Journal of Industrial and Engineering Chemistry 29 (2015) 1–11

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

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

Review

Synthesis and application of epoxy resins: A review

Fan-Long Jin a,*, Xiang Li b, Soo-Jin Park c,**
a
Department of Polymer Materials, Jilin Institute of Chemical Technology, Jilin City 132022, People’s Republic of China
b
Department of Chemical Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
c
Department of Chemistry, Inha University, Incheon 402-751, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: Epoxy resins have been widely used for coatings, electronic materials, adhesives, and matrices for fiber-
Received 8 January 2015 reinforced composites because of their outstanding mechanical properties, high adhesion strength, good
Received in revised form 15 March 2015 heat resistance, and high electrical resistance. The final properties of cured epoxy resins are affected by
Accepted 28 March 2015
the type of epoxy resin, curing agent, and curing process. This paper aims to review the synthesis, curing
Available online 4 April 2015
process, and application of epoxy resins.
ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Keywords:
reserved.
Epoxy resins
Composites
Curing agent
Synthesis
Application

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Synthesis of epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Bisphenol-A epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Cycloaliphatic epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Trifunctional epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Tetrafunctional epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Novolac epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Biobased epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Fluorine-containing epoxy systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Phosphorus-containing epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Silicon-containing epoxy resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Curing process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Epoxy curing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Amine type curing agent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Alkali curing agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Anhydride curing agent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Catalytic curing agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Curing systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Room-temperature curing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Heat curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Photo-curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

* Corresponding author. Tel.: +86 432 62185319; fax: +82 32 8675604.

** Corresponding author. Tel.: +82 32 8767234; fax: +82 32 8675604.
E-mail addresses: jinfanlong@163.com, psjin@krict.re.kr (F.-L. Jin), sjpark@inha.ac.kr (S.-J. Park).

http://dx.doi.org/10.1016/j.jiec.2015.03.026
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
2 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11

Epoxy-based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Thermoplastic-modified epoxy systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Epoxy/inorganic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Epoxy/carbon fiber composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Epoxy/clay nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Epoxy/carbon nanotube composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Application fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Paints and coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Industrial tooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Aerospace industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Electronic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Biomedical systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Introduction bisphenol A-based epoxy resins. The resulting epoxy resins are
highly viscous liquids. Wu et al. [30] synthesized liquefied
Epoxy resins were discovered in 1909 by Prileschajew [1]. Epoxy bamboo–bisphenol A copolymer epoxy resins in a two-step
resins are defined as low-molecular-weight pre-polymers contain- process. The copolymer epoxy resin curing process can occur at
ing more than one epoxide group of the form [2]: room temperature after addition of triethylene tetramine, since
curing is an exothermic reaction.

