3 Epoxy Resins
Epoxy resins are formed from an oligomer containing
at least two epoxide groups and a curing agent, usu-
ally either an amine compound or a diacid com-
pound. A great variety of such resins is on the market.
There are many monographs on epoxy resins available
[1,2].
3.1 History
N. Prileschajew discovered in 1909 that olefins can
react with peroxybenzoic acid to form epoxides [3].
Schlack claimed in 1939 a polymeric material based
on amines and multifunctional epoxides [4]. Castan,1
in the course of searching for dental materials,
claimed the preparation of bisphenol A diglycidyl
ether (DGEBA) [5,6]. A similar material, but higher
in molecular weight, was invented by Greenlee [7].
Epoxy resins came on the market around 1947.
The first major intended application was as coating
material.
3.2 Monomers
3.2.1 Epoxides
Epichlorohydrin is the monomer used for the synthe-
sis of glycidyl ethers and glycidyl esters. Epichlorohy-
drin (1-chloro-2,3-epoxypropane) is synthesized from
propene via allyl chloride. A number of epoxides are
shown in Table 3.1. Reactive diluents, i.e., monofunc-
tional epoxide compounds, are shown in Table 3.2.
The curing of cycloaliphatic epoxides proceeds eas-
ily with anhydrides, but is too slow with amines. Syn-
thetic procedures for including styrenic, cinnamoyl,
or maleimide functionalities into cycloaliphatic epoxy
compounds have been described [8].
3.2.1.1 Epoxide Equivalent Weight
The equivalent weight of the epoxide used is an impor-
tant parameter for the amount of curing agent needed.
The common method to determine the equivalent
weight is the titration procedure with HBr in glacial
1 Pierre Castan, born in Bern 1899, died in Geneva 1985.
Fink: Reactive Polymers Fundamentals and Applications. http://dx.doi.org/10.1016/B978-1-4557-3149-7.00003-6
© 2013 Elsevier Inc. All rights reserved.
acetic acid. However, a method for the determination
of the epoxide equivalent weight in liquid epoxy resins
using proton nuclear magnetic resonance (1 H-NMR)
spectroscopy has been described [9].
3.2.2 Phenols
Bisphenol A is the most important ingredient in stan-
dard epoxy resins. It is prepared by the condensation
of acetone with phenol. The latter two compounds can
be prepared in the Hock process by the oxidation of
cumene (see Figure 3.1).
Phenolic products are shown among others in
Table 3.3 and Figure 3.2. The hydroxyl and amino
functions are epoxidized with epichlorohydrin.
3.2.3 Specialities
3.2.3.1 Hyperbranched Polymers
Hyperbranched polymers are highly branched macro-
molecules that are prepared through a single-step
polymerization process [33]. Many polymers of this
type are also known as dendrimers, because their
structure resembles the branches of a tree. Also, star-
like and comb-like polymers belong to the class of
hyperbranched polymers. However, hyperbranched
polymers are built up from dendritic, linear, and ter-
minal units. They can be synthesized via three routes:
1. Step-growth polycondensation of ABx
monomers.
2. Self-condensing vinyl polymerization of AB∗
monomers.
3. Multibranching ring opening polymerization of
latent ABx monomers.
The methods of synthesis available allow a wide
variety of different polymer types. Further special
properties can be imparted by suitable end capping
reactions. This type of polymer has unique properties
that are characteristic for dendritic macromolecules,
such as low viscosity, good solubility, and high
functionality.
95
96 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

Table 3.1 Epoxides

Epoxide Remark/Reference
Epichlorohydrin Used for the formation of glycidyl ethers and esters
Butadiene diepoxide
1,4-Butanediol diglycidyl ether (1,4-BDE) [10]
Glycerol diglycidyl ether
1,3-Didodecyloxy-2-glycidyl-glycerol Amphiphilic polymers, for potential use as
emulsifiers and solubilizing agents [11]
Poly(butadiene) epoxides Flexible
Vinylcyclohexene epoxide Both with vinyl and epoxy function
Styrene oxide (= ethenylphenyloxirane) Both with vinyl and epoxy function [12]
Glycidyl methacrylate (GMA) Both with vinyl and epoxy function
Epoxidized linseed oil [13]
Epoxy methyl soyate [14]
Epoxy allyl soyate [14]
Vernonia oil Naturally epoxidized, E-12,13-epoxyoctadeca-E-9-
enoic acid esters [15–17]
Triglycidyl isocyanurate
Triglycidyloxy phenyl silane Flame retardant [18]
2-(6-Oxy-6H-dibenz[c,e][1,2]oxa-phoshorin-6-yl)-1,4-benzenediol Flame retardant [19]
3,4-Epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate Coatings
2,3,8,9-Di (tetramethylene)-1,5,7,11-tetraoxaspiro[5.5]undecane Dental applications [20]
Bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate Dental applications [20]
Epoxidized cyclololefins Multifunctional, cf. Figure 3.1
Fluoro-epoxides [21]
Biphenyl-based epoxies Liquid crystalline, cf. Figure 3.3
Terephthaloylbis(4-oxybenzoic) acid DGEBA adduct Liquid crystalline [22]
Bis[3-(2,3-epoxypropyl thio)phenyl]sulfone Optical applications [23]
4,4 -Dihydroxychalcone-epoxy oligomer Optical applications [24]

Table 3.2 Reactive Diluents

Reactive Diluent Remark/Reference

Phenyl glycidyl ether
Styrene oxide
Allyl glycidyl ether
Tetraethyl orthosilicate caprolactone diol adducts Cationic curable coatings [25]
2-Hydroxy-4(2,3-epoxypropoxy) benzophenone Reactive photostabilizer for wood [26]
exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalimidocaproic acid Polymers show anticarcinogenic activity [27]
exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride Polymers show anticarcinogenic activity [28,29]

Dendrimers are used in medical fields, as carriers
of organic compounds. Hyperbranched polymers are
easier to synthesize in large quantities and are used
as tougheners, plasticizers, antiplasticizers, and cur-
ing agents [34,35]. Hyperbranched polymers (HBP)
with hydroxyl terminal groups can initiate curing
by a proton donor–acceptor complex. In curing a
tetrafunctional epoxy resin, the activation energy is
lower than in an epoxy system with linear polymers
[36]. Hyperbranched polymers strongly enhance the
curing rate due to the catalytic effect of hydroxyl
groups [37]. The gel time increases with increasing
functionality from DGEBA to tetraglycidyl-4,4 -di-
aminodiphenylmethane (TGDDM) [38]. A hydroxyl
3: EPOXY RESINS 97

O
CH 2 O C HO CH 2 OH HO NH 2

O O
Bisphenol-F p-Aminophenol
CH 3 H3 C

HO OH CH 3
O O O
HO C OH
CH 3
O
CH CH
Bisphenol-A

O
H 2N CH 2 NH 2
HO OH
O O
Figure 3.1 Cycloaliphatic epoxides. Tetrakis(4-hydroxyphenyl)ethane 4,4 -Diaminodiphenylmethane

OH OH OH
functionalized HBP reduced the gel time of the blends
because of the accelerating effect of −OH groups to CH 2 CH 2 CH 2

the epoxy curing reaction.

Star-like epoxy polymers can be rooted from
poly(hydroxyfullerene) with a cycloaliphatic epoxy
monomer [39]. Around 8 to 10 epoxy units can be
attached to the fullerene core.
The addition of small amounts of hyperbranched
polymer to an epoxy system enhances dramati-
cally its toughness. The critical strain energy release
rate of DGEBF resin can be increased by a fac-
tor of 6 by the addition of only 5% of hyper-
branched polymer [40]. At higher concentrations, a
Novolac
Figure 3.2 Compounds for epoxide resins.
phase separation is indicated by two glass transition
temperatures [41].
In composite materials, resins modified by
hyperbranched polymers allow higher volume frac-
tions of fibers for producing void-free laminates in
comparison to unmodified resins [42].

Table 3.3 Compounds for Glycidyl Functionalization for Epoxide Resins

Compounda Remark/Reference
Bisphenol A Standard resins
Bisphenol F
Phenol novolak
Naphthyl or limonene-modified Bisphenol A formaldehyde Improved mechanical properties, reduced water
novolak absorption [30]
Cresol novolak
Tetrakis(4-hydroxyphenyl)ethane Increases crosslinking density
p-Aminophenolb Higher reactivity at amine curing
Aminopropoxylate [31]
4,4 -Diaminodiphenylmethaneb
Hexahydrophthalic acidc
1,3-Bis(3-aminopropyl)tetramethyl disiloxane [32]
Tetrabromobisphenol A For flame retardant formulations
Bishydantoin
Isocyanurate Powder coatings
Cresol Reactive diluent
1,4-Butanediol Reactive diluent

a Compounds are epoxidized at the hydroxyl function with epichlorohydrin

b Compounds are epoxidized at the amino function with epichlorohydrin
c Compounds are epoxidized at the carboxyl function with epichlorohydrin
98 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

3.2.3.2 Liquid Crystalline Epoxide O O

Resins
Initially a few technical terms concerning liquid crys-
tals are recalled. There are textbooks on liquid crys-
tals, e.g., that of Collings and Hird [43].
Liquid Crystal. Liquid crystals were discovered by
the Austrian chemist and botanist Friedrich Reinitzer,
who found that cholesterol benzoate did not melt into
a clear liquid, but remained turbid. On further heating
the turbid liquid suddenly turned clear. This transition
point is now called the clearing point. For this reason,
in addition to the common states of aggregation, the
liquid crystalline state was established. The term liq-
uid crystal goes back to the German physicist Otto
Lehmann.
Liquid crystals are formed mostly by rod-like
molecules. They are sometimes addressed as meso-
morphic phases. Materials that can form such phases
are called mesogens. An ordinary fluid is called
isotropic, i.e., its properties are independent of direc-
tion. A liquid crystal is orientated, or likewise an
anisotropic liquid. This means that the molecules are
oriented preferably in a certain direction. Such an
anisotropic fluid is a nematic liquid crystal. A liq-
uid crystal more similar to a solid is a smectic phase.
Here the molecules are arranged in layers, but within
the layers the molecules have no fixed positions.
Polymers. Liquid crystalline polymers exhibit a
number of improved properties in comparison with
traditional plastics, in particular increased elastic
moduli at high temperatures, reduced coefficients of
thermal expansion, increased decomposition onset
temperatures, and reduced solvent absorption.
Suitable epoxide monomers are based on biphenyl
moieties [44]. Monomers for liquid crystalline epox-
ide resins are shown in Figure 3.3. It is believed
that micro-Brownian motion in the polymer chain is
increasingly suppressed as the mesogen concentration
increases. This effect causes an increase in the ther-
mal decomposition onset temperatures, a decrease of
the coefficient of thermal expansion, and a decrease
in water absorption.
When the diglycidyl ether of bisphenol A is cured
with sulfanilamide, a crosslinked network with liquid
crystalline properties is obtained [45]. Sulfanilamide
has two different amine functions of unequal reac-
tivity. This causes the formation of a smectic phase
CH 2 C CH 2 O O CH 2 C CH2
H H
H 3C CH 3
O O
CH 2 C CH 2 O O CH 2 C CH2
H H
H 3C CH 3
O O
O O
C H 2 C (CH 2 ) n CH 2 CH 2 (CH 2) n C CH 2
H H
Figure 3.3 Monomers for liquid crystalline epoxide
resins.
when it is used as a curing agent. Polarized optical
microscopy indicates that the epoxy monomer does
not show a liquid crystalline (LC) phase. Also a mix-
ture of sulfanilamide and diglycidyl ether of bisphe-
nol A does not show LC properties. An isotropic
liquid is formed above the melting point. However,
when the reaction between epoxy and amine proceeds,
an LC texture is developed, which is locked in the
crosslinked network by the nematic arrangement.
3.2.4 Manufacture
3.2.4.1 Epoxides
Epoxides can be manufactured by the epoxidation
reaction, in particular:
1. by direct oxidation,
2. via peroxyacids,
3. in situ epoxidation,
4. by hypochlorite reaction, and
5. by reaction with fluoro complexes.
Direct Oxidation. Olefins can be epoxidized by
oxidizing them in the vapor phase in the presence of
a silver catalyst. The catalyst is activated by adding
small amounts of dichloroethane to the reaction mix-
ture. The direct oxidation with oxygen is less impor-
tant for the synthesis of epoxies used for epoxy resins,
in favor of peroxyacids.
Certain Schiff bases that are attached on polymers
allow the direct oxidation of olefins. A polymer bound
Schiff base ligand is prepared from poly(styrene)
3: EPOXY RESINS
bound salicylaldehyde and glutamic acid. With com-
plexes of these catalysts, cyclohexene, 1-octene,
1-decene, 1-dodecene, and 1-tetradecene can be oxi-
dized by molecular oxygen [46].
Peroxyacids. Also, organic peroxides can serve as
an oxygen source. Unsaturated fatty acids and their
esters are epoxidized with peroxyacetic acid. Origi-
nally peroxybenzoic acid was used, which is highly
selective. However, this reagent is comparatively
expensive. Several other peroxyacids have been inves-
tigated; they are in general less efficient. The reaction
of olefins with peroxyacids is a single-step reaction.
Hydrogen peroxide itself is a rather poor epox-
idation oxidant; however, it is used to generate
peroxyacids that are much more active. The peroxy-
acids are prepared by reacting hydrogen peroxide with
the corresponding acid. The reaction is an equilibrium
reaction. Highly concentrated peroxyacids can be
obtained by adding anhydrides, or removing the water
by azeotropic distillation. Another route to prepare
peroxyacids starts from the anhydride and sodium
peroxide, in the presence of an acid as catalyst. There
should not be even traces of heavy metals present
that cause a loss in activity of the hydrogen peroxide.
For technical synthesis, peroxyacetic acid is used
most frequently, because it has a high equivalent
weight, a high efficiency for epoxidation, and suffi-
cient stability.
In Situ Epoxidation. Theperoxyacidscanberegen-
erated during the epoxidation reaction with hydrogen
peroxide. In this way all the hazards in preparation
and handling of the peroxyacids as such are avoided.
The reaction is heterogeneous and the peroxyacid has
to be regenerated under conditions that would result
in ring opening of the epoxide. Therefore, only fast
epoxidation reactions can be conducted utilizing the in
situ technique. For this reason, the most reactive per-
oxyacids are also selected. These are in particular the
3-nitroperoxybenzoic acid and 4-nitroperoxybenzoic
acid.
Less reactive olefins must still be epoxidized with
the peroxyacids formed in a previous step. The ring
opening of the epoxide with the acid formed from the
peroxyacid can be minimized, allowing the phases
utmost separation. This means there should be only
small agitation. On the other hand, with certain solvent
combinations the epoxide and the acid are mutually
insoluble.
99
Hypochlorite. Partially fluorinated epoxides can be
prepared by the oxidation of the corresponding olefins
by NaOCl or NaOBr with phase transfer catalysts,
e.g., methyltricaprylylammonium chloride [47]. For
example, hexafluoroisobutene reacts with the solu-
tion of sodium hypochlorite in water at 0–10 ◦ C
giving the corresponding epoxide in a yield of
65–70%.
Fluoro Complex. By reacting diluted fluorine with
aqueous acetonitrile, a complex HOF · CH3 CN is
formed. This complex is a very efficient oxygen trans-
fer agent. It was shown to be useful to obtain various
types of epoxides that are otherwise difficult to syn-
thesize. The products can be obtained in a single-step
reaction with high yield [48].
3.2.4.2 Glycidyl Ethers
In the simplest case a glycidyl ether for an epoxy
resin is prepared by the reaction of bisphenol A (and
epichlorohydrin), as pointed out in Figure 3.4. In the
first step DGEBA is formed; however, the conden-
sation can proceed further. The reaction proceeds in
two steps. First the epoxide ring is opened and then
the ring is formed again, as shown in Figure 3.5.
Hydrogen chloride is evolved during the condensa-
tion and captured with caustic soda. The ring opening
occurs such that the primary carbon atom is attacked
and thus a 1,2-chlorohydrin (CH2 CH(OH)CH2 Cl)
is formed, as shown in Figure 3.5.
However, in a side reaction the secondary carbon
atom is also attacked and thus a 1,3-chlorohydrin
O CH 3
CH 2 CH CH 2 Cl + HO C OH
CH 3
O CH 3
C H2 CH CH 2 O C O
CH 3 CH 2
CH OH
O CH 3 CH 2 n
CH 2 CH CH 2 O C O
CH 3
Figure 3.4 Synthesis of an epoxide oligomer.
100
O thus the hydrophobicity is enhanced. Fluorinated
OH + CH 2 CH CH 2 Cl
OH
O CH2 CH CH 2 Cl
-HCl
O
O CH2 CH CH 2
Figure 3.5 Formation of the glycidyl ether.
(HOCH2 CH()CH2 Cl) is formed. If the degree
of dehydrochloration is not complete, then 1,2-
chlorohydrin end groups also may be present.
Concerning the nomenclature, the situation is
confusing. There are many synonyms for the
glycidyl ethers. The Chemical Abstracts name
for DGEBA is 2,2 -[(1-methylethylidene)bis(4,1-
phenyleneoxymethylene)]bis(oxirane), and there are
some 12 other synonyms of chemical names in use,
besides the trade names.
We focus back on the main reaction. The newly
formed epoxide groups from the second step of the
reaction may again undergo a reaction with the phe-
nolic group, and in the case of a bifunctional phenol,
such as bisphenol A, the molecule grows. The degree
of oligomerization (n − 1 in Figure 3.4) can vary from
1 to approximately 25. The oligomer is liquid at room
temperature when n is smaller than one and becomes
solid when n is larger than two.
The degree of polymerization that can be achieved
depends on the ratio of bisphenol A to epichlorohy-
drin. If epichlorohydrin is in excess, then the digly-
cidyl ether will be the main product. Impurities such
as water can substantially decrease the degree of
polymerization by side reactions. Water reacts with
epichlorohydrin to form a glycol.
3.2.4.3 Fluorinated Epoxides
The incorporation of fluorine enhances the chemical
and thermal stability, and the weathering resistance.
Furthermore, the surface tension is lowered and
REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS
epoxy monomers have been synthesized from
fluorinated diols, such as 2,2,3,3,4,4,5,5-octafluoro-
hexane-1,6-diol or 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-
hexadecafluoro-decane-1,10-diol by etherification
with allyl chloride and subsequent oxidation of
the allyl group [21]. In UV curing, the monomers
showed a higher reactivity than hexanediol diglycidyl
ether.
The adduct of 2-chlorobenzotrifluoride and gly-
cerol diglycidyl ether (DGEBTF) has been co-reacted
with DGEBA using 4,4 -diaminodiphenylmethane as
hardener [49]. The introduction of the trifluoromethyl
group into the chain of the epoxy resin results in an
improvement of the dielectric and mechanical proper-
ties. Also, the glass transition temperature is lowered.
The glass transition temperature of a pure DGEBA
resin is 193 ◦ C whereas the glass transition tempera-
ture of the DGEBTF resin is 105 ◦ C. This indicates
that the introduction of fluorine enhances the mobility
of the network.
3.3 Special Additives
3.3.1 Crosslinking Agents
Formaldehyde novolak resins based on 4,4 -
methylenedianiline and p-nonylphenol were
synthesized using an acid catalyst. The resins
were eventually modified by allylation and methacry-
lation. This modification makes them suitable as
crosslinking agents for epoxy resin and bismaleimide
resin formulations [50]. Characterization of the
curing behavior of the original formaldehyde novolak
resins by differential scanning calorimetry shows a
single exothermic peak. This indicates cure reactions
only between epoxy ring and amine protons. In
contrast, epoxy resins, bismaleimide resins, and the
modified formaldehyde novolak resins show two
exothermic peaks [50].
3.3.2 Toughening Agents
Highly crosslinked epoxy resins are brittle. For
various applications they need to be toughened.
Toughening agents are summarized in Table 3.4.
Extensive literature on toughening of polymers is
available [51–54]. The toughening mechanisms of
elastomer-modified epoxy systems are different from
flexibilized epoxy systems.
3: EPOXY RESINS 101

