18

Polymer Matrix: Epoxy Resins

18.1 Introduction
The term “epoxy resin” represents a broad class of cross-linked polymers
with the cross-linking derived from the oxirane or epoxy group:

C C
(18.1)

This ring approximates as an equilateral triangle, which makes it

strained, thus highly reactive.
Epoxies were developed, independently, principally by Ciba AG
(Switzerland) and Devoe and Reynolds Co. (USA) [1].
Epoxy resins are employed extensively in structural and speciality com-
posite applications since they offer a unique combination of properties that
are not attainable from other thermosetting resins. They are available in a
wide variety of physical forms from low-viscosity liquid to high-melting
solids. High strength, low shrinkage, excellent adhesion to various sub-
strates, outstanding electrical insulation properties, chemical and solvent
resistance, and relatively low cost are some of the noteworthy attributes of
the epoxy polymers. They cure with ease. No volatiles or by-products are
evolved during the cure [2].
The primary cross-linking of epoxy resin takes place through the ring
opening reaction of the epoxy group.

18.2 Resin Preparation

General-purpose epoxy resins are prepared by reacting epichlorohy-
drin and bisphenol A to give diglycidyl ether of bisphenol A (DGEBA)
with a molecular weight of 340 (Figure 18.1). Higher-molecular-weight

R. N. Kumar and A Pizzi. Adhesives for Wood and Lignocellulosic Materials, (403–423) © 2019
Scrivener Publishing LLC

403
404 Adhesives for Wood and Lignocellulosic Materials

CH3

HO C OH O

CH3 Cl CH2 HC CH2

Bisphenol-A Epichlorohydrin

(18.2) (18.3)

Figure 18.1 Raw materials for epoxy resin.

resins in the liquid, semisolid, to hard crystalline forms can be pro-

duced by increasing the ratio of bisphenol A to epichlorohydrin during
manufacturing. They are linear polyethers with glycidyl end groups
(Figure 18.3).
The details of preparation and the mechanism of reaction as well as the
relationship between molecular weight, the softening point, and epoxy
equivalents are given by Saunders [1].

18.3 Characteristics of Epoxy Resins

Epoxy resins used in commercial composite applications can be catego-
rized as those suitable for structural and high-temperature applications
and those best suited to nonstructural or low-temperature applications.
A primary indicator of service temperature is the glass transition tem-
perature (Tg). The Tg is the temperature below which a polymer exists
in the glassy state, whereas above this temperature, individual segments
are able to move relative to each other in what is termed as the “rubbery
state”.

18.3.1 Epoxy Equivalent

Another key characteristic that determines the resin suitability for use is
the epoxy equivalent (EEW), which is defined as the weight of the resin
per epoxy group. The equivalent weight of the polymer is used to calcu-
late the stoichiometric ratio between the epoxy resin and the curing agent.
Dividing the molecular weight of the resin by the number of epoxy groups
per molecule is the equivalent weight of the resin.
 Polymer Matrix: Epoxy Resins 405

18.3.2 Enhancement of Properties

Rigidity can be built into the cured matrix in several ways:

(1) Through incorporation of aromatic groups

(2) By Increasing the number of reactive sites (epoxy groups)
per molecule
(3) By reducing the distance between reactive sites

18.3.3 Types of Epoxy Resins

The three primary classes of epoxies used in composite applications are as
follows:

(1) Phenolic glycidyl ethers

(2) Aromatic glycidyl amines
(3) Cycloaliphatic epoxies

18.3.4 Bisphenol A Glycidyl Ethers

They are formed by the condensation of epichlorohydrin with a phenolic
group. Different types of resins can be formed by the choice of the appro-
priate structure of phenol-containing molecule and the number of pheno-
lic groups per molecule.
The first commercial resin in this category is the DGEBA, which is widely
used today [1, 3, 4]. The structure of DGEBA is shown in Figure 18.2.

CH3 O
HO C OH + 2 Cl H2C HC CH2

CH3 Epichlorohydrin
Bisphenol A NaOH

O CH3 O

H2C CH CH2 O C O H2C HC CH2

CH3
Diglycidylether of Bisphenol A (DGEBA)

Figure 18.2 Structure of DGEBA.

406 Adhesives for Wood and Lignocellulosic Materials

18.4 Preparation of DGEBA Epoxy Resin

The preparation consists of first producing DGEBA as given by structure
in Figure 18.2. This is then followed by a chain extension to increase the
molecular weight to produce epoxy oligomer (Figure 18.3).
The advantage of this epoxidation strategy is the possibility of tailor-
ing the prepolymer’s length and molecular weight. The molecular weight
and softening point depends on the ratio of epichlorohydrin and bisphe-
nol A as mentioned earlier. The chain extension reactions are given below
(where ECH is epichlorohydrin and BPA is bisphenol A):
The typical experimental details of the preparation of epoxy resin are
given by Saunders [1].
Various types of epoxy resins are available from multiple suppliers. The
primary distinction between these resins is their viscosity, which can range
from 14 Pa.s to 5000–14,000 Pa.s at 25°C. The molecular weight increases
as the ratio of ECH to BPA decreases. The viscosity depends on the molec-
ular weight. Lower-molecular-weight materials have lower viscosities.
Aromatic benzene rings of bisphenol A can be replaced by cyclohexane
rings to produce a cycloaliphatic material. This results in a low-viscosity,
moderately reactive resin with a structure analogous to the DGEBA type.