O Cycloaliphatic epoxy resins

CH2 CH R
The cycloaliphatic epoxy resin (CAE), 30 ,40 -epoxycyclohexyl-
Epoxy resins are thermosetting resins, which are cured using a methyl 3,4-epoxycyclohexanecarboxylate is synthesized by react-
wide variety of curing agents via curing reactions. Their properties ing 30 -cyclohexenylmethyl 3-cyclohexenecarboxylate with
depend on the specific combination of the type of epoxy resins and peracetic acid. Fig. 3 shows the chemical structure of CAE. This
curing agents used [3–15]. Because of their excellent mechanical epoxy resin has an aliphatic backbone and a fully saturated
properties, high adhesiveness to many substrates, and good heat molecular structure, which contribute to its excellent UV stability,
and chemical resistances, currently epoxy resins are intensively good weatherability, good thermal stability, and excellent electri-
used across a wide range of fields, where they act as fiber- cal properties. These properties are crucial for resins used to
reinforced materials, general-purpose adhesives, high-perfor- fabricate structural components requiring application in high-
mance coatings, and encapsulating materials [16–25]. temperature environments [31,32].
In this paper, the synthesis and curing process of epoxy resins Tao et al. [33] synthesized imide ring and siloxane-containing
are reviewed in detail. In addition, the preparation and application CAE, 1,3-bis[3-(4,5-epoxy-1,2,3,6-tetrahydrophthalimido) propyl]
of epoxy-based composites are discussed. tetramethyldisiloxane (BISE), by a two-step procedure. Fig. 4
shows the chemical structure of BISE. The fully cured BISE epoxy
Synthesis of epoxy resins resin has good thermal stability and a relatively low glass
transition temperature (Tg) compared with commercially available
Bisphenol-A epoxy resins CAE, as shown in Table 1.
Gao et al. [34] also synthesized transparent cycloaliphatic
The diglycidyl ether of bisphenol-A (DGEBA) is produced by epoxy-silicone resins through a two-step reaction route for use in
reacting epichlorohydrin with bisphenol-A in the presence of a opto-electronic devices packaging. In comparison with CAE, the
basic catalyst. Fig. 1 shows the chemical structure of DGEBA. The cured cycloaliphatic epoxy-silicone resins exhibited better thermal
properties of the DGEBA resin depend on the number of repeating stability, lower water absorption, and higher UV/thermal resis-
units. Low-molecular-weight molecules tend to be liquids and tance.
higher-molecular-weight molecules tend to be more-viscous
liquids or solids [26,27]. Trifunctional epoxy resins
Yang et al. [28] synthesized a low viscosity epoxy resin by
reaction of polyethylene glycol and DGEBA epoxy resin. The epoxy A trifunctional epoxy resin, trimethylol propane-N-triglycidyl
resin cured using a cationic photoinitiator under UV light, and the ether, can be prepared by the reaction of trimethylol propane and
curing degree of the epoxy resin was beyond 90% within 40 s, as epichlorohydrin, as shown in Fig. 5. This epoxy resin is a low-
shown in Fig. 2. Czub [29] synthesized high-molecular-weight viscosity, non-crystalline, plastic material that can be cured at low
epoxy resins from modified natural oils and bisphenol A or temperatures [35,36].

CH3 OH CH3
CH2 CH CH2 O C O CH2 CH CH2 O C O CH2 CH CH2
O n O
CH3 CH3

Fig. 1. Chemical structure of DGEBA.

 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11 3

Table 1
1.0 Thermal properties of the cured epoxy resina [33].

Sample T5 (8C) T10 (8C) Tg (8C)

0.8 BISE/HHPA 348 365 127

Degree of curing

CAE/HHPA 343 357 246

a
T5: decomposition temperature at 5% of weight loss; T10: decomposition
0.6 temperature at 10% of weight loss; HHPA: hexahydrophthalic anhydride.

0.4
O CH2 CH CH2
0.2 CH2 O
0 20 40 60 80 100
Time (s) CH3CH2 C CH2 O CH2 CH CH
2
Fig. 2. Curing degree of the epoxy resin as a function of time [28]. CH2 O

O CH2 CH CH2
O
O
Fig. 5. Chemical structure of trimethylol propane-N-triglycidyl ether.
O
O O

Fig. 3. Chemical structure of CAE. CH2 CH CH2 CH2 CH CH2

O N N O
CH2 CH CH2 CH2 CH CH2
O O
Tetrafunctional epoxy resins (a)
Tetrafunctional epoxy resins are synthesized by reacting 1,3-
CH2 CH CH2 H CH2 CH CH2
diaminobenzene or 4,40 -aminodiphenyl methane with epichloro-
hydrin. Fig. 6 shows the chemical structures of these epoxy resins. O N C N O
CH2 CH CH2 CH2 CH CH2
These epoxy resins have high epoxy functionality and high cross- H
linking densities, and thus, they are used in applications where O O
high-temperature resistance is required. The cured epoxy resins (b)
show excellent chemical resistance, high modulus, good UV- Fig. 6. Chemical structures of tetrafunctional epoxy resins.
blocking effect, and good thermal stability [37,38].
Aouf et al. [39] synthesized a multi-functional epoxy resin. The
cured epoxy resin showed a higher cross-linking density and a
higher char yield than DGEBA cured under the same conditions.
O O O
Novolac epoxy resins OCH2 CH CH2 OCH2 CH CH2 OCH2 CH CH2

