (PA6) blend by introducing the epoxy resin
and epoxy asphalt showed similar curing efficiency. Epoxy in PA6 =ABS-g-MA) and (maleic anhydride functionalized
asphalts can be cured at 120
or 60
C and its viscosity at acrylonitrile-butadiene-styrene copolymer) blends. It was
120
C can meet the demands of asphalt mixture. noted that the impact strength of PA6=ABS-g-MA could
The chemical reaction of epoxy resin in epoxy asphalt was be improved from 253 to 800 J=m with the addition of
slow and reaction occurs not only with the curing agent but epoxy resin when the ABS-g-MA content was set at 25 wt%.
also carboxylic acid in epoxy asphalt. The softening point The effects of epoxy resin contents on rheological
and tensile strength of epoxy asphalt increased with increas- properties of epoxy-asphalt binders were studied[58] by
ing epoxy resin contents. The softening point and tensile using dynamic shear rheometer. Experimental results indi-
strength of epoxy asphalt were markedly improved when cated that the viscoelastic performance, and elasticity of
epoxy resin content was more than 30 wt%, which is attrib- asphalt binder was improved at high temperatures when
uted to formation of continuous structure of epoxy resin. epoxy resin is added.
In earlier, the epoxy resins had limited application was Epoxy resins, because of their adhesive properties, have
due to their brittle nature and poor thermal conductivity. been widely used for shoulding or blending of polymers.
Rubber modification was introduced, as a major toughen- The adhesive property of epoxy resins are depend on the
ing approach to overcome the inherent brittleness of epoxy curing condition and temperature, although it is inferior
polymers, a large number of investigations have been con- at ambient temperature, improved at high temperature.
ducted to elucidate different aspects of rubber-toughened Gouri et al.[59] studied the adhesive and thermal character-
epoxies[53]. The ultimate aim of the study was to modify istics of maleimide-functional novolac resins. When the
the brittle epoxy matrix by the liquid rubber to improve resins were co-cured with imide and malemine, the adhesive
toughness characteristics by the synthesis of an epoxy resin properties improved significantly and showed a strong
based on nonglycidyl ether and varying content of carboxyl- dependence on the nature of the epoxy resin. Optimum
terminated (poly)butadiene acrylonitrile (CTBN) copoly- adhesive properties were obtained for novolac resins with
mer[54] was cured by using an aromatic amine hardener. a moderate concentration of maleimide groups (Fig. 6),
Blends samples exhibited better properties as compared taken on a 1: 1 hydroxyl-epoxy stoichiometry with a novo-
to pure epoxy resin in terms of increase in impact strength lac epoxy resin. In comparison to the conventional novolac,
and elongation-at-break of the casting and gloss, scratch the imide-novolac contributed to improve adhesion and
 114 P. MOHAN