18.4.1 Curing Agents

The epoxy resin as depicted by the structure in Figure 18.3 is linear and
therefore thermoplastic in nature. The uncross-linked resins will have
poor mechanical, chemical, and heat resistance. However, by opening the
epoxy ring, three-dimensional cross-linked structures can be obtained.
The carbon atoms of the epoxy ring are electrophile because of different
electronegativity of carbon and oxygen. This atomic arrangement thus
shows enhanced reactivity. Thus, epoxies or the epoxy functions are highly
reactive and usually undergo ring-opening reactions with nucleophiles [5].
This can be achieved by using appropriate hardeners or curing agents. Most
of the curing agents in common use can be classified into three groups [1]:

(a) Tertiary amines

(b) Polyfunctional amines
(c) Acid anhydrides
 CH3 OH CH3
O

H 2C CH CH2 O C O H2C CH O C OH

CH3 CH3

ECH

O CH3 OH CH3

H 2C CH CH2 O C O H 2C CH O C O

CH3 CH3
O
BA/ECH H 2C CH CH2

CH3 OH CH3
O

H2C CH CH2* O C O H2C CH *O C O

CH3 CH3
O
n
Polymer Matrix: Epoxy Resins

H2C CH CH2

Figure 18.3 Epoxy oligomer based on bisphenol A.

407
408 Adhesives for Wood and Lignocellulosic Materials

18.4.1.1 Tertiary Amines

Examples of tertiary amines used as curing agents for epoxy resins include
benzyldimethylamine (6), 2-(dimethylaminomethyl)-phenol (DMP) (7),
2,4,6-tris(dimethylaminomethyl)-phenol (DMP-30) (8), triethanolamine
(9), and N-n-butylimidazole (10) (Figure 18.4) [1].
The reaction between an epoxy resin and a tertiary amine is thought to
proceed as shown in Figure 18.5 [1].
The fact that chemically bound nitrogen is found in the final product
confirms the above reaction scheme. Tertiary amines are called “catalytic”
curing agents since they only induce the linkage of epoxy groups to each
other and do not participate in the reaction [1].

18.4.1.2 Polyfunctional Amines

Polyfunctional primary amines are an important class of hardeners for
epoxy resins. Primary amines react with the epoxide group to form a
hydroxyl group and a secondary amine. The secondary amine can fur-
ther react with an epoxide to form a tertiary amine and an additional
hydroxyl group. The amine type will alter both the processing properties
like mechanical, temperature, and heat resistance of cured copolymer net-
works [5].

CH2-N(CH3)2 OH

CH2-N(CH3)2

Benzyldimthylamine (BDMA) 2-(Dimethylaminomethyl)- Phenol

6 7

OH N
N(CH2CH2OH)3
N(CH3)2-CH2 CH2-N(CH3)2
Triethanolamine N
9
CH2-N(CH3)2 C4H9
2,4,6-tris(dimethylaminomethyl)-phenol N-n-butylimidazole
8 10

Figure 18.4 Tertiary amines curing agents.

 Polymer Matrix: Epoxy Resins 409

(i) Formation of quaternary base

O
O
+
R3N: H2C CH R3N CH2 CH

(ii) Protonation of quaternary base with the formation of an anion

O OH

+ + + R'O
CH2 + R'OH R3N CH2 CH
R3N CH

O OH

+ + + OH
R3N CH2 CH + H2O R3N CH2 CH

(iii) Polymerization through epoxy group (initiated by the above-formed anion)

O
O
O
H2C CH
R'O R'O CH2 CH
H2C CH

O O

CH2 CH O CH2 CH
O
O
CH2 CH
H2C CH
R'O CH2 CH O
etc
R'O CH2 CH

11

Figure 18.5 Scheme of reaction of epoxy resin with tertiary amines.