Novolac epoxy resins are glycidyl ethers of phenolic novolac

CH2 CH2
resins that have been synthesized by reacting phenolic novolac
resin with epichlorohydrin. Fig. 7 shows the chemical structure of n
novolac epoxy resins. The multiple epoxide groups in novolac
epoxy resins contribute to their high cross-linking densities, which Fig. 7. Chemical structure of novolac epoxy resins.

result in excellent thermal, chemical, and solvent-resistance

properties [8,40].
Lin et al. [41] synthesized multifunctional phosphorus-contain-
ing epoxy resins from an addition reaction of 9,10-dihydro-9-oxa- Biobased epoxy resins
10-phosphaphenanthrene 10-oxide and novolac epoxy resin.
These cured epoxy resins exhibited high Tg and thermal stability, Polymers derived from renewable natural resources, such as
and achieved an impressive V-0 grade in the UL-94 vertical carbohydrates, starch, proteins, fats, and oils, have attracted
flammability test, as shown in Table 2. increasingly interest because of their low cost and biodegradability.

O O
CH3 CH3
O N CH2CH2CH2 Si O Si CH2CH2CH2 N O
CH3 CH3
O O
Fig. 4. Chemical structure of BISE.
4 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11

Table 2 8
Thermal and flame-retardant properties of cured epoxy resina [41].

T5 (8C) Tg (8C) VL-94 grade LOI (%)

371 178 V-0 33 6 b

a
LOI: Limiting oxygen index.

Dielectric constant
a
4

Vegetable oils are complex multi-component mixtures of different

triacylglycerols, i.e., esters of glycerol and fatty acids. Triglycerides 2
containing a large variety of unsaturations sites can be easily
epoxidized with organic peracids or H2O2, and epoxidized vegetable
oils show excellent potential as inexpensive, renewable materials
for industrial applications [42,43]. 0
0 2 4 6 8 10
Park [44–46] and Thulasiraman et al. [47] synthesized
Frequency (GHz)
epoxidized soybean oil (ESO) and epoxidized castor oil (ECO) by
reacting soybean or castor oil with glacial acetic acid/H2O2. Fig. 8 Fig. 10. Dielectric constant of DGEBA-F/DDM (a) and DGEBA/DDM (b) systems as a
shows the chemical structures of ESO and ECO. function of frequency [52].

Fluorine-containing epoxy systems

CF3
Using fluorinated monomers and oligomers to modify epoxy
resins is attractive because the presence of fluorine imparts unique
characteristics, such as outstanding chemical resistance, low
coefficient of friction, low dielectric constant, low water absorp- O
tion, and broad use temperature. It is possible to fabricate entire CH2OCH2CH CH2
products from specialty polymers, e.g. fluorine-containing poly- OCH
mers, which enhance their appeal for commercial use [48–51]. CH2OCH2CH CH2
Park et al. [52] synthesized a CF3-group-containing DGEBA O
epoxy resin, whose chemical structure in shown in Fig. 9. The cured
Fig. 11. Chemical structure of fluorine-containing epoxy resin.
epoxy resin shows a lower dielectric constant (Fig. 10) and superior
mechanical properties compared to regular DGEBA.
Park et al. [53,54] also synthesized fluorine-containing epoxy
resins (Fig. 11). With increasing fluorine content, the total surface
energy of the tetrafunctional epoxy resin/fluorine-containing ethane (BGTF), through a four-step procedure. Fig. 12 shows the
epoxy resin blends gradually decreased, while the water repellency chemical structure of BGTF. The fully cured BGTF epoxy resin has
of the blends increased. good thermal stability with a Tg of 170–175 8C. The BGTF epoxy
Tao et al. [55] synthesized a fluorinated epoxy resin, 1,1-bis(4- resin also exhibited improved dielectric properties compared with
glycidylesterphenyl)-1-(30 -trifluoromethylphenyl)-2,2,2-trifluoro- the DGEBA epoxy resin.