Table 3.4 Toughening Agents for Epoxy Resins

Compound Class Reference

Poly(ethylene) phthalates [55]
Poly(ethylene phthalate-co-ethylene terephthalate) [56]
Hyperbranched aliphatic polyester [57,58]
Hyperbranched block copolyethers [59]
Epoxidized soyabean oil [14,60,61]
Copolymers of 2-ethylhexyl acrylate and acrylic acid [62]
Methacrylic microgels [63]
Terpolymers of N-phenyl maleimide, styrene and p-hydroxystyrene [64]
Triblock copolymer poly(styrene-b-ethylene-co-butene-b-styrene) [65]
Poly(benzimidazole) [66]
Poly(phenylene oxide) [67]
Silicon-modified poly(urethane) oligomers [68]
Poly(dimethyl siloxane) polymers
Epoxy-aminopropyltriethoxysilane [69]
Poly(ether ether ketones) [70]
Polyetherimides [71–73]
Carboxylated polymers [74]
Phenolic hydroxy-terminated polysulfones [75,76]
Liquid rubbers [77]
Liquid rubbers carboxyl-terminated with poly(2-ethylhexyl acrylate) [78–80]
Poly(vinyl acetate) [81]
Rubbery epoxy-based particles [82]
Glass beads [83,84]