410 Adhesives for Wood and Lignocellulosic Materials

Both aliphatic and aromatic compounds having at least three active

hydrogen atoms present in the primary and/or secondary amine groups
are widely used as curing agents for epoxy resins. Examples of such poly-
functional amines are shown in Figure 18.6.
The reaction between an epoxy resin and a polyamine results in a cross-
linked polymeric structure as illustrated by the reaction with triethylene
tetramine (with six reactive hydrogens) (Figure 18.7):

H2N-CH2-CH2-NH2 H2N-(CH2)2-NH-(CH2)2-NH2 H2N-(CH2)2-NH-(CH2)2-NH2-(CH2)2-NH2

Ethylenediamine Diethylenetriamine Triethylenetetramine

12 13 14

NH2

H2N CH2 NH2

NH2
4,4' Diaminodiphenylmethane
15 m-Phenylenediamine (MPD)
17

O
=

H2N S NH2
=

O
4,4' Diaminodiphenylsulphone
16

Figure 18.6 Polyamines as curing agents.

H2N-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2 + 6 H2C CH

CH OH
OH

CH2 CH2
CH
(CH2)2 N (CH2)2 N (CH2)2 N
N
CH CH2 CH2
CH2 CH2

OH CH OH
CH OH CH OH

Figure 18.7 Polyamines–epoxy curing reaction.

 Polymer Matrix: Epoxy Resins 411

In general, aliphatic amines provide fast cures and are effective at room
temperature while aromatic amines are somewhat less reactive and give
products with higher heat distortion temperatures.

18.4.1.3 Calculations of the Proportion of Amines for Curing Epoxy

Resins
The desired stoichiometric quantity of amine by weight per 100 gram of
epoxy resin is calculated from the following equation:

Equivalent weight of amine

× 100
Equivalent weight of epoxy resin
Molecular weight of amine
Equivalent of amine =
Number of active hydrogen atoms
Molecular weight of epoxy resin
Equivalent of epoxy resin =
Number of epoxy groups

Example:
The molecular weight of diethylenetriamine (DETA)

H2N CH2 CH2 NH CH2 CH2 NH2

is around 103 g/mol, and the number of active hydrogen atoms of DETA
is 5.
Hence, the equivalent weight of DETA = 103/5 = 20.6.
The molecular weight of the epoxy resin (DGEBA, EPON 828) is about
340 g/mol, and the number of epoxy groups of the epoxy resin is 2.
Hence, the equivalent weight of epoxy = 340/2 = 170.
The desired stoichiometric quantity of amine by weight per 100 gram of
epoxy resin is = 20.6/170 = 0.121.
In accordance with the above equations, therefore, the stoichiometric
DETA/epoxy ratio is = (103/5)/(340/2) = 12/100 (w/w).

18.4.1.4 Special Amines

There are curing agents that have less than three hydrogen atoms available
for reaction with epoxy groups. Examples are diethanolamine (18), piperi-
dine (19), and dimethylaminopropylamine (20) (Figure 18.8).
412 Adhesives for Wood and Lignocellulosic Materials

H2
C
H2C CH2

H2C CH2
N
NH(CH2CH2OH)2 H
Diethanolamine Piridine
18 19

(CH3)2N-CH2-CH2-CH2-NH2
Dimethylaminopropylamine
20

Figure 18.8 Special amines.

These curing agents react in two steps:

(1) Firstly, the active hydrogen atoms of primary and second-

ary amines react in a manner similar to those present in
polyfunctional amines.
(2) The resulting tertiary amine is sufficiently reactive to ini-
tiate polymerization of epoxy groups as a catalytic curing
agent described earlier.

18.4.1.5 Acid Anhydrides

Cyclic anhydrides widely employed as curing agents for epoxy resins are as
follows: maleic anhydride (21), dodecenylsuccinic anhydride (22), endometh-
ylenetetrahydrophthalic anhydride (23), hexahydrophthalic anhydride (24),
phthalic anhydride (25), and pyromellitic dianhydride (26) (Figure 18.9).

18.4.1.6 Anhydride Curing Mechanism

The interaction between an acid anhydride and epoxy resin is complex. In
general, two main types of reaction occur:

(a) Opening of the anhydride group to form carboxy groups

(b) Opening of the epoxy ring

(i) Reaction of the anhydride group:

The anhydride groups may open to form one or two carboxy groups by

(a) Water (traces of which may be present in the system) or

 Polymer Matrix: Epoxy Resins 413

O
CH C CH3 CH3 CH3
O
O
CH3 CH2 CH2 CH CH2 C=CH C CH C
CH C
O
O CH3
CH C
Maleic anhydride Dodecenylsuccinic anhydride O
21 22

H O
C H O
HC C C
CH C
O H 2C CH
CH2
O
HC CH C
H 2C CH C
C
CH3 H O C
H O

Endomethyl enetetrahydrophthalic anahydride Hexahydrophthalic anhydride

23 24

O O O
=

=
=

C C C
O
C O O
C C
=

O
=
=

O O
Phthalic anhydride
25 Pyromelliticdi anhydride
26

Figure 18.9 Anhydrides for epoxy resin curing.