OH
O O
O O
OH
O O O O O
O O
OH
O O O O O
O O
O O
(a) ESO (b) ECO
Fig. 8. Chemical structures of ESO and ECO.

CH3 CH3
CH2 CHCH2 O C O CH 2 CH CH2 O C O CH2CH CH2
O n O
CH3 O CH3

CF3

Fig. 9. Chemical structure of CF3 group-containing DGEBA epoxy resin.

 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11 5

O CF3 O
CH2 CHCH2 O C C C O CH2 CH CH2
O O

CF3
Fig. 12. Chemical structure of BGTF.

Phosphorus-containing epoxy resins phosphorus-containing epoxy resin and the nitrogen-containing

curing agent result in a great improvement of the flame retardant
Phosphorous compounds could impart high flame-retardant behavior.
character into epoxy resins through flame inhibition in the gas Finally, Liu et al. [59] synthesized hexakis(4-hydroxyphenoxy)-
phase and char enhancement in the condensed phase. They also cyclotriphosphazene, which they subsequently reacted with
have been found to generate less toxic gas and smoke than DGEBA to form a new phosphazene-based epoxy resin (PN-EP).
halogen-containing compounds. Incorporating covalently bonded The cured epoxy resin has high Tg and decomposition temperatures
phosphorus into epoxy resins could be achieved using phosphorus- and excellent flame retardancy (Table 3).
containing oxirane compounds [56–59].
Liu et al. [57] synthesized phosphorus-containing epoxy resins Silicon-containing epoxy resins
for reworkable environment-friendly electronic packaging mate-
rials, as shown in Fig. 13. The cured epoxy resins were transparent Silicon is regarded as an environmentally friendly flame
and have a high Tg of 227 8C and high mechanical modulus. retardant because it has a less harmful impact on the environment
Wang et al. [58] synthesized phosphorus-containing epoxy than existing materials. Silicon-containing epoxy resins can be
resins for use as flame retardant materials. The experimental synthesized by the following two approaches. One method is to
results indicated that synergistic effects from combining the introduce siloxanes into the epoxy compounds using hydrosilyla-
tion reactions. Another method utilizes the transetherification
between alkoxyl silane and glycidol, or the condensation of
O
hydroxyl-terminated siloxanes with epoxy resins or epichlorohy-
O O P O drin. These epoxy resins display advantages of both epoxy resins
O O
O P O O and silicone resins [60–64].
O O Mercado et al. [62] synthesized silicon-containing epoxy resins,
O
and their chemical structures are shown in Fig. 14. The cured epoxy
resins have a moderate Tg and a high limited oxygen index (LOI)
O value.
(a) (b) Liu et al. [63] synthesized two novel silicon-containing
cycloaliphatic epoxy resins for electronics packaging applications.
Fig. 13. Chemical structures of phosphorus-containing epoxy resins. Fig. 15 shows the chemical structures of the epoxy resins. The
cured epoxy resins have high Tg, good thermal stabilities, and good
mechanical properties.
Table 3
Park et al. [64] synthesized silicon-containing epoxy resins
Flame-retardant properties of PN-EP cured with various curing agentsa [59].
(DGEBA-Si) by addition of DGEBA with dichlorodiphenyl silane
Sample UV94 grade LOI value (%) using triphenylphophine as catalyst. The cured epoxy resin
PN-EP/DDM V-1 28.5 possessed a lower Tg and enhanced mechanical properties
PN-EP/DICY V-0 31.2 (Table 4) than of the pure DGEBA epoxy resin.
PN-EP/novolak V-0 33.5 Wang et al. [65] synthesized epoxy-terminated siloxane-
PN-EP/PMDA V-0 32.9
containing resins, and the cured epoxy resin has good thermal
a
DDM: 4,40 -diaminodiphenylmethane; PMDA: pyromellitic dianhydride; DICY: stability, high tensile strength, and high lap shear.
dicyandiamide.