• Flexibilized epoxy systems reduce mechanical
damage through lowering modulus or plasticiza-
tion; this allows stress to be relieved through dis-
tortion of the material [85].
• Elastomer-toughened epoxy systems in general
maintain a large percentage of the modulus and
temperature resistance of the unmodified resin sys-
tem. Stress is absorbed by cavitation of the elas-
tomer particles and shear banding in the cavitated
zone. Elastomer-toughened epoxy systems can tol-
erate a certain degree of damage by preventing
growth of a crack. In this way the damaged region
remains local [86].
When using thermoplastic-modified thermosets,
compromises between toughness and thermal stability
associated with the rubber toughening of thermosets
can be avoided. Another advantage of using the
reaction-induced phase separation procedure is that by
the adequate selection of cure cycles and initial formu-
lations, a variety of morphologies can be generated.
However, the fracture toughness is significantly
improved with a nonreactive thermoplastic only
when bicontinuous or inverted phase structures are
formed. On the other hand, when the phase separation
produces thermoplastic-rich particles that are dis-
persed in a continuous thermoset-rich matrix, little or
no improvement of the fracture properties is obtained.
This is mainly due to the poor adhesion between the
phases [65].
Basically, functionalized thermoplastics are capa-
ble of forming a chemical linkage between the phases.
This interphase bonding can improve the adhesion
properties. However, the reactivity of the modifier can
also complicate the behavior and the control of the
phase separation process.
3.3.2.1 Polyvinyl Compounds
Many polyvinyl compounds increase the flexibility
and are used as toughening agents.
Poly(styrene). Blends of poly(styrene) with an
epoxy monomer (DGEBA) and a tertiary amine,
benzyldimethylamine (BDMA), are initially misci-
ble at 120 ◦ C. However, at very low conversions a
phase separation occurs. Here, at the cloud point, a
sharp decrease of the light transmittance is observed.
There is a significant difference between the refrac-
tive indices of poly(styrene) and the DGEBA/BDMA
102 REACTIVE POLYMERS FUNDAMENTALS
solution. The refractive index of the epoxy network
increases in the course of polymerization. Due to
the continuous increase of the refractive index of
the epoxy phase during curing, finally the refractive
indices of both phases match, so that the final materi-
als at complete conversion appear transparent [87].
Copolymers of Styrene and Acrylonitrile. In
an epoxy system containing TGDDM and a 4,4 -
diaminodiphenyl sulfone (DDS) hardener, blends
with poly(styrene-co-acrylonitrile) (SAN) up to 40
phr show complete miscibility over the entire range
[88]. The glass transition temperature and the curing
characteristics can be modeled with various theories
[89]. In several systems autocatalytic curing kinetics
is observed [90–94].
Copolymers of Phenyl Maleimide, Benzyl
Methacrylate, and Styrene. The vinylic com-
pounds can be polymerized in situ during the curing
of the epoxy system [95]. A suitable monomer system
consists of three monomers: phenyl maleimide, ben-
zyl methacrylate, and styrene. An advantage is that
by the admixing of the monomers the viscosity of the
uncured resins drops significantly.
Graft Polymers of Ethylene/vinyl Acetate onto
Methyl Methacrylate. A graft polymer synthe-
sized by grafting ethylene/vinyl acetate (EVA) onto
poly(methyl methacrylate) (PMMA) results in a
poly(ethylene-co-vinyl acetate) graft-PMMA that
gives a characteristic performance. The EVA moi-
eties are initially immiscible in the uncured epoxide
formulation. The PMMA moieties are initially mis-
cible; however, they separate during curing. There-
fore, EVA-g-PMMA as modifier yields stable disper-
sions of EVA blocks, favored by the initial solubility
of PMMA blocks. So the PMMA acts initially as a
compatibilizer for the epoxy moieties [96].
Blends of Poly(methyl methacrylate) and
Poly(ethylene oxide). Blends of poly(ethylene
oxide) (PEO) and PMMA form a single phase in
the melt. In solid mixtures of these polymers, phase
separation is often observed. In blends of an epoxy
resin with PMMA, PEO acts as a compatibilizer. The
morphology of the resulting polymer mixture may
be changed dramatically by only small amounts of
PEO. The stiffness is controlled by the corresponding
AND APPLICATIONS
matrix of the ternary mixture, but both strength and
fracture toughness are a function of the resulting
morphology [97].
Poly(benzimidazole). The incorporation of poly-
(benzimidazole) into a difunctional epoxy resin
matrix enhances both the glass transition temperature
of the matrix and its toughness [66].
Multilayer Particles. Multilayer particles of PM-
MA can be manufactured by emulsion polymeriza-
tion. They consist of alternate glassy and rubbery
layers. The outer layer bears glycidyl groups to allow
chemical bonding of the particles onto the cured resin.
This type of toughening particle is more effective
than acrylic toughening particles or a liquid carboxyl-
terminated butadiene acrylonitrile rubber [98].
3.3.2.2 Polycondensates
Aromatic polyesters that are prepared from aromatic
dicarboxylic acids and 1,2-ethanediol improve the
toughness of bisphenol A diglycidyl ether epoxy
resins. In particular, phthalic anhydride, isophthalic
acid, terephthalic acid, and 2,6-naphthalene dicar-
boxylic acid, and mixtures of these compounds, are
used. The aromatic polyesters are soluble in the epoxy
resin without solvents and are effective modifiers for
toughening the epoxy resins [55]. The inclusion of
20% poly(ethylene phthalate) increases the fracture
toughness of a cured resin by 130% with no loss of
mechanical and thermal properties [56].
Instead of 1,2-ethanediol, 1,4-cyclohexane-
dimethanol can be used to obtain poly(1,4-cyclo-
hexylenedimethylene phthalate) [99]. Other flex-
ibility enhancers are polyamide, polyetherimides
[71,72], carboxylated polymers [74], phenolic
hydroxy-terminated polysulfones [75], and fatty
diamines.
Polyetherimide. In blends of an epoxy system of
diglycidyl ether of bisphenol A and nadic methyl
anhydride, a phase separation occurs by the addi-
tion of polyetherimide in the course of curing. The
phase separation is not observed without polyether-
imide. By increasing the amount of polyetherimide
in the blends, the final conversion is decreased. This
indicates that polyetherimide hinders the cure reac-
tion between the epoxy and the curing agent [100].
3: EPOXY RESINS
Homogeneous structures are formed at low polyether-
imide concentration (5 phr) [101].
Poly(ether ether ketone). Poly(etheretherketone)
(PEEK) is a tough, semicrystalline high-performance
thermoplastic polymer with good thermal and
mechanical properties. Because of its semicrystalline
nature, it is difficult to blend this material with epoxy
resins.
Phenolphthalein poly(ether ether ketone)
(PEEK-C) is miscible with TGDDM. Several
methods, including dynamic mechanical analysis,
Fourier transform infrared spectroscopy, and scanning
electron microscopy, indicate that the cured blends
are homogeneous. With increasing PEEK-C content,
the tensile properties of the blends decrease slightly.
The fracture toughness factor also decreases. This
happens presumably due to the reduced crosslink
density of the epoxy network. Inspection of the
fracture surfaces of fracture toughness test specimens
by scanning electron microscopy shows the brittle
nature of the fracture for the pure epoxy resins
and its blends with PEEK-C [102]. A lower curing
temperature favored the homogeneous morphology
in amine cured DGEBA PEEK-C blends [103].
In general, the processing of blends with PEEK
should be easier using PEEK with terminal func-
tional groups and bulky pendant groups. However,
poly(ether ether ketone) based on tertiary butyl
hydroquinone (PEEK-T) showed a decreasing rate
of reaction with increasing PEEK-T content. The
rate of reaction also decreased with the isother-
mal curing temperature. This can be explained by
the phase separation. As the curing reaction pro-
ceeds, the thermoplastic component undergoes a
phase separation. The separated thermoplastic can
retard the curing reaction. The dispersed particle size
increases with the lowering of curing temperature
and with an increase in the thermoplastic material
added [70]. Poly(ether ether ketone)s are shown in
Figure 3.6.
Chain Extended Ureas. The synthesis of chain
extended ureas runs via a two-stage process. In the
first stage, a prepolymer with isocyanate end groups
is synthesized by the reaction of poly(propylene)
glycol and toluene diisocyanate. In the second
step, the prepolymer is end capped with dimethyl-
amine or imidazole, to result in an amine-terminated
103
O
O O C
C
O
C
O
PEEK-C
CH3
H3 C
C
CH3 O
O O C
PEEK-T
Figure 3.6 Poly(ether ether ketone)s.
chain-extended urea or an imidazole-terminated chain
extended urea, respectively, with flexible spacers
[104]. This type of toughening agent accelerates the
curing of the epoxide groups significantly because of
the amino functions in the molecule.
A bisphenol A-based epoxy resin was tough-
ened with a thermoplastic hydroxyl-terminated
poly(urethane) elastomer by blending in solution.
Measurements of tensile and flexural behavior
revealed that the toughened composites enhance
the properties in comparison to the neat epoxy
resin [105].
3.3.2.3 Liquid Rubbers
The addition of elastomers to epoxy adhesives can
improve peel strength, fracture resistance, adhe-
sion to oily surfaces, and ductility. Liquid rubbers,
like carboxyl-, amine-, or epoxy-terminated buta-
diene/acrylonitrile rubbers, are used as toughening
agents [77,106]. Liquid rubber modifiers are initially
miscible with the epoxy resin. However, in the course
of curing a phase separation takes place.
Carboxy-terminated butadiene/acrylonitrile co-
polymers (CTBN) are particularly suitable because of
their miscibility in many epoxy resins. The carboxyl
group can react easily with an epoxy group. If a CTBN
is not prereacted with an epoxy resin, the carboxylic
acid groups can react during curing.
Solid nitrile butadiene rubbers (NBRs), in particular
with high content of acrylonitrile, are also suitable
tougheners [107]. A high content of acrylonitrile in
104
the rubber imparts better compatibility between NBR
and the epoxy resin.
3.3.2.4 Silicone Elastomers
CTBN and amine-terminated butadiene acrylonitrile
elastomers lose the desired mechanical properties
in the high-temperature region and in the low-
temperature region. Silicone rubbers are superior in
this aspect. However, silicone rubbers are completely
immiscible with epoxy resins and cannot be used for
this reason. The addition of a silicone grafted PMMA
is effective to stabilize the interface of the silicone
rubber and the epoxy resin and helps to disperse the
silicone rubber in the epoxide matrix in this way. The
molecular weight of the silicone segment strongly
affects the effectiveness of the compatibilizer. With
increasing particle diameter of the silicone the fracture
toughness decreases and eventually drops below the
unmodified resin [108].
For a carboxyl-terminated dimethyl siloxane
oligomer used as a rubber modifier, aramid/silicone
block copolymers were used as compatibilizers [109].
The aramid-type blocks have phenolic groups on the
aromatic rings. These groups can react with the epoxy
resin to cause the compatibilization.
The toughness of an epoxy resin can be
improved by an epoxy-miscible allyl polyoxyethy-
lene polyoxypropylene ether by adding relatively low
amounts [110].
3.3.2.5 Rubbery Epoxy Compounds
Instead of liquid rubber, rubbery epoxy-based parti-
cles obtained from an aliphatic epoxy resin can be
blended with another epoxy resin to act as toughen-
ing agents themselves [82]. One of the limitations of
epoxy-CTBN adducts is their high viscosity; however,
there are also low-viscosity types available.
3.3.2.6 Phase Separation
During curing of polymer resin blends, a phase
separation occurs. The phase separation can be
characterized by:
1. small angle X-ray scattering,
2. light transmission,
3. light scattering,
4. transmission electron microscopy, and
5. atomic force microscopy.
REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS
The viscosity at the cloud point can have a strong
effect on the final morphology and mechanical prop-
erties of the resin. The phase separation mechanisms
are dependent on the initial modifier concentration
and on the ratio of the phase separation rate to the cur-
ing rate. The curing temperature has a strong effect on
the extent of phase separation. Annealing allows the
phase separation process to proceed further [72].
The extent of phase separation depends on the cure
cycle, as shown in blends of a standard epoxy resin and
PMMA. The extent of phase separation can be dimin-
ished or suppressed by longer precuring times at lower
temperatures, before the main curing is started [111].
In addition, the phase separation can be con-
trolled by the choice of curing agent. In the case
of PMMA as modifier, in an epoxy system, based
on DGEBA some hardeners effect a phase separa-
tion before gelation and others do not. For example,
DDS and 4,4 -methylenedianiline (MDA) result in a
phase separation, but for 4,4 -methylene bis(3-chloro-
2,6-diethylaniline) (MCDEA) no phase separation is
observed [112].
3.3.2.7 Preformed Particles
Preformed particles do not require phase separation
and remain in that shape in which they were added to
the neat resin or composite. Therefore, these particles
may be synthesized prior to the resin formulation and
then added to the thermosetting resin or formed in
situ, i.e., during the formulation of the resin, before
the resin is cured [113].
Prereacted urethane microspheres can be formed
by a dynamic vulcanization method in liquid digly-
cidyl ether of bisphenol A. The prereacted particles
are then added to an uncured epoxy resin system and
cured. The mechanical and adhesion properties do
not depend on any curing condition of epoxy resin
because the particles are stable, in contrast to a process
where a phase separation occurs during curing [114].
3.3.2.8 Inorganic Particles
In contrary to rubber, the toughening of inorganic
particles is rather modest. However, the toughening
by inorganic particles has an advantage insofar as it
can also improve the modulus. Rubber toughens such
that the increase in toughness is accompanied at the
expense of a decrease in the modulus.
The toughening of inorganic particles is explained
by the crack front bowing mechanism [115–117].
3: EPOXY RESINS
A crack front increases its length by changing its
shape when it interacts with two or more inhomo-
geneities in a brittle material. The inorganic parti-
cles inside the polymer matrix can resist a crack
propagation.
When a crack propagates in a rigid particle-filled
composite, the rigid particles try to resist. Because of
this resistance, the primary crack front has to change
its direction between the rigid particles (bowing), thus
forming a secondary crack front. The bowed sec-
ondary crack front now has more elastic energy stored
than the straight unbowed crack front. A crack front
starts to bow out between particles, when it meets the
particles.
Microcracking with debonding has been proposed
as one of the toughening mechanisms of glass
bead-filled epoxies. Three types of micro-mechanical
deformations can be distinguished [83]:
1. Step formation.
2. Debonding of glass beads and diffuse matrix
shear yielding.
3. Micro-shear banding.
Among the micro-mechanical deformations, micro-
shear banding is considered the major toughening
mechanism for glass bead-filled epoxies. Step for-
mation and combined debonding and diffuse matrix
yielding are secondary toughening mechanisms [84].
Glass Beads. The mechanical properties of hybrid
composites based on an epoxy resin have been inves-
tigated. The epoxy resion is based on the diglycidyl
ether of bisphenol A and triethylenetetramine is used
as the curing agent [118]. The impact strength is
increased by around 120% and 200% by the addition
10 phr of glass beads or 10 phr poly(urethane) resin.
However, the strain at break decreases with increasing
amount of glass beads.
3.3.3 Antiplasticizers
Antiplasticizers are additives for increasing the
strength and modulus of the respective mate-
rial. They act via strong interactions with the
epoxide matrix. Epoxides with antiplasticizers
characteristically [119]:
1. Have a sufficiently high value of the glass transi-
tion temperature as needed for the applications.
105
2. Exhibit higher modulus and higher toughness
around room temperature.
3. Exhibit lower water uptake at equilibrium.
Antiplasticizers for epoxide resins are shown
in Figure 3.7. The addition of the reaction
product of 4-hydroxyacetanilide and 1,2-epoxy-3-
phenoxypropane to an epoxide resin increases the ten-
sile strength and the shear modulus of the cured sys-
tem [120]. The mechanism of antiplasticization can
be formulated in terms of hindrance of the short-
scale cooperative motions in the glassy state due to
a dynamic coupling between the epoxy polymer and
the antiplasticizer molecule [121].
In systems where the antiplasticizers have a poor
affinity to the resin, a phase separation during curing
occurs. The mobility of the constituent groups can
be characterized by nuclear magnetic resonance tech-
niques [122].
3.3.4 Lubricants
In automotive, aviation and related industries, there is
a tendency to use metallic materials with polymeric
materials. For many parts in such applications, good
tribological properties are required [123]. Fluorinated
polymers are known as low friction materials. This
property arises due to their low surface energies (see
Figure 3.7).
Fluorinated poly(aryl ether ketone) (12F-PEK) can
be added to epoxy resins to improve the tribologi-
cal properties. At low concentrations of 12F-PEK,
OH
O
O CH 2 CH CH 2 O NH C
CH 3
EPPHAA
OH
O CH 2 CH CH 2 O CH 3
AM
CH 3
O
O CH 2 CH CH 2 O CH 3
AO
Figure 3.7 Antiplasticizers for epoxide resins.
106 REACTIVE POLYMERS FUNDAMENTALS
homogeneous systems are obtained after curing.
Above 10% 12F-PEK, a phase separation is observed.
At still higher concentrations, an inversion of the mor-
phology is observed. With fluoropolymer concentra-
tions of 10% 12F-PEK, a friction reduction of 30%
can be obtained [124].
The tribological behavior of an epoxy polyurea
composite was studied [125]. IR spectrometry showed
that the epoxy terminal groups can react with the
end amine group of the polyurea. In this way more
H–O bonds are formed, which enhance the deforma-
tion capacity. The wear resistance of the composite
is greatly improved by the addition of the polyurea
elastomer. This results in low friction coefficients and
wear loss.
3.3.5 Adhesion Improvers
Epoxy poly(urethane) hybrid resins are used in high-
strength adhesives. Elastomer-modified resins are
used for adhesive formulations that cure under water.
3.3.6 Conductivity Modifiers
To modify the thermal and electrical properties, ther-
mally and electrically conductive materials are added.
Silicon nitride, boron nitride, alumina, and silicon
carbide were used as heat-conducting insulating fillers
for epoxy resins. By a proper choice of the materials
and amounts of fillers, the heat conductive properties
of epoxy resin can be tailored. Further, by choosing
the curing agent and accelerator, the viscosity can also
be controlled [126].
3.3.7 Reinforcing Materials
3.3.7.1 Composites and Laminates
Composites and laminates are made by reinforcing
the polymers with continuous fibers. About 1/4 of
the epoxy resins are reinforced materials. Reinforcing
materials are shown in Table 3.5. Traditional com-
posite structures are usually made of glass, carbon,
or aramid fibers. The advances in the development of
natural fibers in genetic engineering and in composite
science offer significant opportunities for improved
materials from renewable resources with enhanced
support for sustainable applications. Biodegrad-
able composites from biofibers and biodegrad-
able polymers will serve to solve environmental
problems [149].
AND APPLICATIONS
Table 3.5 Reinforcing Materials for Epoxides
Material Remark/Reference
Glass fibers [127–129]
Hollow glass fibers [130]
Carbon fibers [131–133]
Carbon nanotubes [134–137]
Graphite [138–144]
Aluminum [145,146]
Boron
Aluminum borate whiskers [147]
Paper
Poly(ethylene) fibers
Polyaramid fabric Low density and extremely
high strength
Cotton
Flax [148]
Often the surface of the fiber is chemically modified
to increase the adhesion properties to the resin matrix.
For example, glass fibers are coated with a silane cou-
pling agent. The interfacial bonding between carbon
fiber and epoxy resin can be improved by modification
with poly(pyrrole) (PPy). PPy can be deposited on car-
bon fibers via the oxidation-polymerization of pyrrole
(Py) with ferric ions [150].
The surface damage by solid particle erosion of
composite materials depends on many factors. Most
important is the content of the fibers and the fiber
orientation [151]. The influence of fiber loading
and orientation on mechanical properties and on the
erosion behavior of glass fiber-reinforced epoxy com-
posites has been tested. Composites with 30◦ fiber
orientation show a better micro-hardness than other
fiber orientations. This is independent of the fiber
loading. The same is also true for other mechanical
properties, such as tensile strength, flexural strength,
and impact strength.
The modification of carbon fibers by plasma treat-
ment was tested [152]. The surface morphology and
the chemical composition of the surface of the fibers
were investigated. In comparison to untreated car-
bon fibers, plasma-treated fibers are roughened, and