(b) Hydroxyl groups, which are either present as pendant

groups in the original resin or which may be produced by
reaction (iia) below:
O=

O=

(a) C O + H2O C OH
C C OH
=O

O=

OH
O=

O=

C O C OH
(b) + CH2 CH CH2
C C O
O=

O=

CH2 CH CH2
414 Adhesives for Wood and Lignocellulosic Materials

(ii) Reaction of the epoxy group

The epoxy group may be opened by reaction with (a) carboxy groups
[formed by reaction (1a,b)] or (b) hydroxyl groups [which may be present
as pendant groups in the original resin or which may be produced by reac-
tion (iia)].
OH
O
O=

O=
C OH C O CH2 CH
(a) + H2C CH
C O C O
O=

O=
CH2 CH CH2 CH2 CH CH2

OH

OH O CH2 CH
O

(b) CH2 CH CH2 + H2C CH CH2 CH CH2

The reaction between epoxy groups and anhydride is slow and hence
addition of a catalyst, usually a tertiary amine, accelerates the reaction by
the following mechanism:
O
O=

+ H2C CH
O=

C O NR3
+ R3N C
C C O-
O=

O=
O=

C O
O=

+
C NR3 C
O=

+
O=

C O CH R3 NR3
CH2 C
O=

C O CH2 CH
O-
O=

CO O
CO-O-

18.5 Other Types of Epoxy Resins

18.5.1 Epoxidized Novolac
Novolac resins derived from phenol or substitute phenols can be allowed to
react with epichlorohydrin to produce epoxidized novolacs such as epoxy
phenol novolacs (EPN) and epoxy cresol novolacs (ECN) (Figure 18.10).
 Polymer Matrix: Epoxy Resins 415

H2C H2C H2C

O O O
HC HC HC

CH2 CH2 CH2

O O O
CH2 CH2

Figure 18.10 Epoxidized novolac.

These are highly viscous or solid resins and possess high temperature and
chemical resistance but low flexibility [5].
High epoxy resin functionality and high cured Tg characterize these
resins and differentiate them from difunctional bisphenol A resin. Phenol
novolacs are highly viscous liquids, while cresol novolacs are typically
solids at room temperature. They are of general interest because excellent
temperature performance can be achieved at a relatively modest cost.

18.5.2 Tetrabromo Bisphenol A Epoxy Resins

An important variant is the epoxy resins produced from tetrabromo
bisphenol A.
These brominated resins are used to impart flame retardancy to the
final product and are commonly used in electrical applications. A variety
of products are available with wide ranges of both bromine content and
molecular weight. This category of resins ranges from pure diglycidyl ether
of tetrabromo bisphenol A to high-molecular-weight analogs similar to
those available with standard bisphenol A.
Flame retardants are either additive or reactive. Reactive flame retar-
dants are added during the polymerization process and become an integral
part of the polymer. TBBPA is mainly used in epoxy resins on the market as
a reactive flame retardant. It has to be pointed out that halogenated flame
retardants in particular are often toxic or even carcinogenic by themselves.
Environmental persistence and the ability to bio-accumulate add more
concerns [6].
Recently, researchers have synthesized epoxy resin by incorporat-
ing tris(2-hydroxypropyl)borate (THPB) and OPOSS (octaminophenyl
416 Adhesives for Wood and Lignocellulosic Materials

polyhedral oligomeric silsesquioxane) having boron and silicon in the cur-

ing system. It was found that there was an increase in the limited oxygen
index value of the epoxy resin with an improved heat-resistant layer and a
decrease in the release of flammable gas [5].

18.5.3 Epoxidized Vegetable Oils

There is a growing interest in the use of vegetable oils, which are sustain-
able resources needed for transition to green economy. Vegetable oils are
triglycerides of saturated and unsaturated fatty acids. The double bonds
present in the fatty acid moieties of vegetable oils can be epoxidized to
form epoxidized vegetable oils.
Epoxidation of double bonds in the oil is carried out by peracids. During
the epoxidation of double bonds, an oxygen atom is transferred from the
peracid to the C=C double bond, thus forming an oxirane ring. The epox-
idation agent of choice is m-chloroperbenzoic acid (mCPBA) (Figure
18.11).
Example
Other peracids used are peroxybenzoic acid, peroxyacetic acid, and per-
fluoroacetic acid. The latter is prepared in situ from acetic acid and hydro-
gen peroxide. The reactivities of the peroxy-acids are given in Figure 18.12.
The above method is employed for the epoxidation of the double bonds
in vegetable oils and natural rubber. Epoxidation of natural rubber gives
epoxidized natural rubber (ENR). The reaction of alkenes with peracids is
often called the Prilezhaev (Prileschajew) reaction [7]. Prileshajev epoxida-
tion consists of the formation in situ of a peracid by the action of hydro-
gen peroxide on organic acid (acetic or formic) in the presence of a strong
Bronsted acid (H2SO4 typically).
O=

O
Cl
C CHCl3
CH2 CH=CH2 + OOH CH3 CH2 CH CH2
CH3

m-Chloroperbenzoic acid +
mCPBA
O=

Cl
C
OH

m-Chlorobenzoic acid

Figure 18.11 Peroxy-acids for epoxidizing unsaturated compounds.