CH2
O
CH
CH2
O O O O O
CH2 C CH2 O Si O CH2 C CH2 CH2 C CH2 O Si O CH2 C CH2
H H H H

Fig. 14. Chemical structures of silicon-containing epoxy resins.

6 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11

CH3 Alkali curing agent

CH3 O Si O Alkali curing agents can be divided into imidazoles and tertiary
O O
O amines. Imidazoles are used primarily as accelerators in reactions
O Si O
O O between epoxy resins and other curing agents. They can also be
O used as the sole curing agent [69]. Tertiary amines are also
commonly used as accelerators for other epoxy resin curing agents.
They are typically used in conjunction with amines, polyamides,
O
amidoamines, mercaptans, polysulfides, and anhydrides to accel-
Fig. 15. Chemical structures of silicon-containing epoxy resins. erate the epoxy-hardener reaction. They also offer long room
temperature pot life [70].

Anhydride curing agent

Anhydride curing agents have excellent electrical properties,
Table 4
good chemical resistance, and good physical properties. These
Mechanical properties of DGEBA/DDM and DGEBA-Si/DDM systems [64].
curing agents have very long pot lifes. Curing with anhydride
Sample Fracture Flexural Elastic curing agent is usually catalyzed by amine. The more common
toughness strength modulus
anhydrides include phthalic anhydride (PA), 3,4,5,6-tetrahy-
(MPa m1/2) (kPa) (GPa)
drophthalic anhydride (3,4,5,6-THPA), methyl tetrahydrophthalic
DGEBA/DDM 3.53  0.11 118  2.4 2.9  0.22 anhydride (MTHPA), hexahydrophthalic anhydride (HHPA), meth-
DGEBA-Si/DDM 4.48  0.1 151  2.7 4.1  0.25
yl hexahydrophthalic anhydride (MHHPA), etc. [71–74]. Fig. 18
shows the chemical structures of PA and HHPA. Fig. 19 shows the
cure reaction mechanism of anhydride and epoxide in the presence
of tertiary amine [74].
Curing process
Catalytic curing agents
Epoxy curing agents Catalytic curing agents are inert under normal conditions, such
as ambient temperature and indoor lighting, but they exhibit
Epoxy curing agents promote or control the epoxy resin curing activity with external stimulation, such as heating or photo-
reaction. Epoxy resin curing is accomplished by adding a curing irradiation. The curing proceeds by cationic polymerization
agent. Irreversible changes in the epoxy resin occur during the initiated by the catalytic curing agent. The use of catalytic curing
curing process. The cure kinetics and Tg of epoxy resins are agents increases the storage stability and handling of epoxy resins.
dependent on the molecular structure of the curing agents Catalytic curing agents can be divided into benzylsulfonium,
[66]. Curing agents can be divided into amine-type curing agents, benzylpyridinium, benzylammonium, and phosphonium salts
alkali curing agents, anhydrides, and catalytic curing agents [4,75–81]. The chemical structures of N-benzylpyrazinium hexa-
according to their chemical compositions. fluoroantimonate (BPH) and N-benzylquinoxalinium hexafluor-
oantimonate (BQH) are shown in Fig. 20. Fig. 21 shows the cure
Amine type curing agent reaction mechanism of epoxide initiated by BPH [45].
Amine type curing agents are one of the basic curing agents for
epoxy resins, and they can be classified into three major categories: Curing systems
aliphatic, aromatic, or cycloaliphatic amines. Amine type curing
agents react with epoxide rings by nucleophilic addition. Fig. 16 Epoxy resin curing systems comprise the chemical reactions of
shows the chemical structures of 4,40 -diaminodiphenyl methane the epoxide groups in the epoxy resins with a curing agent to form
(DDM) and 4,40 -diaminodiphenyl sulfone (DDS) [67,68]. Fig. 17 a highly cross-linked, three-dimensional network [82,83].
shows the cure reaction mechanism of amine and epoxide.
Room-temperature curing
Epoxy resin curing that takes place at room temperature uses
room-temperature curing agents, such as aliphatic polyamines,
H O alicyclic polyamines, low molecular weight polyamide, and
H2N C NH2 H 2N S NH2 modified aromatic amines. Room temperature curing provides a
H O lower Tg, higher flexibility, greater impact resistance, and greater
electrical and thermal shock resistance [84,85].
(a) DDM (b) DDS
Fig. 16. Chemical structures of DDM and DDS. Heat curing
Generally, epoxy resins that are cured at elevated temperatures
employ aromatic polyamines, acid anhydrides, resol resins, amino