of epoxy resins on the adhesive property of the blends of

mono-carboxyl-terminated poly(2-ethylhexyl acrylate-co-
methyl methacrylate) was studied by Garcia et al.[63] by
using three different aliphatic amine epoxy hardener. They
observed that biggest lap shear strength of blends using
FIG. 6. Meleimide.
1-(2-aminoethyl)piperazine (AEP Fig. 7) as hardener was
most effective adhesive for steel-steel joints.
Parveen et al.[64] studied antimicrobial activity of aniline-
better adhesive property retention at higher temperature formaldehyde resin modified by adding piperazine moiety
when cured with the novolac-epoxy resin. and its metal polychelates. It was concluded that all the
Along with the adhesive property of epoxy resins in the metal polychelates had higher thermal-resistance property
field of polymer, Motawie and Sadek[60] prepared a wood compared to the common resin (AFP) and all the synthe-
adhesives epoxy resins, based on bis (4-hydroxy phenyl) sized metal polychelates showed excellent antibacterial
1,1-cyclohexane. It was prepared and modified with various activities against the selected bacteria. Improvement of
types of the phenolic resins such as phenol-, cresol-, resorci- lap shear strengths of adhesive copper joints by sulfur-
nol-, and salicylic acid-formaldehyde resins. Then it was containing modifiers.
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characterized by high tensile shear strength values. The effect Epoxy resins are widely used in electronics and electrical
of the structure of phenolic resins on the tensile shear industries because of their superior properties. In recent
strength values of formulated resin indicated that the more years, excellent bonding properties for metals (e.g., copper,
suitable conditions are 1:2 weight ratio of phenol-or cresol- gold, aluminium, silver, etc.), to which it was hard to
formaldehyde to epoxy resin in the presence of phthalic anhy- adhere, have become desirable for epoxy resins in the elec-
dride (20 wt%) of the resin content as a curing agent at 150
C tric and electronics industrial fields. However, epoxy resins
for 80 min. Resorcinol-or salicylic acid-formaldehyde=epoxy have only poor bonding strength to the metals. To increase
resins formulated at 1:2 weight ratio were cured in the pres- the hetero-junction strength between epoxy resins and cop-
ence of paraformaldehyde (20 wt%) at 150
C for 60 min. per, Hirano et al.[65] introduced sulfur (MPS polythioe-
Metallic and glass coatings from the previous resins were also sters), which provided strong interactions with metals.
prepared and evaluated as varnishes or paints. The epoxy resins containing sulphur moiety and a curing
In another pioneer publication Murakami et al.[59] syn- agent were cured between copper plates at 120
C for 2 h
thesized wood-based epoxy resins from resorcinol-liquefied and at 170
C for 2 h. The effect of the added modifiers
wood, and epichlorohydrin under alkali condition. The flex- was evaluated by the lap-shear testing method. It could be
ural strength (150–180 MPa) and the modulus of elasticity demonstrated that MPS polythioesters have a beneficial
(3.2 GPa) of the highly cross-linked, wood-based epoxy effect on the enhancement of the epoxy resin=copper
resin were equivalent to those of the commercially available hetero-junction. The most effective example was the
DGEBA epoxy resins. The shear adhesive strength of the addition of 20 phr of the MPS_7 polythioester, which
wood-based epoxy resin was higher than that of DGEBA increased the lap shear strength from 5.7 to 17 Mpa.
when plywood was used as the adhesive substrate. The Basically epoxy resins are known for its insulating pro-
mechanical and adhesive properties suggested that the perty, but when it is used as an adhesive between conducting
wood-based epoxy resins would be well suited for matrix object then the conductivity breaks down. So the modifi-
resins of natural plant-fiber reinforced composites. cation of epoxy resins for improving the electrical conduc-
For improving the adhesive property and the fracture tivity was done by the addition of different transition
toughness in the epoxy resins[62], it was blended with a dia- metals acrylates during the synthesis of epoxy resins[66–70]
llyl phthalate resin. An allyl ester compound [1,4-diallyloxy in our previous lab. It was observed that the epoxide
carbonyl-2,5-benzenedicarboxylic acid (DAPY)]was used as equivalent weight of these modified epoxy resins was greater
compatibilizer, which reacted with the diallyl phthalate resin than that of blank epoxy resins. On the bases of IR,
and epoxy resin to have allyl groups and carboxylic acids on 1H-NMR, and 13C-NMR spectroscopy it was concluded
the end of the molecular chain. The results suggested that
the secondary hydroxyl group generated by the addition
reaction of the epoxy resin and DAPY and the secondary
hydroxyl group existing in the molecular chain of the epoxy
resin formed hydrogen bonds with the hydroxyl group of
water existing on a metal surface, and as a result, the
adhesive strength to metal such as steel increased.
The fracture toughness of the diallyl phthalate resin was
increased by modification with the epoxy resin. The effect FIG. 7. 1(2-aminoethyl) piperazine.
 MODIFICATION, PROPERTIES, AND APPLICATIONS OF EPOXY RESINS 115