the oxygen content on the surface increases. Also,
the interfacial shear strength is improved. In contrast,
the fiber strength does not significantly change after
plasma treatment.
In the same way, basalt fibers were plasma treated.
The change in the contact angle was used to examine
the changes in wettability. Functional groups of oxy-
gen and nitrogen were formed on the fiber surface.
The interlaminar fracture toughness of basalt epoxy
3: EPOXY RESINS
composites can be improved by 16% by plasma
treatment [153].
The introduction of aluminum particles to the
epoxy composites hardly influences the thermal sta-
bility. However, thermal and dielectric properties are
changing. An aluminum epoxy composite with 48%
of aluminum particles content has a high thermal con-
ductivity and a high dielectric permittivity, but a low
loss factor [154].
Laminates are used for insulation. Impregnated
sheets of woven glass, paper, and polyaramid fabric
or cotton are laminated in large presses. These sheets
are used for printed circuit boards in the electronics
industry.
Insulating films for printed circuit boards were fab-
ricated from a variety of epoxy resin formulations.
using different amounts of accelerator. The curing
behavior was investigated by viscosity measurements.
The peel strength of the epoxy films with a copper
layer was directly dependent on their surface rough-
ness [155].
3.3.7.2 Nanocomposites
Polymer nanocomposites, in particular polymer-
layered silicate nanocomposites, are a radical
alternative to macroscopically filled polymers. The
preparation of epoxy resin-based nanocomposites was
first described by Messersmith and Giannelis [156].
Extensive work on epoxy-based nanocomposites has
been done and is reviewed among other polymers in
the literature [157,158].
The state of dispersion of carbon nanotubes plays
an important role with respect to the mechanical
properties of carbon nanotube reinforced composites.
The addition of carbon nanotubes to an epoxy resin
reduces the total heat of curing as found by DSC [159].
This heat loss depends both on concentration of the
carbon nanotubes and on the state of dispersion. It is
suspected that carbon nanotubes hinder the crosslink-
ing reaction.
On the other hand, the addition of multiwalled car-
bon nanotubes to an epoxy resin accelerates the pro-
cess of curing as indicated by the rate of disappearance
of the epoxy band in IR spectroscopy [160].
The viscosity of suspensions of nanosilica in epox-
ies depends on the content of the silica nanoparticles,
the particle size, and their size distribution. Studies on
the viscosity indicated an interaction of the nanopar-
ticles. Nanosilica particles can be used to lower the
viscosity of the composites [161].
107
Organoclays. Organoclays are used as precur-
sors for nanocomposites in many polymer systems.
Usually montmorillonite is used for organoclays.
Montmorillonite belongs to the 2:1 layered silicates.
Its crystal structure consists of layers of two silica
molecules and a layer of either aluminum hydrox-
ide or magnesium hydroxide. Water and other polar
molecules can enter between the unit layers because
of the comparatively weak forces between the lay-
ers. Substitution of the ions originally in the layers
by such ions with different charges generates charged
interlayers. The stacked array of clay sheets separated
by a regular spacing is called a gallery.
For true nanocomposites, the clay nanolayers must
be uniformly dispersed in the polymer matrix, to
avoid larger aggregations. Small aggregations are
still referred to as nanocomposites, as intercalated
nanocomposites, ordered exfoliated nanocomposites,
and disordered exfoliated nanocomposites [162].
Originally, intercalation was the insertion of an
extra day into a calendar year. Exfoliation refers to
the peeling of rocky materials into sheets due to
weathering.
Clay nanolayers in elastomeric epoxy matrices dra-
matically improve both the toughness and the tensile
properties [156,163]. The dimensional stability, the
thermal stability, and the chemical resistance can also
be improved with clay nanolayers [164].
Exfoliated clays are formed when the clay layers
are well separated from one another and individually
dispersed in the continuous polymer matrix. Since
exfoliated nanocomposites exhibit a higher phase
homogeneity than the intercalated clays, exfoliated
clays are more effective in improving the properties
of the nanocomposites.
Successful nanocomposite synthesis depends not
only on the cure kinetics of the epoxy system but
also on the rate of diffusion of the curing agent
into the galleries, because it affects the intragallery
cure kinetics. The nature of the curing agent influ-
ences these two phenomena substantially and there-
fore the resulting structure of the nanocomposite. The
curing temperature controls the balance between the
extragallery reaction rate of the epoxy system and
the diffusion rate of the curing agent into the gal-
leries [165]. It was found that the activity energy
decreases with the addition of organic montmoril-
lonite [166]. Hexahydrophthalic anhydride is usually
used for hot curing of epoxy resins. With an alkoxysi-
lane, it also acts as a condensation agent [167]. Hot
curing of montmorillonite-layered silicates has been
108 REACTIVE POLYMERS FUNDAMENTALS
described with 3-methyl-1,2,3,6-tetrahydrophthalic
anhydride [168].
An exfoliated epoxy clay nanocomposite structure
can be synthesized by loading the clay gallery with
hydrophobic onium ions and then allowing diffusion
in the epoxide and a curing agent. The degree of exfo-
liation increases with decreasing curing agent [169].
Clays exert catalytic effects on the curing of epoxy
resins [170].
Organically modified montmorillonite, prepared by
a cation exchange reaction between the sodium cation
in montmorillonite and dimethyl benzyl hydrogenated
tallow ammonium chloride, is suitable for high
degrees of filling for epoxy resins [171]. Nanocom-
posites exhibit a significant increase in thermal stabil-
ity in comparison to the original epoxy resin [172].
Quaternary ammonium ions both catalyze the
epoxy curing reactions and plasticize the epoxy mate-
rial. This causes a large reduction in glass transition
temperature and lowers the storage modulus. Plasti-
cization is small for aromatic epoxy resins, but large
for aliphatic resins. Therefore, aromatic epoxy clay
systems may result in a complete exfoliation of the
clay galleries, whereas mixtures of aliphatic and aro-
matic epoxy may produce intercalated systems [173].
Poly(oxypropylene) amine intercalated montmoril-
lonite is highly organophilic and compatible with
epoxy materials [174].
Star branched functionalized poly(propylene
oxide-block-ethylene oxide) was used with an
organophilic modified synthetic fluorohectorite as
compatibilizer for nanocomposites. The polarity of
the polyol could be tailored by the type of functional-
ization. A mixture of two epoxy resins, tetraglycidyl
4,4 -diaminodiphenylmethane and bisphenol A
diglycidyl ether, cured with 4,4 -diaminodiphenyl
sulfone, was used as matrix material [175]. The hybrid
nanocomposites were composed of intercalated clay
particles as well as separated poly(2,6-dimethyl-
1,4-phenylene oxide) spheres in the epoxy matrix.
Phenolic alkylimidazolineamides were also used to
exchange the interlayer sodium cations of the layered
silicates [176].
Electric capacitors based on epoxy clay nanocom-
posites can be integrated into electronic devices [177].
3.3.8 Graphene
Chemically converted graphene oxide epoxy resin
nanocomposites can be prepared from graphene oxide
AND APPLICATIONS
sheets by a two-phase extraction. The mechani-
cal properties are significantly improved by adding
0.0375% graphene oxide sheets into the epoxy
resin [178].
3.3.9 Interpenetrating Polymer
Networks
Interpenetrating polymer networks are ideally com-
positions of two or more chemically distinct polymer
networks held together exclusively by their permanent
mutual entanglements [179]. In practice, interactions
of both networks beyond entanglement may occur, for
instance intercrosslinking.
In a simultaneous interpenetrating polymer net-
work, the two network components are polymerized
concomitantly. In a sequential interpenetrating poly-
mer network, the first network is formed and then
swollen with a second crosslinking system, which is
subsequently polymerized.
Interpenetrating polymer networks are known to
remarkably suppress creep phenomena in polymers.
The motion of the segments in interpenetrating poly-
mer networks is diminished by the entanglement
between the networks.
Interpenetrating polymer networks including epox-
ide resins as one of the components are summarized
in Table 3.6.
3.3.9.1 Curing Kinetics
If a thermosetting system is cured at a temperature
below its maximally attainable glass transition tem-
perature, vitrification occurs during cure. The vitri-
fication slows down the reaction. The reaction may
freeze before reaching full conversion.
In contrast, in an interpenetrating network, if one
component (I) reacts more slowly than the other com-
ponent (II), the former component (I) may act as
a plasticizer of the polymeric component (II). This
allows a faster reaction of the second component (II)
and a more thorough cure without vitrification [187].
In the simultaneous curing of a vinylester resin
(VER) and an epoxy resin a reduction in reaction rate
due to the dilution of each reacting system by the other
resin components is observed.
The radical polymerization of an acrylate monomer
is hardly affected by the oxygen inhibition
effect, while the cationic polymerization of an
epoxy monomer is enhanced by the atmospheric
humidity [188].
3: EPOXY RESINS
Table 3.6 Interpenetrating Polymer Networks
Epoxide Further Component
Diglycidyl ether of bisphenol A Unsaturated polyesters
Aliphatic epoxide resin Vinylester resin (bisphenol A glycidyl methacrylate adduct in
styrene with layered silicate nanoparticles)
Diglycidyl ether of bisphenol A Bisphenol A diacrylate
Epoxide bismaleimide resin Cyanate ester
Epoxide-amine network Silica
Diglycidyl ether of bisphenol A Hexakis (methoxymethyl) melamine
Novolak epoxy resin 2,2 -Diallyl bisphenol A
Epoxy resin Polyaniline
The decomposition of peroxides is known to be
accelerated by amines. In fact, if for the radical
curing of the vinylester component peroxides are used
instead of azo compounds, a strong redox interaction
between the peroxide and the amine used for curing
the epoxide component is observed. In such systems
the peroxide decomposes too quickly to develop its
full power for curing the vinylester system.
Further, there is an interaction between the vinyl
groups of the vinylester system and the amine via
a Michael addition. The curing performance of the
epoxide resin is less affected by the radical initia-
tor [189].
3.3.9.2 Unsaturated Polyesters
In mixtures of epoxy based on diglycidyl ether of
bisphenol A and unsaturated polyesters, the curing
monitored with differential scanning calorimetry indi-
cated a higher rate constant than the pure epoxide
resin. It is believed that the hydroxyl end group of the
unsaturated polyester in the blend provides a favorable
catalytic environment for the epoxide curing [180].
The interpretation of the viscosity development
suggests that an interlock between the two growing
networks exists that causes a retarded increase of
the viscosity [190]. The introduction of unsaturated
polyester into epoxy resin improves toughness but
reduces the glass transition temperature [191].
Functional Peroxides. Peroxy ester oligomers
can be obtained by condensation of anhydrides with
poly(ethylene glycol)s and tert-butyl hydroperoxide.
Suitable anhydrides are pyromellitic dianhydride and
the tetrachloroanhydride of pyromellitic anhydride.
The resulting esters contain carboxylic groups and
peroxy groups. These compounds can be used as cur-
ing agents for unsaturated polyesters as such and for
109
Reference
[180]
[10]
[181]
[182]
[183]
[184]
[185]
[186]
hybrid resins consisting of an epoxy resin and an
unsaturated polyester resin [192].
3.3.9.3 Acrylics
For interpenetrating polymer networks consisting of
DGEBA and bisphenol A diacrylate as radically poly-
merizable component, 4,4 -methylenedianiline and
dibenzoyl peroxide are suitable curing agents. The
curing can be achieved between 65 ◦ C and 80 ◦ C.
The kinetics of curing of the epoxide takes place as a
combination of an uncatalyzed bimolecular reaction
and a catalyzed termolecular reaction. The kinetics of
curing of the acrylate runs according to a first-order
reaction [181].
In the mixture, the rate constants are lower than
in the separate systems. Also, the activation ener-
gies in the mixtures are higher. It is believed that
chain entanglements between the two networks cause
a steric hindrance for the curing process. The vitrifi-
cation restrains the chain mobility that is reflected as
a decrease of the rate constants. The incorporation of
the methacryloyl moiety in an epoxide resin improves
the weathering stability and the photostability of the
system [193,194].
3.3.9.4 Urethane-modified Bismaleimide
Urethane-modified bismaleimide (UBMI) can
be introduced and partially grafted to the epoxy
oligomers by poly(urethane) grafting agents.
Afterwards, a simultaneous bulk polymerization
technique can be used to prepare interpenetrating
networks [195]. The tensile strength increases to a
maximum value with increasing UBMI content, then
decreases with further increasing UBMI content.
If the poly(urethane) grafting agent contains poly-
(oxypropylene) polyols the interpenetrating net-
work is a two-phase system, whereas in the case
110 REACTIVE POLYMERS FUNDAMENTALS
of poly(butylene adipate) a single-phase system is
observed. The better compatibility of poly(butylene
adipate) base networks results in a higher impact
strength.
An intercrosslinked network of bismaleimide-
modified poly(urethane)-epoxy systems was pre-
pared from the bismaleimide having ester linkages,
poly(urethane)-modified epoxy, and cured in the
presence of 4,4 -diaminodiphenylmethane. Infrared
spectral analysis was used to confirm the grafting of
poly(urethane) into the epoxy skeleton. The prepared
matrices were characterized by mechanical, thermal,
and morphological studies.
The changes of the properties depend on the relative
amounts of the moieties used. The incorporation of
poly(urethane) into the epoxy skeleton increases the
mechanical strength and decreases the glass transition
temperature, thermal stability, and heat distortion tem-
perature. On the other hand, the incorporation of bis-
maleimide with ester linkages into a poly(urethane)-
modified epoxy system increases the thermal stabil-
ity, tensile and flexural properties, and decreases the
impact strength, glass transition temperature, and heat
distortion temperature [196].
3.3.9.5 Poly(caprolactone) and
Poly(urethane)
Grafted interpenetrating polymer networks based on
poly(caprolactone), poly(urethane), and epoxy moi-
eties have been systematically studied [197].
The damping properties and the thermal stability
showed that these compositions significantly improve
both the damping properties and the thermal stability.
With increasing urethane content, the tensile strength
decreases, but impact strength increases. The iso-
cyanate index has a significant influence on the prop-
erties of the interpenetrating polymer networks [197].
3.3.9.6 Electrically Conductive
Networks
Electrically conductive polymers may find use
in rechargeable batteries, conducting paints, con-
ducting glues, electromagnetic shielding, antistatic
formulations, sensors, electronic devices, light-
emitting diodes, coatings, and others. Low con-
centrations of polyaniline can make the poly-
mer electrically conductive when a co-continuous
microstructure can be achieved.
AND APPLICATIONS
For the preparation of conductive polyaniline epoxy
resin composites, a doped polyaniline is blended
with the epoxy resin. Plasticizers are added to assist
in the dispersion of the conductive polymer. The
curing agent must be selected in order to avoid
dedoping [186].
The grafting onto the nitrogen of polyaniline was
achieved by the ring opening graft copolymerization
of 1,2-epoxy-3-phenoxypropane. By controlling the
degree of grafting, the solubility, the optical, and the
electrochemical properties of the grafted polyaniline
can be tailored [198].
3.3.10 Organic and Inorganic
Hybrids
An organic-inorganic hybrid interpenetrating network
has been synthesized from an epoxide-amine system
and tetraethoxysilane (TEOS). The kinetics of the for-
mation of the silica structure in the organic matrix,
and its final structure and morphology, depend on
the method of preparation of the interpenetrating net-
work. In the sol-gel process, hydrolysis and polymer-
ization of TEOS are performed at room temperature
in isopropyl alcohol. The hybrid network can be pre-
pared by two procedures.
In the one-step procedure, all reaction components
are mixed simultaneously. In the two-step procedure,
TEOS is hydrolyzed in the first step, then mixed with
the organic epoxy components and polymerized under
the formation of silica and epoxide networks.
Large compact silica aggregates, with 100–300 nm
diameter, are formed by the one-stage process of
polymerization. In the two-stage process the partial
hydrolysis of TEOS effects an acceleration of the gela-
tion. This results in somewhat smaller silica struc-
tures. The most homogeneous hybrid morphology
with the smallest silica domains of size 10–20 nm can
be achieved in a sequential preparation of the interpen-
etrating network [183,199]. An increase in modulus
by two orders of magnitude was achieved at a silica
content below 10% [200]. Phenolic novolak/silica and
cresol novolak epoxy/silica hybrids can be prepared
in a similar manner with TEOS [201].
3.3.11 Flame Retardants
Flame retardancy can be imparted by suitable
monomers and curing agents. Flame retardants can
be grouped into halogen-containing compounds,
3: EPOXY RESINS
Table 3.7 Flame Retardants for Epoxide Resins
Compound
Tetrabromobisphenol A-based epoxies
Triglycidyloxy phenyl silane
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)
10-(2,5-Dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DHPDOPO)
Bis(m-aminophenyl) methylphosphine oxide (BAMPO)
Bismaleimide (3,3 -bis(maleimidophenyl)) phenylphosphine oxide (BMPPPO)
Bis(3-glycidyloxy)phenylphosphine oxide
Bis(4-aminophenoxy)phenylphosphine oxide
Tris(2-hydroxyphenyl)phosphine oxides
Bis(3-diethylphosphono-4-hydroxyphenyl)sulfide
Benzoguanamine-modified phenol biphenylene components
Melamine phosphate
2,4,6-Tris (2,4,6-tribromophenoxy)-1,3,5-triazine
2,2 -[(1-Methylethylidene)bis[(2,6-dibromo-4,1-phenylene)oxy]]bis[4,6-bis[(2,4,6-tribromophenyl)-
oxy]]-1,3,5-triazine
Carbon black
a Cf. Figure 3.8
the most important being tetrabromobisphenol A,
halogen-free systems containing aluminum trihydrate
with red phosphorus, and phosphate esters [202].
Flame retardants that are used in epoxide resins are
shown in Table 3.7.
Triglycidyloxy phenyl silane cured with 4,4 -dia-
minodiphenylmethane and others gives highly flame
retardant polymers [18]. Heating in air indicates that a
silicon-containing carbon residue formed is superior
in preventing oxidative burning (see Figure 3.8).
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-
oxide (DOPO) can be synthesized by a multistep
reaction from o-phenylphenol and phosphorus
trichloride.
Fromthiscompound,anadductwithp-benzoquinone,
2-(6-oxy-6H-dibenz[c,e][1,2]oxa-phosphorin-6-yl)-
1,4-benzenediol (ODOPB), can be obtained. ODOPB
can be used as a reactive flame retardant in o-cresol
formaldehydenovolakepoxyresinsforelectronicappli-
cations [19,203]. A related compound, 2-(6-oxy-6H-
dibenz[c,e][1,2]oxaphosphorin-6-yl) methanol, can
be used as flame retardant hardener for o-cresol-
formaldehyde novolak epoxy (CNE) resin in electronic
applications [204]. Some phosphorus-containing
flame retardants are shown in Figure 3.9.
Other phosphorus-containing epoxy resins can be
obtained from the addition reaction of DOPO and the
glycidyl ether of cresol-formaldehyde novolak [205,
206]. The cured products are highly flame resistant.
111
Remark/Reference
[18]
[19,209]
[210]
[207]
[211]
[212]
[213]
[214,215]
[216]
[217]
[218]
[208]a
[208]a
[219]
In the presence of a phosphorus-containing hard-
ener, BAMPO, the volatilization of the cured resin
is reduced and aromatization is accelerated. This
results in a larger yield of stable char. This behav-
ior is attributed to the flame retardant action of
BAMPO. However, at high content of BAMPO this
effect is overwhelmed by flame quenching due to the
volatilization of the phosphorus-containing moieties
from BAMPO [207].
Further, BMPPPO is a phosphorus-containing com-
pound that is soluble in organic compounds. Inter-
penetrating networks can be prepared by simulta-
neously curing an epoxy/diaminodiphenylmethane
system and BMPPPO.
The cured resin system exhibits a glass transition
temperature around 21 ◦ C, thermal stability at temper-
atures beyond 350 ◦ C, and excellent flame retardancy
with a limited oxygen index (LOI) of 40% [211].
Phosphorus-containing diamines have been pre-
pared that act as curing agents for epoxy resins [221].
The compounds and their synthesis are shown in
Figure 3.10. When cured with phosphorus-containing
curing agents, the epoxy resins show extremely high
LOI values of up to 49.
Amine-based curing agents destabilize a bromi-
nated epoxy resin by a mechanism of nucleophilic
substitution of bromine. As a result, a brominated
epoxy resin releases products of pyrolysis about 100◦
C lower than a nonbrominated epoxy resin [222].
112 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