O O

O O

O O

(a) PA (b) HHPA

Fig. 17. Cure reaction mechanism of amine and epoxide. Fig. 18. Chemical structures of PA and HHPA.
 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11 7

O
O
C C OCH
R O + CH R
C C OH
O OH
O
O
O
C OCH O
R C OCH
C OH + CH2 CH R
C OCH2CH
O
O OH

O O
C OCH C OCH
R + CH R
C OH C OCH
OH
O O

( R= , )

Fig. 19. Cure reaction mechanism of anhydride and epoxide in the presence of tertiary amine.

resins, dicyandiamide, or hydrazides, as curing agents. The high-
temperature curing system is generally divided into a pre-curing
stage at low temperature and a post-curing stage at high
temperature. Epoxy resins cured at higher temperatures have a
higher Tg, greater tensile strength, higher heat resistance, and
greater chemical resistance [86,87].
Photo-curing
Epoxy resins can be cured using infrared, ultraviolet light, or
electron beam irradiation in the presence of a photoinitiator.
Photo-curing dramatically reduces the curing time from hours to
minutes. In addition, it provides a more consistent and controlled
process compared to the other curing processes [88–91].
Epoxy-based composites
The highly cross-linked epoxy resins are rigid and brittle and
have relatively poor resistance to crack initiation and growth,
which limit their use in many applications, such as structural
materials. Many attempts have been made to improve their
physical properties using various toughening or strengthening
agents.
Thermoplastic-modified epoxy systems
The toughness of epoxy resins can be improved by dispersion of
thermoplastic components, such as poly(acrylonitrile-co-butadi-
ene-co-styrene) (ABS), poly(ether sulfones) (PES), poly(ether
N N SbF6
imides) (PEI), polysulfones (PSF), poly(ether ketone) (PEK), and
polyimides (PI), into the epoxy matrix [92–95]. Thermoplastic-
modified epoxy systems are usually prepared by polymerization-
induced phase separation of the thermoplastic modifier, which is
initially miscible in the epoxy resin but separates into phases
during polymerization. The final properties of the systems are
determined by the resulting phase-separated morphology and
effective improvement in toughness will be obtained only with a
co-continuous phase or phase inversion structure [96–98].
Epoxy/inorganic composites
Several inorganic particles have been added to epoxy resins in
order to improve the fracture toughness. Incorporation of
inorganic particles leads to an increase in deformation and crack
propagation resistance by toughening mechanisms, i.e., particle
bridging, crack pinning/bowing, and crack path deflection. The
addition of inorganic particles into epoxy resins can increase the
modulus, hardness, and fracture toughness [99–104].
Epoxy/carbon fiber composites
Carbon fibers with high strength and modulus can be
incorporated into a range of matrix materials. When a load is
applied to a carbon fiber composite, the stress is transferred from
one carbon filament to another through the matrix material. If a
fiber-resin bond is weak, this load transfer will weaken or break
bonds between the resin matrix and fiber filaments. Carbon fibers
are usually coated with sizing, a polymeric solution applied to
improve their adhesion with the resin matrix [105–108]. Epoxy/
carbon fiber composites are used more extensively for structural
applications than other high performance composites due to their
overall high specific stiffness and strength properties [109].