 Polymer Matrix: Epoxy Resins 417

O=
O=

O=
C Cl C
C
OOH OOH
CH3 OOH CF3

Peracetic acid m-Chloroperbenzoic acid Perfuoroacetic acid

mCPBA

Increasing reactivity

Figure 18.12 Reactivity of peroxy-acids.

A greener epoxidation method is using lipase-catalyzed chemo-

enzymatic oxidation. This strategy presents several advantages com-
pared to the Prileshajev process. Typical experimental l conditions are
given by the work of Tellez et al. [8].

18.5.4 Epoxidized Natural Rubber

Preparation
ENR is prepared by performic epoxidation. Concentrated NR is diluted
with distilled water to have 20% DRC. Nonionic surfactant (Emulwin W or
Terric 16A-16) is gradually added to maintain the stability of latex. Formic
acid (0.75 mole equiv. to isoprene unit) and 30% H2O2 (0.75 mole equiv.
to isoprene unit) are then slowly dropped in while the mixture is heated
to 50°C. The mixture solution is stirred at 50°C for 2–9 h. After the reac-
tion, the mixture is cooled down to room temperature and sodium sulfite
is added to remove the excess H2O2 followed by neutralization with 25%
ammonia solution. MeOH is then added to precipitate the product. The
white solid bulk obtained is washed with water several times, rinsed with
MeOH, and dried under reduced pressure.

18.6 Green or Sustainable Epoxy Matrix

Bisphenol A is reported to have severe impact on human health as it is able
to alter the human immune and reproductive system behavior within brain
chemistry. Bisphenol A also has estrogenic properties. Thus, several efforts
are being made to replace the traditional DGEBA biobased epoxy mono-
mers or oligomers with comparable high-performance materials.
Natural polyphenols (condensed tannins, lignin) have potential to sub-
stitute bisphenol A. Biobased epoxy resins were synthesized from catechin
418 Adhesives for Wood and Lignocellulosic Materials

molecule or condensed tannins, or one of the repetitive units in natural

flavonoid biopolymers with improved thermal and mechanical proper-
ties, and also from nonfunctionalized gallic acid (from the hydrolysis of
gallotannins). Catechin as a model compound of procyanidin-type con-
densed tannins has been epoxidized either by reaction with epichlorohy-
drin or by alkylation with unsaturated halogenated compound followed
by its oxidation [9, 10]. Benyahya et al. have proposed the direct use of
condensed tannins from green tea for the synthesis of aromatic biobased
epoxy oligomers [11]. More recently, two studies by Jahanshahi et al. [12,
13], one on the formation and testing of commercial polyflavonoid tannin
epoxy resins, were also published, the second of which was of particular
interest as it involved an epoxidized tannin–acrylic polymer that allowed
rapid curing of the epoxy tannin without having to use a hardener [12, 13].
The tannin-based epoxy acrylate resin was prepared from glycidyl ether
tannin (GET) and acrylic acid by reaction between GET and acrylic acid
in the presence of a catalyst and hydroquinone and tested successfully for
block shear strength [13].
Hydrolyzable tannins can also be used to prepare epoxy oligomers.
Thus, gallic acid epoxidation with epichlorohydrin was first reported
by Tomita and Yonezawa [14]. The addition occurs on both the carbox-
ylic acid group and also on at least one phenol group in the presence
of an ammonium-type phase transfer catalyst in anhydrous medium.
Nouailhas et al. also recently proposed another synthesis pathway leading
to epoxy prepolymers from gallic acid allylation followed by double bond
oxidation [10].
Cardanol is a further biocompound that has been tried for bioepoxy
synthesis. A patent exists on the use of commercial epoxidized cardanol
from Weller et al. [15], suggesting the use of cardanol to prepare biobased
epoxy cross-linked polymers. Epoxy monomers and oligomers were also
prepared using cardanol by enzymatic double bond epoxidation with
lipase and acetic acid in toluene [16–19].
Only few publications deal with the modification of lignin for use as
epoxides [20–23]. Three processes have been described in the literature to
prepare epoxidized lignin [24]. The main one is based on the oxypropyla-
tion of lignin to yield a lignin with more accessible hydroxyl groups. These
hydroxyl groups are then converted into epoxide groups by reaction with
epichlorohydrin, and cross-linking occurs by addition of diamines [24].
A variety of epoxide prepolymers that have been obtained from biobased
polyols like glycerol and sorbitol are commercially available [25, 26]. These
are mainly of the aliphatic glycidyl ether type. Equally, there are reports
on the synthesis of epoxide prepolymes from glycerin [27, 28]. Diglycidyl
 Polymer Matrix: Epoxy Resins 419