Br Br Br Br

O N O
O P O O P O
Br Br
N N CH2
OH HO OH
O
Br Br
ODOPM ODOPB
Figure 3.9 2-(6-Oxy-6H-dibenz[c,e][1,2]oxaphospho-
rin-6-yl)methanol (ODOPM), 2-(6-Oxy-6H-dibenz[c,e]
Br [1,2]oxa-phosphorin-6-yl)-1,4-benzenediol (ODOPB).
Br Br Br Br
O O

H 2N C NH 2 P
O N O
Br Br +
N N
H

O O P O H2 SO4 /HNO 3

Br Br
O2N NO 2
O
P
H3 C C CH 3

SnCl 2 /HCl/EtOH
Br Br
O
H2 N NH 2
O
N N O P O
Br Br P
H 2N C NH 2
O N O O P O

Br Br Br Br
Figure 3.8 Top: 2,4,6-Tris(2,4,6-tribromophenoxy)-
2-DOPO-A BAPPPO
1,3,5-triazine. Bottom: 2,2 -[(1-Methylethylidene)-bis-
[(2,6-dibromo-4,1-phenylene)oxy]]bis[4,6-bis[(2,4,6- Figure 3.10 2-DOPO-A, bis(4-aminophenyl)phenyl-
tribromophenyl)oxy]]1,3,5-triazine [208]. phosphine oxide [220,221].

3.3.12 Production Data
Global production data for the most important
monomers used for unsaturated epoxy resins are
shown in Table 3.8.
3.4 Curing
3.4.1 Initiator Systems
The epoxide group reacts with several substance
classes. Only a few of the possible reactions are used
for curing in practice. Curing agents of epoxy resins
can be subdivided into three classes:
1. compounds with active hydrogens,
2. ionic initiators, and
3. hydroxyl coupling agents.
The most commonly used curing reaction is based on
the polyaddition reaction, thereby opening the epox-
ide ring. The glycidyl group can be cured by amines
and other nitrogen-containing compounds such as
3: EPOXY RESINS 113

Table 3.8 Global Production/Consumption Data of Important Monomers

and Polymers [223]

Monomer Mill. Metric Tons Year Reference

Ethylene oxide 14.7 2002 [224]
Ethyleneamines 0.248 2002 [225]
Epichlorohydrin 0.640 1999 [226]
Epoxy resins 0.65 1999 [227]

polyamides. Many of the amines effect curing at room The basic reaction between the glycidyl groups with
temperature. This type of curing is called cold curing. a primary amine is shown in Figure 3.11. The first
The reactivity of an epoxy compound with an amine reaction in Figure 3.11 is the addition reaction of
depends on the structure of the compounds. The rel- primary amine hydrogen with an epoxy group. The
ative reaction rates of the secondary amine to the pri- product of this reaction is a secondary amine. The
mary amine can be explained in terms of substitution secondary amine may react with another epoxy group
effects [228]. Anhydrides are active only at elevated to form a tertiary amine, as shown in the second reac-
temperatures. This type of curing is called hot curing. tion in Figure 3.11. Usually the secondary amine is
less reactive than the primary amine. The ratio of the
3.4.2 Compounds with Activated kinetic constants is approximately 1/2. Both reactions
are autocatalyzed by OH groups formed during the
Hydrogen process.
3.4.2.1 Amines The third reaction shown is the etherification
Both primary and secondary amines can be used. reaction between epoxy functions and hydroxyl
From a chemical point of view, the active hydrogen groups. In most systems, this reaction can be
attached to the nitrogen group effects an addition reac- neglected. However, it has been shown that this
tion, as the epoxide group is opened. The curing of the reaction takes place using MCDEA as curing cat-
diglycidyl oligomer with a diamine occurs in three alyst. On the other hand, with DDS and MDA
stages: as catalysts the etherification was not observed
[112,229].
1. linear coupling of the oligomer, Typical nitrogen compounds used for cold curing
2. formation of a branched structure, and are shown in Tables 3.9 and 3.10, and in Figures 3.12
3. crosslinking. and 3.13. There are many possibilities for formulating
a curing system from primary and secondary amines,
O OH
and with tertiary amines.
Tertiary amines catalyze the reaction. Other cata-
R NH 2 + CH 2 CH R NH CH 2 CH
lysts are complexes of boron trifluoride complexes,
quaternary ammonium salts, thiocyano compounds,
OH OH etc. Retarders are certain ketones and diacetone
CH 2 CH
alcohol.
R NH CH 2 CH
R N Certain cyclic amines, such as 1,2-bis(amino-
O
CH 2 CH methyl)cyclobutane and isomers of diaminotricy-
CH 2 CH OH clododecane, increase the pot life time. Polyamines
and dicyanamide are preferably used for adhesive
formulations.
O OH
Phenolic hydroxyl groups exert autocatalysis at low
R OH + CH 2 CH R O CH 2 CH conversions with respect to the ring opening of the
Figure 3.11 Reaction of the glycidyl group with an epoxide group, thereby adding the amine groups. In
amine and with a hydroxyl group. the later stage of curing the amine groups are largely
114 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

Table 3.9 Amines Suitable for Curing

Compound Remarks
Ethylene diamine Fast curing, low viscosity
Diethylenetriamine Fast curing, low viscosity
Triethylenetetramine Fast curing, low viscosity
Hexamethylene diamine Slower curing, needs elevated temperature, flexible materials
Diethylaminopropylamine Needs elevated temperature, good adhesive
Isophorone diamine
1,2-Diaminocyclohexane
Bis-p-aminocyclohexylmethane
Bisaminomethylcyclohexane
Menthane diamine Needs elevated temperature, good pot-life
N-Aminoethyl piperazine Fast curing
Diaminodiethyl toluene Mixture of 2,6-diamino-3,5-diethyltoluene and 2,4-diamino-3,5-
diethyltoluene
m-Phenylene diamine Chemical resistant materials
4,4 -Diaminodiphenylmethane Chemical resistant materials
3,3 ,5,5 -Tetraethyl-4,4 - Flame retardant [207]
diaminodiphenylmethane
4,4 -Diamino-3,3 -dimethyldicyclohexylmethane Cycloaliphatic diamine [231,232]
1,5-Naphthalene diamine

Table 3.10 Polymeric Amines and Hetero Functional Amines

Compound Remarks
Poly(propylene oxide)diamine
Trimercaptothioethylamine Optical applications [23,233]
Polymercaptopolyamines In combination with customary
amine hardeners [234]
2,4-Diamino-4 -methylazobenzene Optical applications [235]
4,4 -Dithiodianiline Reversible crosslinking [236]
Dicyandiamide Common for adhesives
4,4 -Diaminodiphenyl sulfone Chemical resistant materials
BAMPO [207]
4,4 -Methylene bis(3-chloro-2,6-diethylaniline) [72]
Olefin oxide polyamine adducts Fast curing, low toxicity
Glycidyl ether polyamine adducts Fast curing
Diamide of dimerized linoleic acid and ethlyene diamine For adhesives
Ketimines Low viscosity, long pot-life, latent
hardening catalysts
2,5-Bis(aminomethyl) bicyclo[2.2.1]heptane di(methylisopropylketimine) Norbornane diketimine [237]
Substituted imidazolines, e.g., 2-ethyl-4-methylimidazole, 1-methylimidazole Wide range in stoichiometry
Sulfanilamide [45,238–240]
Polysilazane-modified polyamines Thermal resistant [241]

consumed and the phenolic hydroxyl groups start to 3.4.2.2 Ketimines

react with the residual epoxide groups [230]. A suit-
able accelerator for adhesive formulations is 2,4,6-
tris(dimethylaminomethyl)phenol.
Most low-molecular-weight amines are toxic and
sensitive to the carbon dioxide in air. Therefore, the
various adducts of the amines have been developed to
mitigate this drawback.
Ketimines form the active amine structure by addition
of water; thus they act as delayed-action catalysts.
3.4.2.3 Amino Amides
Amide-based compounds are used to achieve spe-
cial properties and desired curing characteristics, such
3: EPOXY RESINS 115

H2 N CH 2 CH 2 NH CH 2 CH 2 NH2 directly the amide group, but the attached primary and
secondary amino groups present in the molecule. The
Diethylenetriamine amide group is helpful for achieving the other bene-
fits mentioned above. Examples of amino amides are
H2 N CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NH2 adducts of polyamines with fumaric acid or maleic
acid, or fatty acids. Similar to amines, in amine amides
Hexamethylenediamine the reaction can be accelerated with boron trifluoride
complexes, Mannich bases, etc.
CH 3 CH 2
N CH 2 CH 2 CH 2 NH2
Rosin-based imide diacids were used as curing
CH 3 CH 2 agents for epoxies. For comparison, imide diacids
based on trimellitic anhydride were also studied.
Diethylaminopropylamine The rosin-based imide diacids resulted in signifi-
cantly higher glass transition temperatures and better
CH 3
mechanical properties than the imide diacids based on
CH 3
trimellitic anhydride. Thus it was concluded that rosin
H2N C H2 N CH 2 CH 2 N H
acids have great potential to replace conventional cur-
CH 3 NH2
ing agents [245].
Menthanediamine N-Aminoethyl piperazine
Figure 3.12 Aliphatic nitrogen compounds for curing:
3.4.2.4 Metal salts
diethylenetriamine, hexamethylene diamine, diethyl- Zirconium tetrachloride catalyzes effectively the
aminopropylamine, menthane diamine, N-aminoethyl nucleophilic opening of epoxide rings by amines. This
piperazine. has been used for the efficient synthesis of β-amino
alcohols [246]. Zinc bromide and zinc perchlorate are
also active in this manner [247]. However, it seems
NH2
H2 N NH2 that this catalyst is not used for the curing of epoxy
resins.
H2 N
3.4.2.5 Phenols
m-Phenylene diamine 1,5-Naphthalene diamine Bisphenol A is the main ingredient in the manufacture
of glycidyl ethers. Polyfunctional phenols can be used
O
to cure epoxy resins. This method did not find large
commercial use, except in the development of highly
H2 N S NH 2
chemically resistant coatings. The curing reaction is
O
analogous to the curing reaction of amines.
4,4 -Diaminodiphenylsulfone
Phenoplasts. Polyfunctional phenols can be
applied as phenol/formaldehyde condensates of
H2 N CH 2 NH2 the novolak type. In this field a wide variety has
been examined, including phenolic adducts of
chloromethylated diphenyl oxide, tetrabrominated
4,4 -Diaminodiphenylmethane
bisphenol, and phenol adducts of poly(butadiene).
Figure 3.13 Aromatic nitrogen compounds for cur- The effect of the addition of a novolak resin to an
ing: m-phenylene diamine, 1,5-naphthalene diamine,
epoxide oligomer on the curing has been studied by
4,4 -diaminodiphenyl sulfone, 4,4 -diaminodiphenyl-
methane.
rotational viscometry [248].

as lower toxicity, less sensitive final properties to

3.4.2.6 Anhydride Compounds
the stoichiometry, and lower peak temperatures for Typical anhydride compounds used for hot curing
large castings. The active group in curing is not are shown in Table 3.11 and in Figure 3.14. Most
116 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