that the complex was formed between the oxygen of ether between the epoxy and HTBN, forming a urethane linkage
linkage of epoxy resins and the metal having following with the former and an oxazolidone ring with the latter. A
structure (Fig. 8): carbon fiber-reinforced composite was prepared by
The cured resins have excellent thermal and chemical Carfagna et al.[73] with the help of liquid crystalline epoxy
resistance, but these resins were not showed improved elec- resin. It was concluded that the presence of carbon fibers
trical conducting property. Recently, this author[71] investi- did not affect the reaction rate. A conventional isotropic
gated the electrical conducting properties of modified epoxy epoxy resin is used as a model compound in the rheological
resins cured with ylide. The modification was done by the analysis.
introducing metal acrylate during synthesis of epoxy resins. An overview about nanocomposites based on epoxy
It was observed that epoxide equivalent weight and chlorine resins was given by Hartwig et al.[74] The proper character-
content of these modified epoxy resins were increased, ization of the nanocomposites was provided the information
whereas hydroxyl contant decreased in the presence of these that combustion properties, strength and permeation can be
metal acrylates. improved by organically modified layered silicates. A few
The molecular weight of modified epoxy resins was just years later, nonaqueous synthesis of nanosilica in diglycidyl
double of the epoxide equivalent weight. The disappearance ether of bisphenol A epoxy (DGEBA) resin has been
of the epoxy ring at 910–950 cm1 of cured epoxy resins in successfully achieved[75] by the reacting tetraethoxysilane
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IR spectroscopy concluded that the reaction was done (TEOS) directly with DGEBA epoxy matrix, at 80
C for
between curing agent (ylide) and the epoxy group of modi- 4 h under the catalysis of boron trifluoride monoethylamine
fied epoxy resins. DSC data gave the information that the (BF3MEA). BF3MEA was proved to be an effective cata-
Tg of epoxy resins containing cobalt acrylate was lower lyst for the formation of nanosilica in DGEBA epoxy under
than that of blank epoxy resins as well as other modified thermal heating process.
epoxy resins containing metals such as Ni[69], Bi[70], Zn[66]. It was found that the nanosilica containing epoxy exhib-
The epoxy resins containing cobalt acrylate had good ited the same curing profile as pure epoxy resin, during the
electrical conductivity than that of blank epoxy resins as curing reaction with 4,40 -diaminodiphenysulfone (DDS). It
well as epoxy resins containing other metal acrylates. had higher glass transition temperature (221
C), almost
Composites are applicable in the area of sporting goods, 50
C higher than that of pure DGEBA-DDS-BF3MEA-
biomedical devices, electronics, transportation and civil cured resin network.Yu et al.[76] synthesized epoxy resins
engineering structure and it has also a major part of aero- = calcium carbonate nanocomposite. Dispersion of nano-
space industry. The behavior of the polymer composites particles in resins matrix was confirmed by SEM analysis.
strongly depends on the properties of the interphase between Novel epoxy nanocomposites based on a diglycidyl ether
polymer and the reinforcing material. The epoxy resins have of bisphenol A (DGEBA)[77] were synthesized by epoxy
occupied a dominant position in the manufacture of high functionalized hyperbranched polymer (HTTE) and nano-
performance composites. Applied force can be completely Al2O3. The effect of the nano-Al2O3 particles and HTTE
exchanged between the resins matrix and the reinforcing on the structure and properties of epoxy nanocomposites
phase using the whole stability range of both fiber and the were studied. The improvement in impact properties of
polymer. The fiber-reinforced epoxy resin matrix composite these nanocomposites indicated that the incorporation
was prepared by the chemical modification of DGEBA of nanoparticles and hyper-branched epoxy effectively
using reactive liquid rubber (HTBN [hydroxy-terminated improved the toughness of epoxy composites without sacri-
poly (butadiene-co-acrylonitrile)]) and TDI (tolylene ficing thermal conductivity and bulk resistivity compared to
di-isocyanate) by Sankaran and Chandra[72]. the neat epoxy and Al2O3=DGEBA, obtaining a well
The study of reaction and the structural changed during dispersion of nanoparticles in epoxy matrix and solving
the modification showed that TDI acted as a coupling agent the drawbacks for single fillers filled epoxy resins.