ethers of isosorbide as well as oligo-glycidyl ethers of isosorbide have also

been synthesized, leading to oligomers of epoxidized isosorbide by reac-
tion with epichlorohydrin [29–34]. Lactic acid also seems usable to pre-
pare either linear or hyperbranched epoxide prepolymer, depending on the
experimental conditions used [35]. Finally, epoxy monomers from sugars
can also be prepared. They are usually obtained by double bond oxidation,
needing the use of strong oxidative agents in large excess [28].
Furthermore, the industry can use epichlorohydrin derived from
biobased glycerol, which is an inexpensive and abundant source from soap
industry. Epichlorohydrin from such a source, named biobased epichloro-
hydrin, is now commercially available.
Researchers are also interested in epoxidized plant oils and fatty acids
as alternatives because they display interesting and comparable thermal
properties to commercial DGEBA. ENR is another interesting biobased
material that has been employed as toughening agent with petroleum-
derived epoxy resin [36–40].

18.7 Epoxy-Matrix-Based Biofiber Composites

Natural-fiber-based epoxy resin composites provide a unique combina-
tion of great versatility, high performance, and production at cheaper rates
compared to synthetic thermoplastics. Study also shows that the physical
and mechanical properties of epoxies are improved in the greater majority
of cases by the incorporation of natural fibers.
Jawaid and Abdul Khalil developed oil palm-jute-reinforced epoxy
matrix composites and studied their dynamic mechanical properties
and thermal degradation [41]. Thermogravimetric analysis indicated an
increase in thermal stability when jute fibers are incorporated along with
oil palm empty fruit bunches (EFB). A DGEBA-type epoxy resin was used
together with a reactive polyamide as curing agent.
Oil palm EFB and woven jute (Jw) fiber-reinforced epoxy matrix com-
posites were prepared by Jawaid, employing a hand lay-up method [41].
An epoxy resin was used as matrix, and trilayer hybrid composites of EFB/
woven jute/EFB and woven jute/EFB/woven jute were prepared by keeping
the EFB/woven jute fiber weight ratio constant at 4:1. The chemical resis-
tance properties of the EFB/woven jute/EFB and woven jute/EFB/woven
jute fiber-reinforced hybrid composites were studied by using three acids,
three alkalis, and three solvents. It was found that all the composites are
resistant to various chemicals. It was observed that a marked reduction in
void content of the composites occurred with the hybridization of oil palm
420 Adhesives for Wood and Lignocellulosic Materials

EFB with woven jute fiber. A density and moisture content study demon-
strated that density and moisture content property was enhanced in hybrid
composites. The hybrid composites showed lower impact properties than
pure EFB composites. The Izod impact strength of EFB/woven jute/EFB
and woven jute/EFB/woven jute hybrid was found to be 72.4 and 57.9 J/m,
respectively. The impact fracture surface of the composites was studied
with the help of scanning electron microscopy.
Ojinmah et al. presented the results on the effect of a semi-nanofiller from
rice husk on the mechanical properties of ENR [42]. This was studied and
compared with carbon black-filled epoxidized natural rubber composites.
The particle size distribution of the milled rice husk was determined using
optical microscopy and digital imaging technique. The semi-nanopowder
obtained by ball milling of the rice husk was characterized for pH, iodine
value, cellulose content, lignin content, hemicellulose content, moisture
content, bulk density, and loss on ignition. The result of the physicochem-
ical analysis showed excellent values that compared favorably with other
literature reports. Optical microscopy and digital imaging of the rice husk
nanofiller showed a spherical particle of average size 221 nm. The results
of the mechanical testing presented similar trends and close values for
both carbon black-filled ENR and rice husk semi-nanofilled ENR at filler
loading in the range 10–50 phr. Consequently, rice husk nanofiller can be
a good substitute for carbon black for products where cost, compression
set, and rebound resilience properties are critical.

References
1. Saunders, K.J., Organic Polymer Chemistry, Chapman and Hall, London,
1973.
2. Boyle, M.A., Martin, C.J., Neuner, J.D., Epoxy Resins, ASM Handbook, vol. 21,
pp. 78–89, Composites, ASM International, Almere, The Netherlands, 2001.
3. H.A. Newey and E.C. Shokal, Glycidyl ether composition and method of
using same. US Patent 2,575,558, 1951, Assigned to Shell Development Co.
4. E.C. Shokal, H.A. Newey, T.F. Bradley, Nitrogen containing polyethers
and process for curing glycidyl polyethers to resinous products. US Patent
2,643,239, 1953, Assigned to Shell Development Co.
5. Shirude, S.R., Shambharkar, S.Y., Bhosale, H.B., Patil, V.U., Patil, A.G., A sur-
vey on epoxy resins. Int. J. Innov. Res. Sci. Eng. Technol., 6, 14861–14867,
2017.
6. Rakotomalala, M., Wagner, S.S., Döring, M., Recent developments in halo-
gen free flame retardants for epoxy resins for electrical and electronic appli-
cations. Materials, 3, 4300–4327, 2010.
 Polymer Matrix: Epoxy Resins 421