N N SbF6 Epoxy/clay nanocomposites

BPH BQH
Montmorillonite-based clay is a 2:1 layered silicate with sheets
Fig. 20. Chemical structures of BPH and BQH. that carry negative charges, which are balanced by the presence of
8 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11

Heat
(a) CH2 N N SbF6 CH2 SbF6 + N N

R1
SbF6 R1
CH2 SbF6 + O CH2 O

R2 R2

R1 R1 R1
R1
CH2 O + O CH2 O CH CH O
SbF6 R2 SbF6
R2 R2 R2

H
Heat
(b) CH2 N N SbF6 + R OH R O CH2 + N N
SbF6

R O CH2 + H+SbF6- + N N

R1

O
R1 R1 R1
R1
R2
H+SbF6- + O O HO CH CH O
SbF6 SbF6
R2
R2 R2 R2

R1 R1 R1
R1 R1 R1
O + HO CH CH O HO CH CH CH CH O + H+SbF6-
SbF6 R2 SbF6 R2 R2 SbF6
R2 R2 R2

R1
R1
(c) O + R OH HO CH CH OR + H+SbF6-
SbF6
R2
R2
Fig. 21. Cure reaction mechanism of epoxide initiated by BPH.

interlayer cations (Na+ and Mg2+ ions). The fabrication of polymer/
clay composites can easily result in agglomeration of the clay,
resulting in degradation of the mechanical properties and wear
resistance. The most common way to overcome this difficulty is to
replace the inorganic Na+ cations on the clay surface with the
desired organic cations, particularly alkyammonium ions. When
these surface-treated clays are introduced into the host polymer
matrix, two morphology types form: intercalated or delaminated/
exfoliated nanocomposite structures [110–114].
Epoxy/clay nanocomposites with low clay concentrations
exhibit markedly improved mechanical strength, thermal
stability, permeability, and flammability compared to pristine
epoxy matrices and traditional micro/macro composites. The
superior performance of the epoxy/clay composites arises from
the ultra high interface/volume ratio in the nanocomposites,
resulting from the nanometer scale clay particles dimensions
[115–118].
Epoxy/carbon nanotube composites
Carbon nanotubes (CNTs) are constructed with length-to-
diameter ratios that are significantly higher than that of any other
materials, providing them with extraordinary mechanical, elec-
tronic, and thermal properties. Thus, CNTs would be useful fillers
to improve the performance of the resulting composites
[101,119–121].
However, the low dispersibility and weak interfacial interac-
tions of CNTs within epoxy matrices have limited their application
in this area. Ultrasonic dispersing and high-shear mixing are
examples of commonly used mechanical methods. Physical
methods involve the adsorption and/or wrapping of polymers or
surfactants on the CNT surfaces, and chemical methods consist of
covalent chemical bonding of polymer chains to the CNT surfaces,
dramatically improving interfacial interactions between them and
the epoxy matrix [122–124].
 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11
A homogenous dispersion of aligned CNTs with favorable
chemical interactions with the epoxy resins can achieve efficient
load transfer and provide a conductive pathway for electrons and
phonons. Epoxy/CNT composites present unique mechanical,
thermal, and electrical behaviors [125–127].
Application fields
Paints and coatings
Epoxy resins are widely used as heavy-duty anticorrosion
coatings because of their exceptional properties, such as easy
processing, high safety, excellent solvent and chemical resistance,
toughness, low shrinkage on cure, mechanical and corrosion
resistance, and excellent adhesion to many substrates. Metal cans
and containers are often coated with epoxy resins to prevent
rusting, especially when packaging acidic foods like tomatoes.
Epoxy resins are also used for high performance and decorative
flooring applications such as terrazzo, chip, and colored aggregate
flooring [128–130]. Fig. 22 shows the application fields of epoxy
resins.
Adhesives
Epoxy adhesives are a major part of the class of adhesives called
‘‘structural adhesives’’. These high-performance adhesives are
used in the construction of aircraft, automobiles, bicycles, boats,