CURING MODIFICATIONS WITH ENGINEERING

APLICATIONS
The single most valuable property of epoxy resins is their
ability to transfer liquid state into the solid state. This con-
version is done by the addition of chemically reactive com-
pound (curing agent) without elimination of by-products. A
reactive curing agent or hardener has two or more reactive
groups in a molecule. It reacts with the epoxy group and is
coupled directly into the cured system as a structural mem-
ber of the polymer. The curing agents or hardeners are cate-
FIG. 8. Structure of epoxy resin-metal acrylate complex. gorized as either catalytic or coreactive[78]. The catalytic
 116 P. MOHAN

FIG. 9. Reactionscheme: Catalytic curing.

curing agent initiates resinhomopolymerization. It was

initiated by Lewis acid (BF3) or Lewis base (tertiary amine)
(Fig. 9).
Coreactive curing agents are ploy functional compounds
having hydrogen and act as a co-monomer in the polymer-
ization process (Fig. 10). Generally multifunctional amine,
amide derevative, anhydride, polyphenol, polycarboxylic
acid are used as co-reactive hardeners.
The curing mechanism of epoxy resins may occur in one
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of the two different ways: either anionically or cationically.

Both types of reactions are important in epoxy resins tech-
nology[78]. In the anionically mechanism, the epoxy group FIG. 12. Cationic curing.
may be opened by the formation of anion (Fig. 11):
However, in the cationic mechanism (Fig. 12), the epoxy
group may be opened by a active hydrogen to produced a aromatic amine > cycloaliphatic amine > aliphatic amine,
new chemical bond and a hydroxyl group through the depending on the curing agents. Meanwhile, many excellent
formation of cation. research studies had been compiled by this author[1] in 1997,
The curing temperature and thermal stability are most which highlighted the use of different acidic, basic and other
important factor in determining the application of the epoxy hardeners to improved the characterstic properties of epoxy
resins. The curing temperature and thermal stability of epoxy resins. The data using different catalytic and coreactive curing
resins depend on the type of curing agents and curing con- agents are summarized in Table 1.
dition. Nakamura and Arima[79] studied the curing
temperature and thermal stability of various compounds ALTERNATE METHODS OF MODIFICATION WITH
and concluded the curing temperature and thermal stability ENGINEERING PROPERTIES
decreased was as follows: acid anhydride > Phenol ¼ Progress in the chemistry of epoxy resins results, the
introduction of new methods for modifications of epoxy
resins. Liaw and Shen[109] gave two processes (Taffy Pro-
cess, Advance Process), by which bisphenol A was success-
fully replaced with bisphenol S derivatives (i, ii, iii, iv, v).
1. [4-(b-hydroxyethoxy)-phenyl]sulfone (HEPS) (Fig. 10),
2. bis [4-(b-hydroxy(iso)propoxy)-phenyl]sulfone(HPPS),
3. 3,30 ,5,50 -tetrabromobis phenol-S(TBS),
4. bis[3,5-dibromo-4-(b-hydroxyethoxy)-phenyl]sulfone
(HEETBS)
5. bis[3,5-dibromo-4(b-hydroxy(iso)propoxy)phenyl]-
sulfone (HPETBS).
(a) The taffy process in which direct addition of epi-
FIG. 10. Reaction scheme: Co-reactive curing.
chlorohydrin to bisphenol-S derivatives and (b) advance-
ment process in which the main constituent was in melt
condition. The product formed by ‘‘taffy’’ (direct addition
of epichlorohydrin to bisphenol-S derivatives) process con-
taining both odd- and even-numbered diepoxide oligomers
is in contrast to the ‘‘advancement’’ (main constituent was
in melt condition) process which leads to products contain-
ing predominantly even-numbered diepoxide oligomers.
FIG. 11. Epoxy chain. Epoxy equivalent, melting points (Tm), Tg, and melt
 Downloaded by [Pennsylvania State University] at 09:50 16 March 2013