7. Prileschajew, N., Oxydation ungesättigter Verbindungen mittels organischer

Superoxyde. Chem. Ber., 42, 4, 4811–4815, 1909. http://www.chemgapedia.
de/vsengine/vlu/vsc/en/ch/2/vlu/oxidation_reduktion/epxo_per_1.vlu.
html.
8. Tellez, G.L., Vigueras-Santiago, E., Hermandez-Lopez, S., Characterization
of linseed oil epoxidized at different percentages. Superf. Vacio, 22, 5–10,
2009.
9. B. Boutevin, S. Caillol, C. Burguiere, S. Rapior, H. Fulcrand, H. Nouailhas,
Novel method for producing thermosetting epoxy resins. Patent WO
2010136725, 2010. Assigned to Centre National de la Recherche Scientifique,
France.
10. Nouailhas, H., Aouf, C., Le Guerneve, C., Caillol, S., Boutevin, B., Fulcrand,
H., Synthesis and properties of biobased epoxy resins. Part 1: Glycidylation
of flavonoids by epichlorydrin. J. Polym. Sci., Part A: Polym. Chem., 49,
2261–2270, 2011.
11. Benyahya, S., Aouf, C., Caillol, S., Boutevin, B., Fulcrand, H., Functionalized
green tea tannins as phenolic prepolymers for bio-based epoxy resins. Ind.
Crops Prod., 53, 296–307, 2014.
12. Jahanshahi, S., Pizzi, A., Abdolkhani, A., Doosthoseini, K., Shakeri, A., Lagel,
M.-C., Delmotte, L., MALDI-TOF and 13C-NMR and FT-MIR and strength
characterization of glycidyl ether tannin epoxy resins. Ind. Crops Prod., 83,
177–185, 2016.
13. Jahanshahi, S., Pizzi, A., Abdolkhani, A., Shakeri, A., Analysis and testing of
bisphenol-A-free bio-based tannin epoxy-acrylic adhesives. Polymers, 8, 143,
2016.
14. H. Tomita and K. Yonezawa, Epoxy resin and process to prepare the same.
European Patent EP 0095609, 1983. Assigned to Kanegafuchi Chemical Ind.
15. C.G. Weller, E.J. Siebert, Z. Yang, R.K. Agarwal, W.E. Fristad, B.D. Bammel,
Autodeposition compositions for polymeric coatings of reduced gloss, good
corrosion resistance and uniform appearance. Patent WO 2003026888,
2003.
16. Devi, A. and Srivastava, D., Enzymatic epoxidation and polymerization
of cardanol obtained from a renewable resource and curing of epoxide-
containing polycardanol. J. Appl. Polym. Sci., 102, 2730–2737, 2006.
17. Unnikrishnan, K.P. and Thachil, E.T., Synthesis and characterization of
cardanol-based epoxy systems. Des. Monomers Polym., 11, 593–607, 2008.
18. He, J., Xu, S., Xu, X., Study on the anacardiol modified epoxy resin. Tuliao
Gongye, 29, 5–11, 1999.
19. Nieu, H.N., Tan, T.T.M., Huong, N.L., Epoxy–phenol–cardanol–formalde-
hyde systems: Thermogravimetry analysis and their carbon fiber composites.
J. Appl. Polym. Sci., 61, 2259–2264, 1996.
20. Simionescu, C.I., Rusan, V., Macoveanu, M.M., Cazacu, G., Lipsa, R., Vasile,
C., Stoleriu, A., Ioanid, A., Lignin/epoxy composites. Compos. Sci. Technol.,
48, 317–323, 1993.
422 Adhesives for Wood and Lignocellulosic Materials