golf clubs, skis, snowboards, and other applications where high
strength bonds are required. When used as adhesives in cryogenic
Fig. 22. Photos of epoxy resins used in (a) paints and coatings, (b) adhesives, (c) electronic materials, and (d) aerospace industry.
9
engineering applications, it is necessary to optimize the epoxy
shear strength at both cryogenic and room temperatures.
Commercial epoxy adhesives are engineered for optimal toughness
by incorporating phase-separated thermoplastics, rubber particles,
or rigid inorganic particles into the matrix. Typically, the adhesives
are cured at elevated temperatures to increase their strength and
activate chemical bonding at the substrate/adhesive interface
[131–135].
Industrial tooling
Epoxy systems are used in industrial tooling applications to
produce molds, master models, laminates, castings, fixtures, and
other industrial production aids. This ‘‘plastic tooling’’ replaces
metal, wood, and other traditional materials, and generally
improves the process efficiency while either lowering the overall
cost or shortening the lead-time for many industrial processes.
Fiber-reinforced epoxy composites have proven effective in
repairing metallic components and tubular pipes. The composites
also act as load-bearing units in hydrogen storage cylinders [136–
139].
Aerospace industry
Epoxy resins have been extensively used for structural adhesive
applications in the aerospace industry because of their high
adhesive properties and low cost. Epoxy resins reinforced with
high strength glass, carbon, Kevlar, or boron fibers have the
greatest potential for use in the aerospace industry [140,141].
10 F.-L. Jin et al. / Journal of Industrial and Engineering Chemistry 29 (2015) 1–11
Electronic materials
Epoxy resin formulations are important in the electronics
industry, and are employed in motors, generators, transformers,
switchgear, bushings, and insulators. Epoxy resins are excellent
electrical insulators and protect electrical components from short
circuiting, dust, and moisture. Metal-filled polymers are exten-
sively used for electromagnetic interference shielding [142]. Epoxy
molding compounds (EMCs) are popularly used as encapsulation
materials for semiconductor devices protect the integrated circuit
devices from moisture, mobile-ion contaminants, and adverse
environmental conditions such as temperature, radiation, humid-
ity, and mechanical and physical damage [143,144]. Epoxy
composites containing particulate fillers, such as fused silica,
glass powder, and mineral silica have been used as substrate
materials in electronic packaging applications [145,146].
Biomedical systems
Epoxy resins are widely used in biomedical applications.
Collagen-based materials have been used in human clinical
applications as wound dressings, vascular grafts, and aortic heart
valves [147]. Shape memory polymer foams have significant
potential for biomedical applications such as embolic sponges
[148,149]. Nanodiamond-epoxy derivatives have found consider-
able application in biomedical systems because they exhibit a
combination of extreme hardness, outstanding chemical inertness,
low electrical and high thermal conductivities, wide optical
transparency, and other unique properties [150,151].
Conclusions
In this paper, we have reviewed various epoxy resins and curing
agents. The properties of cured epoxy resins depend on the type of
epoxy resin, curing agent, and curing process used. The toughness
of epoxy resins can be improved by incorporating thermoplastic
components, inorganics, carbon fibers, clay, and carbon nanotubes.
Epoxy resins have a wide range of application including coatings,
aerospace industry, electronic materials, and biomedical systems.
Acknowledgement
This work was supported by the Carbon Valley Project by
Ministry of Trade, Industry and Energy.
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