Table 3.11 Anhydrides for Hot Curing

Anhydride Remark/Reference
Dodecenyl succinic anhydride Liquid
Hexahydrophthalic anhydride
3-Methyl-1,2,3,6-tetrahydrophthalic anhydride N,N-Dimethylbenzylamine as accelerator [242]
Hexahydro-4-methylphthalic anhydride
Tetrahydrophthalic anhydride
3-Methyl-1,2,3,6-tetrahydrophthalic anhydride
Phthalic anhydride
Methyl nadic anhydride Liquid
HET anhydride
Pyromellitic dianhydride
5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene- [243]
1,2-dicarboxylic anhydride
Glutaric anhydride Biodegradable formulations [244]
Styrene maleic anhydride copolymers Low-molecular-weight copolymers

anhydrides need elevated temperatures to be active. 3.4.2.8 Polybasic Esters

The anhydride group is not active in the absence of To obtain tough materials, the epoxides can be cured
acidic or basic catalysts; instead the anhydride group by the insertion reaction into ester groups. The curing
must be converted into the carboxyl group. This can agent is formed in situ by the radical polymerization
be achieved by hydrolysis, by natural occurring mois- of N-phenyl maleimide and p-acetoxystyrene [251].
ture, or by alcoholysis.
The reaction of an anhydride is accelerated by a
O O
tertiary amine or by complexes of metal salts, such
C 12 H 23
as ferric acetylacetonate [249]. The reaction of the
O O
anhydride group as well as the acid group with the
epoxide group results in an ester linkage, with all the
O O
advantages and disadvantages of the ester link.
Anhydrides are in some cases preferred over amines
because they are less irritating to the skin, have longer
pot-life times, and low peak temperatures. Aromatic
and cycloaliphatic anhydrides find wide applications O O
for molding and casting techniques.
When anhydrides are used for curing, curing accel- O O
erators are normally used. The accelerator is typically
used to accelerate the reaction between epoxy resin O O
and a hardener [250]. Many types of accelerators, such
as tertiary amine, boric acid ester, Lewis acid, organic
metal compounds, organic metal salts, and imidazole,
are widely used.
H3 C CH
O O O

O O O
3.4.2.7 Polybasic Acids
The carboxyl group is capable of opening the epoxide O O O

group. Theoretically, the optimum stoichiometry is

one acid group by one epoxide group. In practice an
excess of acid is used. Figure 3.14 Anhydrides for hot curing.
3: EPOXY RESINS
O O H 3C
H 3C O + CH 2 CH CH 2 O CH2
CH CH 2 CH
O N O O N O
Figure 3.15 Insertion of the epoxide into a pendant
ester group.
2,5-Dimethyl-2,5-bis(benzoylperoxy)hexane is suit-
able, because its decomposition temperature of
110 ◦ C is close to the desired cure temperature of
100 ◦ C. The two monomers copolymerize satisfac-
torily in the absence of the epoxy compound. The
advantage of using the in situ technique of poly-
merization is that the initial composition has low
viscosity.
The insertion mechanism is shown in Figure 3.15.
Compared to epoxy systems cured with a phenol
resin, the copolymer of N-phenyl maleimide and
p-acetoxystyrene shows a significantly higher glass
transition temperature.
3.4.3 Coordination Catalysts
Coordination catalysts consist of metal alkoxides,
such as aluminum isopropyloxide, metal chelates, and
oxides. Coordinative polymerization results in high
molecular weight and stereospecific species.
3.4.4 Ionic Curing
3.4.4.1 Anionic Polymerization
The anionic polymerization of epoxides can be initi-
ated by metal hydroxides, and secondary and tertiary
amines. The rate of curing is low in comparison to
other curing methods. Therefore, anionic polymeriza-
tion has not found wide industrial application. More-
over, the mechanical properties of the final materials
are not satisfactory.
3.4.4.2 Cationic Polymerization
Cationic polymerization can lead to a crosslinking
process if diepoxides are taken as monomers. Thus, a
wide variety of compounds can be used catalytically
117
O
as cationic curing initiators for epoxy resins that act
C O at a high rate. Moreover, their low initial viscosities
CH CH 2
and fast curing make them good candidates for rapid
reactive processing.
Cationic polymerization is initiated by Lewis acids.
A lot of metal halogenides have been shown to be
CH2
active, such as AlCl3 , SnCl4 , TiCl4 , SbCl5 , or BF3 , but
the most commonly used compound is boron trifluo-
ride. In practice, boron trifluoride is difficult to handle
and the reaction runs too quickly. Therefore, the com-
pound is used in complexed form, e.g., as an ether
complex or an amine complex. The strength of the
ether and amine complexes can be related to the base
strength of the ether and amine, respectively. Since
the reactivity of a complex depends on the dissocia-
tion constant, some predictions on the activity of the
complex can be made.
Water or alcohols cause chain transfer reactions.
The alcohol attacks the positively charged end of the
growing polymer chain and forms an ether linkage
or a hydroxyl group, respectively. The released pro-
ton can initiate the growth of another polymer chain.
Diols and triols yield polymers with pendant hydroxyl
groups. Therefore, diepoxides or higher functional
epoxides are polymerized in the presence of diols or
triols, etc. Branched and crosslinked products may
appear.
In the cationic UV curing of an aliphatic epoxy com-
pound it was observed that the polymerization rate
decreased strongly after a conversion level of less than
10%. This effect was not caused by the glass transition
temperature. However, the addition of 1,6-hexanediol
raised the conversion at room temperature [252].
There are photolatent and thermolatent catalyst sys-
tems. A great variety of those catalysts have been
reviewed [253]. Besides the direct thermolysis of the
initiator, indirect methods are also viable. Table 3.12
provides a list of latent catalysts.
Spiroorthocarbonate. The cationic curing reac-
tion of a bisphenol A-type epoxy resin in the presence
of a spiroorthocarbonate (SOC) can be performed
with boron trifluoride dietherate. The SOC undergoes
a double ring opening reaction [254]. The conversion
of the epoxy groups increases as the content of the
SOC increases.
3,9-Di(p-methoxybenzyl)-1,5,7,11-tetra-oxaspiro-
[5.5]undecane (cf. Figure 3.16) as SOC can be
synthesized by the reaction of 2-methoxybenzyl-1,3-
propanediol with dibutyltin oxide.
118 REACTIVE POLYMERS FUNDAMENTALS
Table 3.12 Latent Catalysts
Compound
N-Benzylpyrazinium hexafluoroantimonate
N-Benzylquinoxalinium hexafluoroantimonate
Benzyl tetrahydrothiophenium hexafluoroantimonate
o,o-Di-tert-butyl-1-piperidinylphosphonamidate
o-tert-Butyl-di-1-piperidinylphosphonamidate
o,o-di-tert-Butyl phenylphosphonate
o,o-Dicyclohexyl phenylphosphonate
O O
H3 C O O CH 3
O O
3,9-Di(p-methoxy-benzyl)-1,5,7,11-tetra-oxaspiro(5,5)undecane
O O O
O OO
3,23-Dioxatrispiro[tricyclo[3.2.1.0<2,4>]octane-6,5 -
1,3-dioxane-2,2 -1,3-dioxane-5 ,7 -tricyclo[3.2.1.0<2,4>octane]
Figure 3.16 3,9-Di(p-methoxybenzyl)-1,5,7,11-tetra-
oxaspiro[5.5]undecane and 3,23-dioxatrispirotricyclo
[3.2.1.0[2.4]]octane-6,5 -1,3-dioxane-2 ,2 -1,3-di-
oxane-5 ,7 -tricyclo[3.2.1.0[2.4]octane].
Differential scanning calorimetry shows two
peaks that are attributed to the polymerization
of the epoxy group, and to the copolymerization
of the SOC with epoxy groups or homopolymer-
ization, respectively. Copolymers containing an
SOC are capable of yielding a hard, non-shrinking
matrix resin. Examples of these copolymers include
a 2,3,8,9-di(tetramethylene)-1,5,7,11-tetraoxaspiro-
[5.5]undecane spiroorthocarbonate, and 3,23-dioxatr-
ispirotricyclo[3.2.1.0[2.4]]octane-6,5 -1,3-dioxane-
2 ,2 -1,3-dioxane-5 ,7 -tricyclo[3.2.1.0[2.4]
octane] and cis,cis-, cis,trans-, and trans,trans-
configurational isomers of 2,3,8,9-di(tetramethyl-
ene)-1,5,7,11-tetraoxaspiro[5.5]undecane.
These SOCs were determined to undergo an
expansion of 3.5% during homopolymerization
and demonstrated acceptable cytotoxicity and
genotoxicity properties. These properties make them
promising components of composite resin matrix
materials [20].
Trifluoromethanesulfonic Acid Salts. Triflic
acid, i.e., trifluoromethanesulfonic acid, CF3 SO3 H,
AND APPLICATIONS
Reference
[255]
[255]
[256]
[257]
[257]
[258]
[258]
is a known strong acid. Lanthanide triflates are Lewis
acids and they maintain their catalyst activity even in
aqueous solution. The strong electronegativity of the
trifluoromethanesulfonate anion enhances the Lewis
acid character of the initiator. Therefore, lanthanide
triflates are excellent catalysts in the ring opening of
the epoxy compounds [259].
Phosphonic Acid Esters. Phenylphosphonic
esters decompose into phenylphosphonic acid and
the corresponding olefins at 150–170 ◦ C. In the
presence of ZnCl2 they can initiate a cationic
polymerization of glycidyl phenyl ether (GPE) to
molecular weights up to 2000–7000 Da [258].
Examples are o,o-di-1-phenylethyl phenylphos-
phonate, o,o-di-tert-butyl phenylphosphonate, and
o,o-dicyclohexyl phenylphosphonate. These com-
pounds can be synthesized from phenylphosphonic
dichloride and the corresponding alcohols.
Phosphonamidates. Phosphonamidates are ther-
mally latent initiators, suitable for the polymerization
of epoxides [257]. These compounds, such as o,o-di-
tert-butyl-1-piperidinylphosphonamidate and o-tert-
butyl-di-1-piperidinylphosphonamidate, can be syn-
thesized from phosphorus oxychloride and piperidine
in the presence of triethylamine, followed by the reac-
tion with tert-butyl alcohol in the presence of sodium
hydride. No polymerization of epoxide resins occurs
below 110 ◦ C, whereas the curing proceeds rapidly
above 110 ◦ C. At room temperature a mixture of epox-
ide and phosphonamidate is stable for months.
3.4.5 Photoinitiators
Photoinitiation is one of the most efficient methods for
achieving very fast polymerization. Often the reaction
can be completed within less than one second [260].
Curing with ultraviolet light has been developed for
the coating area, printing inks, and adhesives. The
3: EPOXY RESINS
Table 3.13 Photoinitiators for Epoxides
Compound
Aryl diazonium tetrafluoroborates
4,4-Bis(N,N-dimethyl-N-(2-ethoxycarbonyl-1-propenyl) ammonium
hexafluoro antimonate) benzophenone
Calixarene derivatives
9-Fluorenyl tetramethylene sulfonium hexafluoroantimonate
Cyclopentadiene-Fe-arene hexafluorophosphate
mechanism of photo curing consists mostly of a
cationic photopolymerization of epoxides. The kinet-
ics of the photoinduced reactions can be monitored by
differential photocalorimetry [261]. The major draw-
back of differential photocalorimetry is the rather long
response time in comparison to the curing rate.
The well-known use of radical generating photoini-
tiators in vinyl-containing systems is not applicable
in pure epoxy systems. There is an exception when
the epoxide resin is mixed with a vinyl monomer that
bears the hydroxyl functionality or the amide func-
tionality. The radical generating photoinitiator reacts
then with the vinyl monomer [262].
Common photoinitiators for epoxy systems are
shown in Table 3.13.
In the photoinduced curing of epoxides, the propa-
gating polymer cations cannot deactivate one another,
but require deactivation by another species present
in the polymerization mixture. Therefore, after the
light is switched off, a pronounced postpolymeriza-
tion reaction can be monitored [263]. The conversion
in the dark may contribute up to 80% of the total curing
process. The overall polymerization quantum yield
reaches ca. 200 mol per photon.
It has been shown that polyglycols, i.e., polyols
from 1,2-diols, slow down the cationic polymeriza-
tion, whereas polyols made from 1,4-diols do not
show this effect [256]. Also, the addition of small
amounts of crown ethers (12-crown-4 ether) retards
the polymerization. This behavior is attributed to com-
plexes that are formed only with glycol-like struc-
tures that reduce the effective concentration of cations
available to initialize the polymerization.
3.4.5.1 Aryl Diazonium
Tetrafluoroborates
The azo group in aryl diazonium tetrafluoroborates
decomposes on ultraviolet radiation into the aromatic
compound, nitrogen, and boron trifluoride. The latter
compound initiates a cationic polymerization of the
119
Reference
[264]
[265]
[266]
[267]
epoxide resin. The evolution of nitrogen limits the
applications to thin films.
3.4.5.2 Aryl Salts
Other efficient photoinitiators are based on the pho-
tolysis of diaryliodonium and triaryl sulfonium salts,
that when decomposed liberate strong Brønsted bases.
These bases initiate the cationic polymerization.
It has been shown that diaryliodonium hexafluo-
roantimonate initializes photochemically the cationic
copolymerization of 3,4-epoxycyclohexylmethyl-
3 ,4 -epoxycyclohexane carboxylate and triethylene
glycol methylvinyl ether [268]. Epoxy-functionalized
silicones can be synthesized by rhodium-catalyzed,
chemoselective hydrosilation of vinyl ethers with
siloxanes or silane [269].
Epoxidized soyabean oil accelerates the crosslink-
ing reaction of aromatic diepoxides in the presence of
a triaryl sulfonium photoinitiator [270]. The photoini-
tiated copolymerization leads within seconds to a fully
cured insoluble material showing increased hardness,
flexibility, and scratch resistance.
In interpenetrating networks, constructed by vinyl
polymers and epoxides by photo curing, a mix-
ture of a radically decomposing photoinitiator and
a cationic photoinitiator is used. Examples are a
mixture of a hydroxyphenylketone and a diaryliodo-
nium hexafluorophosphate salt. During the UV cur-
ing of a mixture of acrylate and epoxide monomers,
the epoxides react slower than acrylates [188]. The
low efficiency of the initiation process is caused by
the low ultraviolet absorbance of cationic photoini-
tiators. However, photosensitizers can improve the
performance.
Combinations of photo curing and thermal curing
in interpenetrating networks of a vinyl polymer and an
epoxide are possible. Such a combination of crosslink-
able resins allows the partial or complete cure of each
component independent of the other [271].
120 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

O hydroxyl group does not react with an epoxide group.