21. Feldman, D., Lacasse, M., Beznaczuk, L.M., Lignin–polymer systems and
some applications. Prog. Polym. Sci., 12, 271–276, 1987.
22. Tai, S., Nagata, M., Nakano, J., Migita, N., Studies on utilization of lignin. IV.
Epoxidation of thiolignin. Mokuzai Gakkaishi, 13, 102–107, 1967a.
23. Tai, S., Nakano, J., Migita, N., Studies on utilization of lignin. V. Adhesive
from lignin epoxide. Mokuzai Gakkaishi, 13, 257–262, 1967b.
24. Koike, T., Progress in development of epoxy resin systems based on wood
biomass in Japan. Polym. Eng. Sci., 52, 701–717, 2012.
25. Shibata, M. and Nakai, N., Preparation and properties of biocomposites
composed of bio-based epoxy resin, tannic acid, and microfibrillated cellu-
lose. J. Polym. Sci., Part B: Polym. Phys., 48, 425–433, 2010.
26. Takada, Y., Shinbo, K., Someya, Y., Shibata, M., Preparation and properties of
bio-based epoxy montomorillonite nanocomposites derived from polyglyc-
erol polyglycidyl ether and -polylysine. J. Appl. Polym. Sci., 113, 479–484,
2009.
27. Acierno, D., Russo, P., Savarese, R., Oxidation of maltitol and sorbitol as a way
to bioepoxies, Polymer Processing Society, PPS-24, Salerno, Italy, 2008.
28. Sachinvala, N.D., Winsor, D.L., Menescal, R.K., Ganjian, I., Niemczura, W.P.,
Litt, M.H., Sucrose-based epoxy monomers and their reactions with dieth-
ylenetriamine. J. Polym. Sci., Part A: Polym. Chem., 36, 2397–2413, 1998.
29. A. East, M. Jaffe, Y. Zhang, L. Catalani, Thermoset epoxy polymers from
renewable resources such as anhydrosugars. Patent WO 2008147473, 2008a.
Assigned to New Jersey Techn. Inst.
30. A. East, M. Jaffe, Y. Zhang, L. Catalani, Ethers of bisanhydrohexitols. US
Patent 20080021209, 2008b. Assigned to New Jersey Techn. Inst.
31. Achet, D., Delmas, M., Gaset, A., Biomass as a source of chemicals. VI.
Synthesis of new polyfunctional ethers of isosorbide in solid–liquid hetero-
geneous mixtures. Biomass, 9, 247–254, 1987.
32. Feng, X., East, A.J., Hammond, W., Jaffe, M., Sugar-based chemicals for envi-
ronmentally sustainable applications, in: Contemporary Science of Polymeric
Materials, vol. 1061, L. Korugic-Karasz (Ed.), pp. 3–27, ACS Symp. Ser,
Oxford University Press, 2010.
33. Feng, X., East, A.J., Hammond, W.B., Zhang, Y., Jaffe, M., Overview of
advances in sugar-based polymers. Polym. Adv. Technol., 22, 139–150, 2011.
34. I. Wiesner, J. Kriz, V. Bruthans, J. Kolinsky, Glycidyl ethers of phenols and
polyphenols for synthesis of epoxy resins. Patent CS 113977, 1965.
35. Ma, S., Liu, X., Jiang, Y., Tang, Z., Zhang, C., Zhu, J., Bio-based epoxy resin
from itaconic acid and its thermosets cured with anhydride and comono-
mers. Green Chem., 15, 245–254, 2013.
36. Kumar, R.N., Kong, W.C., Abusamah, A., UV radiation curing of surface
coatings based on ENR-cycloalipahatic di-epoxide-glycidyl methacry-
late system by cationic photointiators—Optimization of process variables
through response surface methodology. J. Coat. Technol., 71, 896, 79–88,
1999.
 Polymer Matrix: Epoxy Resins 423

37. Kumar, R.N. and Mehnert, R., Electron beam curing of the system consisting
of cycloaliphatic diepoxide-epoxidized natural rubber–glycidyl methacry-
late in presence of cationic initiators. Macromol. Mat. Eng., 286, 449–455,
2001a.
38. Kumar, R.N., Mehnert, R., Scherzer, T., Bauer, F., CP MAS NMR spectros-
copy to the characterization of UV/EB cured epoxidized natural rubber
blends. Macromol. Mat. Eng., 286, 598–604, 2001b.
39. Kumar, R.N., Woo, C.K., Abusamah, A., UV curing of surface coating sys-
tem consisting of cycloaliphatic di-epoxide–ENR–glycidyl methacrylate by
cationic photointiators—Charaterization of the cured film by FTIR spectros-
copy. J. Appl. Polym. Sci., 73, 1569–1577, 1999.
40. Rosli, W., Daud, W., Kumar, R.N., Salleh, M.Z., Mahmood, M.H., Studies on
cationic curing of cycloaliphatic diepoxide-epoxidized palm oil (EPO) for
surface coatings. Eur. Polym. J., 39, 593–600, 2003.
41. Jawaid, M. and Abdul Khalil, H.P.S., Effect of layering pattern on the dynamic
mechanical properties and thermal degradation of oil palm–jute fibres rein-
forced epoxy hybrid composites. Bioresources, 63, 2309–2322, 2011.
42. Ojinmah, N., Uchechukwu, T.O., Ezeh, V.O., Ogbobe, O., Studies on the
effect of rice husk semi-nano filler on the mechanical properties of epoxi-
dized natural rubber composites. Eur. J. Adv. Eng. Techn., 4, 164–171, 2017.