TABLE 1
Curing agents and their properties
SN Epoxy Resins Name of Curing Agent Types of Curing Agent Inference Reference
1 Epoxy resins Dodecenyl succinic Coreactive Fig. 13 Tensile strength of epoxy resins were 80
anhydride (DDSA) improved due to the presence of long
hydrocarbon chain having a double
bond at the center of chain.
2 Diglycidyl ether of ethylene The reactions were found to follow 81
glycol first-order kinetics with an activation
energy in the range of 36–84 kJ mol1
3 Tetraglycidyl Diamino diphenyl Catalytic Fig. 14 The curing reaction is auto-catalytic due 82
diaminodiphenyl methane sulfone to presence of aniline.
resin
4 epoxy-multiacrylate resins Autocurable Catalytic Young’s modulus and breaking strength 83
of epoxy resins decreased because
attractable hydrogen decreased
cross-link density of epoxy resins during
curing.
5 DGEBA Trimethoxyboroxine Catalytic Fig. 15 The curing behavior of TBM was good in 84
(TMB) in N2or O2 oxygen atmosphere rather than nitrogen
atmosphere atmosphere.

117
6 Carboxyl-terminated Tris (N,N-dimethyl - Coreactive The curing occurred at room temperature 85
polybutadiene- aminomethyl) phenol due to the presence of CTBN, which
acrylonitrile copolymer provided structure adhesive property.
(CTBN)
7 Hydroxy methylgroup 4,40 -diaminodiphenyl Coreactive The presence of hydroxymethyl group 86
containing epoxy resin methane and m- accelerated an epoxide amine reaction
phenylenediamine which improved heat resistance and
(molar ratio,6:4) cross-link density of fully cured epoxy
resins.
8 EOCN(o-Cresol 4,40 -diaminodiphenyl Coreactive The average molecular weight of the 87
novolac-type epoxy resin) methane and epoxy resin was lower due to the higher
m-phenylenediamine concentration of hydroxymethyl group.
(molar ratio, 6:4) The rate constant (k) and glass
transition temperature (Tg) were higher
but the activation energy (Ea) was
lower.
9 EPCDAMDI(urethane- 4,40 -diaminodiphenyl Coreactive Fig. 16 It was found that onset and peak 88
modified epoxy resins) methane and temperature of the exothermic curing
m-phenylenediamine was lower than 2-cresol novalac-type
(molar ratio 6:4) epoxy resins(EOCN).
(Continued )
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TABLE 1
Continued
SN Epoxy Resins Name of Curing Agent Types of Curing Agent Inference Reference
10 EPCDATDI-DGEBA(uret- 4,40 -diaminodiphenyl Coreactive The toughness and impact strength was 89
hane elastomer modified methane and 60–70% increased when 10 wt%
epoxy resins m-phenylenediamine EPCDATDI was added in it. But the
(molar ratio 6:4) glass transition temperature was
uneffected.
11 Cyanate functionalized Carbamate Catalytic It was found that major cross-reaction 90
resin and epoxy product is a racemic mixture of
functionalized resin enantiomers, which contains an
oxazolidinone ring formed by one
cyanate molecule and two epoxy
molecules. The cross-reaction between
cyanate and epoxy is limited.
12 Epoxy resins Amine Coreactive The curing reaction was studied by NIR 91
spectroscopy, which showed that inter
and intra molecular hydrogen bonding
exist between epoxy and amine
hardener.
13 Blend of amine-cured epoxy Di-aminodiphenylsulph- Catalytic Blending improved ductility and 92