The phenol groups can be restored if a compound is
present that generates acids photolytically [265].
S
3.4.6 Derivatives of Michler’s
Thioxanthone Anthracene Ketone
Figure 3.17 Thioxanthone and anthracene.
4,4-Bis(N,N-dimethyl-N-(2-ethoxycarbonyl-1-pro-
penyl) ammonium hexafluoro antimonate)benzo-
3.4.5.3 Photosensitizers phenone (MKEA) is synthesized from 4,4 -
Photosensitizers can be used to improve characteris- bis(dimethylamino)benzophenone (Michler’s ketone)
tics of photo curing for pigmented materials. These and ethyl α-(bromomethyl) acrylate, cf. Figure 3.19.
photosensitizers exhibit significant UV absorption in MKEA initiates cationic photopolymerization of
the near UV and transfer the absorbed energy to a cyclic ethers, like cyclohexene oxide, via a conven-
cationic photoinitiator [272]. Examples of photosen- tional addition-fragmentation mechanism. MKEA
sitizers are anthracene and thioxanthone derivatives, belongs to the group of addition-fragmentation
such as 2,4-diethylthioxanthone, and isopropylthiox- catalysts.
anthone, cf. Figure 3.17. Photoinitiators are iodonium The mechanism of initiation of MKEA is shown
salts that exhibit a comparatively low triplet state in Figure 3.20. This initiator does not require sup-
energy. plementary free radical sources. It is suggested that
radicals stemming from the photoinduced hydro-
gen abstraction participate in addition-fragmentation
3.4.5.4 Calixarenes
reactions to yield reactive species capable of initiating
Calixarenes are by-products in the phenol/ cationic polymerization [264].
formaldehyde condensation to prepare bakelite. Monomers with strong electron donors such as N-
They found attention for their application as surfac- vinyl carbazole, isobutyl vinyl ether, and n-butyl vinyl
tants, chemoreceptors, electrochemical and optical ether undergo explosive polymerization upon illumi-
sensors, solid-phase extraction phases, and stationary nation of light. In the case of cyclohexene oxide there
phases for chromatography [273]. is an induction period, owing to the trace impurities
The hydroxyl groups in calixarenes (cf. present, but afterwards the polymerization proceeds
Figure 3.18) can be protected with tert- readily.
butoxycarbonyl groups, trimethyl silyl groups, and
cyclohexenyl groups, respectively. In this way the H3 C O
CH 3
N C N + Br CH 2 C CH 2
H3 C CH 3
CH3 C O
O
CH 2
CH 3
H3 C CH2 CH2 CH3
OH
CH 3 O CH 3
OH HO
+ +
H2 C C CH 2 N C N CH 2 C CH 2
CH2 CH2
O C CH 3 CH 3 C O
OH HO
O SBF6- SBF 6- O
OH CH 2 CH 2
H3 C CH2 CH2 CH3 CH 3 CH 3

MKEA

Figure 3.19 Synthesis of 4,4-bis(N,N-dimethyl-N-

CH3
(2-ethoxycarbonyl-1-propenyl)ammonium hexafluoro
Figure 3.18 p-Methylcalix[6]arene. antimonate)benzophenone.
3: EPOXY RESINS 121

CH 3 The second component in the photoinitiator sys-

R* + H 2 C C CH 2 N+ tem is the photosensitizer. Ideally, the photoinitia-
O C CH 3 tor should be sensitized to the visible spectrum to
O allow the polymerization to be initiated at room tem-
perature using visible light. The sensitizer should
CH 2
be soluble in the photopolymerizable composition,
CH 3
free of functionalities that would substantially inter-
fere with the cationic curing process, and capa-
ble of light absorption within the range of wave-
lengths between about 300 and about 1000 nm. Suit-
CH 3
able sensitizers include compounds in the following
N+
categories:
R* H2 C C* CH 2
O C CH 3
O • α-diketones,
CH 2 • ketocoumarins,
CH 3 • aminoarylketones,
• p-substituted aminostyrylketones.

For applications requiring deep cure (e.g., cure of

CH 3
+
R* H2 C C* CH 2 + N*
O C CH 3
O of irradiation for photopolymerization, or alterna-
CH 2
CH 3
Figure 3.20 Mechanism of initiation of 4,4-bis(N,N-
dimethyl-N-(2-ethoxycarbonyl-1-propenyl)-ammo-
nium hexafluoro antimonate)benzophenone.
3.4.6.1 Photoinitiator Systems
paginationVisible light photoinitiator systems include
an iodonium salt, a visible light sensitizer, and an elec-
tron donor compound [20].
Examples of useful aromatic iodonium com-
plex salt photoinitiators include diaryliodonium
hexafluorophosphates and diaryliodonium hexa-
fluoroantimonates, such as (4-(2-hydroxytetradecyl-
oxyphenyl)) phenyliodonium hexafluoro-antimonate,
(4-octyloxyphenyl)phenyliodonium hexafluoroan-
timonate, and (4-(1-methylethyl)phenyl)(4-methyl-
phenyl)iodonium tetrakis pentafluorophenylborate.
These salts are more thermally stable, promote
faster reaction, and are more soluble in inert organic
solvents than are other aromatic iodonium salts of
complex ions. Diphenyliodonium hexafluoroanti-
monate has a photoinduced potential greater than
N,N-dimethylaniline.
highly filled composites), it is preferred to employ
sensitizers having an extinction coefficient below
about 1000 l mol−1 cm−1 at the desired wavelength
tively the initiator should exhibit a decrease in absorp-
tivity upon light exposure. Many of the α-diketones
exhibit this property and are particularly preferred for
dental applications. A suitable photosensitizer is cam-
phorquinone.
The third component of the initiator system is an
electron donor compound. The electron donor com-
pound should be soluble in the polymerizable com-
position. Further, suitable compatibility and interplay
with the photoinitiator and the sensitizer and other
properties, like shelf stability, should be fulfilled. The
donor is typically an alkyl aromatic polyether or an
alkyl, aryl amino compound wherein the aryl group is
optionally substituted by one or more electron with-
drawing groups. Examples of suitable electron with-
drawing groups include carboxylic acid, carboxylic
acid ester, ketone, aldehyde, sulfonic acid, sulfonate,
and nitrile groups.
In practice, the following compounds find
application:
1. 4,4 -bis(diethylamino)benzophenone,
2. 4-dimethylaminobenzoic acid (4-DMABA),
3. ethyl-4-dimethylamino benzoate (EDMAB),
122
4. 3-dimethylaminobenzoic acid (3-DMABA),
5. 4-dimethylaminobenzoin (DMAB),
6. 4-dimethylaminobenzaldehyde (DMABAL),
7. 1,2,4-trimethoxybenzene (TMB), and
8. N-phenylglycine.
3.4.7 Epoxy Systems with Vinyl
Groups
Besides pure epoxy systems, mixed systems such
as epoxy acrylates are in use. These systems can
be cured with radical photoinitiators. Examples
of such initiators are 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) butan-1-one, 2-methyl-1-[4-
(methylthio) phenyl]-2-morpholinopropan-1-one, 2,
2-dimethoxy-1,2-diphenylethan-1-one, and hydroxy-
2-methyl-1-phenyl-propanone [274].
3.4.8 Curing Kinetics
There are various methods to investigate the kinetics
of curing, including:
1. viscometry,
2. differential scanning calorimetry,
3. modulated differential scanning calorimetry,
4. dielectric analysis,
5. dynamic mechanical analysis,
6. in situ Fourier transform infrared spectroscopy,
and
7. fluorescence response.
3.4.8.1 Viscometry
In the course of curing, the crosslinking density and
the viscosity as well as the modulus of the resin system
increase. The viscoelastic properties can be measured
in a torsional motion [275].
3.4.8.2 Differential Scanning
Calorimetry
Differential scanning calorimetry (DSC) is the only
direct reaction rate method which operates in two
modes: constant temperature or linear programmed
mode. Several methods to evaluate the data obtained
by differential scanning calorimetry are available
[276]. The isoconversional method [277] is frequently
REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS
used to calculate the energies of activation and evalu-
ate the dependence of the effective activation energy
on the extent of conversion [278].
Relations are available between the degree of con-
version, the time dependence of the conversion, and
the direct measurable parameters, i.e., viscometry, dif-
ferential scanning calorimetry, and dynamic mechan-
ical analysis. The equation is always second order
although the coefficients of this equation are differ-
ent for the individual methods. The DSC technique
becomes insensitive at conversions shortly after the
gel point [279]. However, changes in the heat capac-
ity can be indicators of the onset and the completion
of the vitrification [232].
Differential scanning calorimetry provides infor-
mation concerning the reaction mechanism of curing.
The ring opening reaction between phenyl glycidyl
ether and aniline was investigated by DSC. The reac-
tion resembles the diepoxy-diamine cure mechanism.
However, it was detected that besides the epoxy ring
opening reaction, another exothermic process in the
last stages of the reaction takes place. It was con-
cluded that the reaction of epoxy ring opening by ani-
line occurs by two concurrent pathways [280,281], an
uncatalyzed one and an autocatalyzed one.
3.4.8.3 Temperature-modulated
Differential Scanning
Calorimetry
In temperature-modulated differential scanning
calorimetry (TMDSC), the sample is subjected to a
sinusoidal temperature change. The instruments are
called differential AC calorimeters. This particular
method can measure the storage heat capacity and
the loss heat capacity, i.e., the reversible part of heat
that can be withdrawn again by cooling, and a part of
heat consumed by chemical reaction. A complex heat
capacity with a real part (storage heat capacity) and
an imaginary part (loss heat capacity) can be defined
[282]. The treatment is similar to other complex
modules in mechanics.
During the curing, the glass transition tempera-
ture rises steadily. The reaction-induced vitrification
takes place when the glass transition temperature rises
above the curing temperature. This transition can
be followed simultaneously with the reaction rate in
TMDSC [283,284].
Modulated differential scanning calorimetry allows
detection of reaction-induced phase separations. The
3: EPOXY RESINS
apparent heat capacity changes as phase separation
occurs. The cloud point can be determined with
optical microscopy, and there is a correspondence
between the optical method and the calorimetry
method [285,286]. In an amine curing system, a com-
plex formed from the primary amine and the epox-
ide was postulated that initiates the curing reaction.
The reactions of the primary amine and the secondary
amine with an epoxy-hydroxyl complex are compara-
tively slow and thus rate determining during the whole
curing process [287,283]. In an epoxy-anhydride sys-
tem some complications have been elucidated [288].
Temperature modulated DSC can be used to
advantage during isothermal curing of semi-
interpenetrating polymer networks [289].
The kinetics of curing of diglycidyl ether dipheny-
lene propane with methyl tetrahydrophthal anhydride
was examined. Two accelerators were used, an accel-
erator of the amine type and an accelerator of the com-
plex type. The accelerator influences the energy of
activation. The kinetics can be well described by an
autocatalytic model [290].
3.4.8.4 Dielectric Analysis
Dielectric analysis [291] is based on the measurement
of the dielectric permittivity ε  and the dielectric loss
factor ε in the course of curing. The complex dielec-
tric constant ε ∗ may be expressed by
ε ∗ = ε  − iε  . (3.1)
The permittivity is proportional to the capacitance
and depends on the orientation polarization. The ori-
entation polarization results from the change in the
dipole moment due to the chemical reaction and from
the change of the concentration of dipoles due to the
volume contraction during the curing reaction. The
loss factor corresponds to the energy loss.
Both dielectric and mechanical measurements are
suitable techniques for monitoring the curing process.
Also, phase separation processes can be monitored by
dielectric analysis, because dielectric measurements
are sensitive to interfacial charge polarization. Dipolar
indicates vitrification through the α-relaxation pro-
cess in both phases [292]. Further, dielectric sensor
measurements have the advantage that they can be
made in the laboratory as well as in situ in the fabrica-
tion tool in a production line [293]. A relation between
the dielectric response and other methods measuring
the gel point has been established in epoxy systems
[232].
123
Dielectric analysis, in combination with other
experimental techniques, can be used to establish a
time-temperature-transition (TTT) diagram. The cur-
ing must be measured in a series of experiments
at different temperatures. In such a diagram gela-
tion, vitrification, full cures, and phase separation are
marked [294].
A technique involving simultaneous dielectric
and near-infrared measurements has been used
for monitoring the curing of blends of a digly-
cidyl ether bisphenol A epoxy resin with a
4,4 -diaminodiphenylmethane hardener and various
amounts of PMMA as modifier [295].
3.4.8.5 In Situ Fourier Transform
Infrared Spectroscopy
During the curing reaction, the appearance or disap-
pearance of various characteristic infrared bands can
be monitored. This method yields more information
than a single parameter, e.g., as obtained from a DSC
measurement. However, there is more work needed to
calibrate the system properly than in a DSC experi-
ment. Multivariate analysis, in particular alternating
least squares, allows calculation of the concentration
profiles and the spectra of all species involved in the
reaction of curing epoxy resins [296].
During curing, the intensity of the epoxy group, at
789−746 cm−1 , decreases [297]. For example, based
on such experiments, in the curing of a dicyanate ester
(1,1-bis(4-cyanatophenyl)ethane) with a bisphenol A
epoxide, the formation of an oxazoline structure has
been proposed [298].
3.4.8.6 Fluorescence Response
Fluorescence is a very sensitive and non-destructive
technique to monitor the curing. The fluorescence
response from chemical labels and probes enables the
changes to be followed in the surroundings of the
chemical label. In the curing process, the viscosity
may change by about six orders of magnitude.
A change in the viscosity of the medium leads to
a decrease in the non-radiative decay rate and conse-
quently a change in the fluorescence quantum yield.
The reaction medium acts as a thermal bath for the
excited fluorescent molecule. When the monomers
become fixed in forming a crosslinked polymer, a
reduction of translational, rotational, and vibrational
degrees of freedom in the bath takes place. There-
fore, a reduction in the number of non-radiative
124
H3 C CH 3
N
NH 2 O S
C Experiments with the diglycidyl ether of bisphe-
O OH CH 2 C H2 NH
DNS-EDA
Figure 3.21 9-Anthroic acid, 5-dimethylaminonaph-
thalene-1-(2-aminoethyl)sulfonamide (DNS-EDA).
deactivation pathways and an increase in fluorescence
intensity occurs.
1-Pyrenesulfonyl chloride was used as a chem-
ical label for silica epoxy interfaces, the surface
coated with (3-aminopropyl)triethoxysilane, because
it reacts easily with amine groups, yielding sulfon-
amide derivatives [299]. Also, 9-anthroic acid, its
ester derivatives and dimethylaminonaphthalene-1-
(2-aminoethyl)sulfonamide, cf. Figure 3.21, are com-
mon fluorescence dyes [300,301].
3.4.9 Thermal Curing
By investigating the curing of a commercial epoxy
prepolymer with imidazole curing agents, it has been
verified that the cure schedule influences the proper-
ties of the end product. The highest thermal stability
of the polymers can be achieved by isothermal cure
schedules. Samples cured by a temperature program
showed lower glass transition temperatures. In a series
of temperature programmed curing experiments, a
lower heating rate resulted in higher transition tem-
peratures and superior thermal stability. The initial
and postcure schedules are thus of critical importance
for the final properties of the polymer [302].
3.4.10 Microwave Curing
Due to increasing application in the aerospace and
microelectronics industries the demand for acceler-
ated curing has emerged. In particular, for the micro-
electronics industry, the curing of thermoset systems
has become a bottleneck of the whole production pro-
cess. Besides photo curing, curing with γ -rays and
electron beams is an alternative.
Microwave curing of materials has the potential to
deliver several major advantages over conventional
thermal processing. One of these is a decrease in the
REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS
time necessary for manufacture since another poten-
tial advantage is that the power is directed to the sam-
ple. The microwave energy is absorbed throughout
the body of the material rather than relying on ther-
mal conduction and convection. Therefore, the energy
O consumed is less than thermal curing.
nol A and three types of curing agents, i.e.,
4,4 -diaminodiphenyl sulfone, 4,4 -diaminodi-
phenylmethane, and m-phenylene diamine with
various energies of microwave energy, showed
that in comparison to thermal curing microwave
curing is faster. The glass transition temperatures are
somewhat lower in the case of the products cured
with microwave technology in comparison to those
cured by thermal methods [303]. However, the curing
performance is strongly dependent on the curing
agent used [304]. The interfacial shear strengths in
those composites cured with microwave techniques
are comparable with being thermally postcured [305].
3.5 Properties
Mechanical properties of epoxy resins can be corre-
lated and traced back to the constituting monomers.
The mechanical properties of epoxy resins depend on
the flexibility of the segments and on the crosslink-
ing density. Epoxy resins shrink less in the course of
curing than vinyl resins.
It is important to distinguish between the shrinkage
that occurs before gelling and after gelling. Only a
shrinkage that occurs after gelling results in residual
stress in the final product.
Epoxy resins can exhibit several thermal transi-
tion regions, depending on the chemical nature of the
monomers. These transitions influence the curing. If
a glass transition occurs during curing at the temper-
ature applied, the individual reactive parts of the pen-
dant molecules can no longer move sufficiently and
the curing reaction freezes at this conversion. How-
ever, raising the temperature affects further curing.
Cycloaliphatic epoxy resins have a low viscosity.
The cured resins exhibit a high glass transition tem-
perature. On the other hand, they exhibit low break
elongation and toughness because of their high
crosslinking density.
Epoxy resins show good electrical properties. Of
course, the electrical properties are affected by the
moisture content. On the other hand, the resins can be
made electrically conductive, by metal particles such
3: EPOXY RESINS
Table 3.14 Epoxies Based on Hybrid Polymers
Compounds
Siloxane polymer with pendant epoxide rings
Epoxy poly(urethane) hybrid resins
Maleimide-epoxy resins
as silver and copper. Epoxy resins adhere by forming
strong bonds with the majority of surfaces; therefore,
an important application is in adhesives. Epoxy resins
have excellent resistance to acids, bases, organic and
inorganic solvents, salts, and other chemicals.
3.5.1 Hybrid Polymers and Mixed
Polymers
Hybrid polymers and mixed polymers are summa-
rized in Table 3.14. These include silicone-epoxy
hybrid polymers, urethane-epoxy hybrid polymers,
and maleimide-epoxy polymers.
3.5.1.1 Epoxy-siloxane Copolymers
A siloxane polymer with pendant epoxide rings on
the side chain of the polysiloxane polymer backbone,
when blended with diglycidyl bisphenol A ether and
cured, increases the mobility of the crosslinked net-
work and the thermal stability. Graft siloxane polymer
with pendant epoxide rings can be synthesized by the
hydrosilylation of poly(methyl hydrosiloxane) with
allyl glycidyl ether [306].
Aminopropyl-terminated poly(dimethyl siloxane)
blended in an epoxy resin shows an outstand-
ing oil and water-repellency in coatings [310].
The peel strength of a pressure-sensitive adhesive
affixed to the modified epoxy resin also decreases.
Polyether/poly(dimethyl siloxane)/polyether triblock
copolymers added in amounts of ca. 5 phr efficiently
reduce the static friction coefficient of the cured
blends upon steel [311].
Silsesquioxanes are organosilicon compounds with
the general formula [RSiO3/2 ]n , cf. Figure 8.1,
on page 217. Silsesquioxane (SSO) solutions were
reacted with diglycidyl either of bisphenol A with 4-
dimethylaminopyridine as initiator, to result in SSO-
modified epoxy networks. The modification with SSO
increased the elastic modulus in the glassy state. This
is explained by an increase in the cohesive energy
density [312].
125
Remark/Reference
[306–308]
[309]
3.5.1.2 Maleimide-epoxy Resins
Maleimide-epoxy resins are based on N-(p-
carboxyphenyl) maleimide and allyl glycidyl ether
[309]. The resin can be cured thermally and is suitable
as one-component resin.
3.5.2 Recycling
3.5.2.1 Solvolysis
The recycling of wastes of epoxy resins is very diffi-
cult, because of the inherent infusibility and insolu-
bility of the materials. Often the composite materials
contain reinforcing fibers, metals, and fillers [313].
Efficient destruction of the organic material in com-
posites can be achieved by thermolysis processes or by
incineration processes. These methods yield consid-
erable amounts of noncombustible residues or decom-
position products that are not attractive for further use.
Valuable recycled materials can be obtained by
solvolysis methods. Here, the depolymerization prod-
ucts and reinforcing fibers can be retrieved.
By glycolysis with diethylene glycol, the ester link-
ages of a bis-epoxide (diglycidyl ether of bisphenol A)
that is cured with a dianhydride are cleaved. The trans-
esterification is catalyzed by titanium n-butoxide.
In the case of 70% glass fiber/epoxide-anhydride
composites, the glass fibers can be recovered. The liq-
uid depolymerization products may be converted to
polyols, components for unsaturated polyester resins,
etc.
The glycolysis of amine-cured epoxide resins
shows no volatile nitrogen compounds. The most
favored path of degradation is the decomposition of
the ether linkage of bisphenol A to yield oligomers
with phenol groups [314]. The separation of the phe-
nolic compounds from the glycolysis products can be
achieved by liquid–liquid extraction.
The glycolysis products can be basically used as a
polyol in production of poly(urethane). However, the
hydroxyl value is much too high for poly(urethane)
production.
126 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