118
resin systems & up to 50% one (DDS) toughness-related properties at 20–40%
polyethersulphone (PES) PES contents.
14 Spiro-orthocarbonate Di-isocyanates Catalytic The spiro compound and di-isocyanates 93
modified epoxy resins controlled the number-average
molecular weights of the pre-polymers.
Rate constants (k) of modified epoxy
resin was greater than others resins.
15 Epoxy resins Urethane Catalytic The interphase between epoxy resins and 94
an urethane through hydroxyl group
and isocynate group, respectively was
conformed by IR spectroscopy.
16 Poly-amide resins(PAs) DGEBA AND TGPAP Catalytic Epoxy-based polyamide was successfully 95
(trifunctional used as curing agent for coating
epoxy resins) application of DGEBA and TGPAP.
17 NC-3000P and EOCN-C Xylok and DCPDP Catalytic The cure kinetics was mainly depending 96
epoxy resin (dicyclopentadiene- on the type of hardener not on the kinds
type phenol resin) of epoxy resins. The highest reaction
rate values were obtained in NC-3000P
and EOCN-C epoxy resin systems with
xylok.
(Continued )
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SN Epoxy Resins Name of Curing Agent Types of Curing Agent Inference Reference
18 LC dimeric epoxy Primary diamines or Catalytic The mesogen structure, in the mesogenic 97
monomers tertiary amines cores affect the ability to form ordered
networks.
19 Nadic methyl anhydride Cycloaliphatic epoxy Catalytic DSC thermogram showed that curing of 98
(NMA)= methyl resins (C1 and C2) C1 started earlier than that of C2. The
tetrahydrophathalic hydroxyl groups formed during
anhydride (MTHPA) esterification were found to catalyze the
epoxy-anhydride reaction.
20 DGEBA Nickel complex of O- as a ligand The onset decomposition temperature and 99
phenylendiamine char yield (at 700
C) of the crosslinked
(OPD) material were 290
C and 27%,
respectively. The activation energy of
the solid-state thermal degradation
process was evaluated by Ozawa
approach, resulting in 95–138 kJ=mol
on a range of 2–20% decomposition
conversion.
21 Bisphenol A dicyanate Reaction between them Thermal, moisture absorption, and 100
(BADCy) and DGEBA mechanical testing showed that
E51-modified BADCy performed better
than DGEBA due to its lower

119
molecular weight. It was also concluded
that the higher molecular weight epoxy
resins (having more hydroxyl groups)
required low curing temperature.
22 DGEAC=DGEB DDM=DETDA The presence of DGEB caused an increase 101
in curing range and exothermic heat.
The reaction follows autocatalytic
kinetic mechanism due to the presence
of the hydroxyl group.
23 Bisphenol-A based Latent curing agent Curing of Na was faster than the Ba. The 102
benzoxazine (Ba) and epoxy resin (Ba) showed good heat
phenol-novolac-based resistance, flame resistance, and
benzoxazine (Na) mechanical properties than those from
epoxy resin (Na).
24 Bisphenol-A based -do- Both types of cured resins showed good 103
benzoxazine (Ba) and heat, flame resistance, mechanical
epoxy resin (Ep) properties, and electrical insulation due
to presence of latent curing agent, than
the cured resin from Ba and Ep without
latent curing agent.
(Continued )
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TABLE 1
Continued
SN Epoxy Resins Name of Curing Agent Types of Curing Agent Inference Reference
25 DGEBA Imidazole derivative Catalytic EMI-g-BGE was an effective curing agent 104
(named as EMI-g- for epoxy resin. The apparent activation
BGE) energy Ea was 71.8 kmol1.
26 Ylide-modified epoxy resins Dimethylsulphonium Ylide played dual nature modifier as well 105
ylide-mercuric chloride as hardener of epoxy resins.
complex
27 Metal acrylate modified Ylide-Pyridiniumdieyan- Catalytic Fig: 17,18 Ylide cured resins had improved 106
epoxy resins omethylide (PDMY), characteristic properties than that of
P-acetylbenzilidenetri- blank epoxy resins. The curing time of
phenylarsoniumylide p-ABTAY cured resins was lesser than
(p-ABTAY) that of PDMY cured epoxy resins, but
both ylides required more curing time

120
than that of polyamide curing agent.
28 Polyurethane (PUs) DGEBA, DGEBC, Coreactive The curing mechanism was studied by 107
DGEBF DSC and concluded that the glass
fiber-reinforced composite had been
laminated and studied its chemical,
mechanical, and electrical properties.
29 PDMS-modified epoxy Auto-catalytic The order of reaction was about 3. The 108
resins PDMS-modified epoxy resins showed
higher early cure reactivity and a lower
cross-linking density due to the
plasticization and restriction effect of
the dispersed PDMS phase.
 MODIFICATION, PROPERTIES, AND APPLICATIONS OF EPOXY RESINS 121

FIG. 15. Trimethyl boroxine.

FIG. 13. Dodecenyl succnic anhydride.
mechanical properties than the PP=epoxy and PP=MAH-
g-PP=epoxy blends with increased impact and tensile
viscosities of epoxy resins were directly proportional to the strength.
concentration of bisphenol S (Fig.19). Czub[113] prepared high-molecular-weight epoxy resins
Meanwhile Castillo et al.[110] used oligomeric waste from modified vegetable oils, such as soybean, rapeseed, lin-
(different composition) for preparation of semi- seed, and sunflower oils as well as hydroxylated soybean and
interpenetrating network (semi-IPN) of epoxy resins. Its rapeseed oils. But it could not reduce the use of petrochemi-
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thermal and tensile properties were dependent on the cal raw materials for the syntheses of high-molecular-weight
composition of oligomer. epoxy resins. Again biobased epoxy resins[114] were synthe-
A new microwave-assisted method[111] was used for the sized from a catechin molecule [condensed tannins formed
synthesis of solid epoxy resins (SER) with desired epoxy- by resorcinol (A) and 4-methylcatechol (B)] (Fig. 21).
groups content. It was based on the poly-addition of 4,40 - During this synthesis the glycidyl ether of catechin (GEC)
isopropyl idenediphenol (BPA). to a lower-molecular- was successfully prepared by the replacement of bisphenol
weight epoxy resin[epoxy value (EV) ¼ 0.57 mol=100 g] in A with the catechin molecule. Resorcinol and 4-methylcate-
the presence of 2-methylimidazole (2-MI) catalyst chol which represent the A and B rings of catechin. GEC
(Fig. 20). The main advantage of the microwave process prepolymer was successfully cured with the curing agent.
is twofold reduction of reaction time in comparison to The thermal property of GEC showed that these new
the conventional heating. It was found that the molecular synthesized epoxy resins displayed interesting properties
weight distribution and degree of branching in resins compared to the commercial diglycidyl ether of bisphenol
synthesized under microwave irradiation was not influ- A (DGEBA). For instance, when incorporated up to 50%
enced by the reduction in reaction time. The values of into the DGEBA resin, GEC did not modify the glass-
EV, Mn, Mw, Mw=Mn, and degree of branching of the transition temperature. Epoxy resins formulated with GEC
products obtained were determined. had slightly lower storage moduli but induced a decrease
Another way for the synthesis of epoxy resins is a of the swelling percentage, suggested that GEC-enhance
dynamic vulcanization process[112], which was used to pre- cross-linking in the epoxy resin networks.
pare the polypropylene (PP)=epoxy blends. The blends In another pioneering work, Wu and Lee[115] prepared
had cross-link epoxy resin particles finely dispersed in the biobased epoxy copolymers by the reaction of liquefied
PP matrix, and they were dynamically cured PP=epoxy Dendrocalamus latiflorus Munro (ma bamboo), bisphenol
blends. Maleic anhydride grafted polypropylene (MAH-g- A, and epichlorohydrin. This pre-copolymer could cure at
PP) was used as a compatibilizer. SEM micrographs room temperature. The higher heat was released during
indicated that the PP=epoxy blends compatibilized with the copolymerization of epoxy resins that enhance the
PP=MAH-g-PP by the reaction between maleic anhydride cross-linking of copolymer epoxy resins with curing agent
groups of MAH-g-PP with epoxy resin. A shift of the at room temperature. The biobased epoxy resins had a
crystallization peak to a higher temperature for all the lower glass transition temperature and better thermal stab-
PP=epoxy blends indicated that uncured and cured epoxy ility. Thulasiraman et al.[116] synthesized chlorinated soy
resin particles in the blends could act as effective nucleating epoxy (CSE) resin from soybean oil and was characterized
agents. The dynamically cured PP=epoxy blends had better by spectral, and titration method. The mechanical proper-
ties such as tensile strength (248–299 MPa), tensile modulus

FIG. 14. 4,40 diaminodiphenyl sulphone. FIG. 16. 4,40 -diphenylmethane di-isocynate (MDI).
 122 P. MOHAN

(2.4–3.4 GPa), flexural strength (346–379 MPa), flexural

modulus (6.3–7.8 GPa) and impact strength (29.7–34.2)
were determined. The impact strength increased with the
FIG. 17. Scheme: Ylide PDMY.
increase in the CSE content. The interlaminor fracture
toughness (GIC) values also increased from 0.6953 KJ=m2
to 0.9514 KJ=m2.

CONCLUSIONS
This is a pivotal time for the modifications of epoxy
resins, for improving their engineering properties, such as:
 Adhesive property of epoxy resins is increased on
increasing the epoxy group, hydroxyl group, phenolic
alcohalic group (wood based epoxy resins)and sulphur
in epoxy resins. Although the presence of hydroxyl
methyl group also increased the heat resistance and
FIG. 18. Scheme: Ylide ¼ p-ABTAY.
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cross-link density because hydroxyl methyl group

accelerated an epoxide amide reaction during curing
condition. The higher molecular weight epoxy resins
required low curing temperature due to presence of
more hydroxyl groups.
 The toughness in the epoxy resins is mainly due to the
presence of bisphenol A. Its toughness and impact
strength was improved by the introduction of urethane,
hydroxyl-terminated polyester in epoxy resins.
 The thermal stability of epoxy resins are responsible for
FIG. 19. I-Bisphenol S, II-[4-(b-hydroxyethoxy)-phenyl]sulfone (HEPS). the presence of aromatic content =cyclic ring= longer
alkyl fragment in prepolymer chain of epoxy resin such
as naphthalene and sulphone. Biobased epoxy resins
also have improved thermal properties.
 The presence of phosphorus in epoxy resins increased the
flame retardant property due to higher limited oxygen
index (LOI) value, which is valuable in encapsulation.
 UV-stabilized bisphenol A type epoxy resins are the
best choice for LED applications.
 Epoxy resins containing cobalt acrylate have better
electrical conducting properties than the blank epoxy
resins and modified resins containing Bi, Ni, Zn, Cu,
and Sb acrylate.
FIG. 20. 2-methylimidazole (2-MI).  Curing agents with long hydrocarbon chains as well as
double bonds near the center of the chain have
improved tensile strength. The curing behavior of
TBM was better in oxygen atmosphere rather than
nitrogen atmosphere.

ACKNOWLEDGMENTS
The author thanks the Rama Institute of Engineering
and Technology for providing the necessary facility & the
Plastic Department of HBTI, Kanpur for technically
suggestions.

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