It has been suggested to use the solvolysis products O

from epoxide resins in combination with other solvol-
O
ysis products, e.g., solvolysis products from wastes O O
from PET for semi-interpenetrating networks based
on PET hydrolyzate and epoxies [315]. O CH3

O
3.5.2.2 Reworkable Epoxies for O O
Electronic Packaging
Application O CH3

Epoxy resins show excellent longevity and resistance O

to aging. This is due to the formation of an insolu- O CH3 O
ble and infusible crosslinked network during the cure
cycle. This property is sometimes seen as a drawback O CH3
from the repairability standpoint.
O
During the manufacture of expensive electronic O CH3 O
parts, such as multichip modules, several chips are
mounted onto one high density board. If one chip is CH3
damaged, then the whole board will become useless. O CH3 O
The same is true if some special electronic parts in O O
CH CH 2
a board need to be modified because of progress in
technology.
Therefore, the availability of a reworkable mate-
rial, that is, one that undergoes controlled network
breakdown, expands the potential routes to repair-
ing, replacing, or removing assembled structures and O CH3 CH3 O
O O
devices. Implementing reworkable materials early C CH
could increase recycling concerns that could be faced CH3
in the near future.
An effective solution is to use thermally reworkable
epoxide resins for underfilling [316,317]. In such sys-
tems, the cured epoxy network can be degraded by Figure 3.22 Epoxides with thermally cleavable
locally heating to a suitable temperature, and a faulty groups for controlled network breakdown: top,
chip can be replaced. esters; bottom, ethers. 1,2-Bis(2,3-epoxycyclohexyl-
Commercialcycloaliphaticepoxidesdegradeatabout oxy)propane, 2-methyl-2,4-bis(2,3-epoxycyclohexyl-
300 ◦ C.Epoxideswithsecondaryortertiaryesterbonds oxy)pentane.
(as shown in Figure 3.22) have been demonstrated to
decomposeattemperaturesbetween200 ◦ Cand300 ◦ C
[318,233].Theepoxidesarecycloaliphaticcompounds
Thio links can be used to form a reversible network
and can be basically derived by the esterification of
[236]. Further diepoxides connected via acetal links
cyclohexenoic acid with α-terpineol with subsequent
can be used for the introduction of reversible chemical
epoxidation. Diepoxides with carbamate and carbon-
links [320]. This type of network can be degraded in
ate groups [319] also degrade in this temperature range.
acidic solvents.
Incomparisontochemicaldegradationmethods,heatto
degrade the network can be localized more easily in the
reworking process, thereby allowing for more precise
controlovertheregionoftheboardthatwillbereworked. 3.5.2.3 Recycled Poly(ethylene
Instead of branched ester structures, ether struc- terephthalate)
tures, cf. Figure 3.22, bottom, are also suitable candi- A method of degradation of poly(ethylene terephtha-
dates for thermolabile linkages in epoxides [249]. late) wastes for the preparation of materials for the
3: EPOXY RESINS
synthesis and modification of epoxy resins has been
presented [321].
The optimization of the composition of the epoxy
resins modified with the recycled materials was the
goal of the research.
Conditions required for a strong degradation of the
waste were chosen. The products of glycolysis were
used as polyhydroxy reagents for the synthesis of
epoxy resins by the reaction with epichlorohydrin.
It was found that the modification of the epoxy
resins with the degraded waste products caused an
improvement of their tensile and flexural strengths,
hardness, and thermal stability. Still better results
were obtained from degradation products with longer
alkyl fragments [321].
3.6 Applications and Uses
3.6.1 Coatings
The largest applications of epoxy resins are in coat-
ings. Epoxy resin coatings have excellent mechanical
strength and adhesion to many kinds of surfaces. They
are corrosion resistant and resistant to many chem-
icals. Coatings find applications in various paints,
white ware, and automotive and naval sectors, for
heavy corrosion protection of all kinds. Epoxy coat-
ing formulations are available both as liquid and solid
resins. Epoxy acrylic hybrid systems are used as coat-
ings for household applications, e.g., indoor and out-
door furniture and metal products.
Waterborne coatings are dispersions of special for-
mulations of the resins with suitable surfactants.
These materials can be applied by electrodeposition
techniques. Powders can be applied as coatings by
fluidized bed techniques.
Environmental friendly coatings based on low-cost
epoxide resins have been developed [322]. These coat-
ings are prepared from a natural nontoxic phenolic
material such as cardanol instead of ordinary phe-
nol. Novolak resins are prepared by the reaction of
cardanol with formaldehyde and subsequently epoxi-
dized with epichlorohydrin.
These products were further modified with
diethanolamine so that tertiary amine moieties are in
the molecules that are needed for self-curing. Films
from these epoxide resins are self-curable at 160 ◦ C
within 30 min. The films exhibit a good chemical
resistance. The coatings can be applied both as a
primer coat and a top coat on metallic substrates [322].
127
An intumescent coating has been designed using
a bisphenol A epoxy resin as binder. The intu-
mescent coating composition contains an expand-
able graphite, ammonium polyphosphate, melamine,
and zinc borate. Melamine acts as the blowing
agent [323].
The curing of epoxy resin latex coatings and
solvent-based coatings was compared. Films formed
from a solvent-based epoxy resin and an amine cur-
ing agent exhibits a high gloss. On the other hand, the
epoxy resin latex has a lower gloss. The gloss becomes
still lower when formulations with longer curing times
are used [324].
MoS2 -doped phenolic epoxy resin can be used
as solid lubricating coatings. The friction and wear
behaviors of the coatings were evaluated using a ball-
on-disk tribometer. During the preparation, the mate-
rials were irradiated with atomic oxygen. This causes
an increase in the friction coefficient and a decrease
in the wear resistance, because this treatment effects
an oxidative degradation of epoxy binder [325].
3.6.2 Foams
Epoxy resins can be fabricated to make foams.
Foamable compositions have been described from
a novolak resin, an epoxy resin, and a blowing
agent. Water can act as a blowing agent, especially
when higher density foams are required. Novolak
resins are typically suspended in an aqueous solu-
tion, which is the blowing agent [326]. Encapsu-
lated calcium carbonate or anhydrous sodium bicar-
bonate are suitable blowing agents [327]. Phos-
phoric acid is used to catalyze the polymeriza-
tion of resin and it also reacts with the car-
bonate core to generate a blowing gas to form
voids.
Epoxy foams were synthesized by simultaneous
crosslinking and foaming. An amine-amide adduct
was used as curing agent and poly(methyl hydrosilox-
ane) was used as a blowing agent. Hydrogen gas is
formed by reaction of the hydrosilane moiety with
the curing agent [328]. The epoxy composition is a
combination of aromatic and aliphatoc epoxy resins,
a foam stabilizer, and nucleating agent.
Foams with different densities of 0.15–0.45
g cm−3 can be prepared by varying the amount of the
blowing agent. The mechanical, thermal, and dielec-
tric properties of the foams were found to be strongly
dependent on the microstructure of the foams [328].
128 REACTIVE POLYMERS FUNDAMENTALS
3.6.3 Adhesives
Approximately 5% of total epoxy resin production is
used in adhesive applications. Epoxide resin adhesives
are formulated two-component systems that cure at
room temperature, and as hot curing systems in the
form of films and tapes. Among others, acrylates are
suitable modifiers for epoxy adhesives.
3.6.4 Molding Techniques
Epoxy resins are used in all known reactive mold-
ing techniques. Non-reinforced articles can be molded
with aluminum molds. This is used for electrical coil
covering, etc. In electronic industries various embed-
ding techniques, i.e., casting and potting, and impreg-
nation are important applications. Laminated sheets
are used for the fabrication of printed circuit boards
in the electronics industry.
Pultrusion and lamination are common techniques.
Laminated articles are also used in building con-
structions for concrete molds, honeycomb cores,
reinforced pipes, etc. Epoxy resins are superior to
polyesters where adhesion and underwater strength
are important.
3.6.5 Stabilizers for Poly(vinyl
chloride)
Epoxy resins with monofunctional epoxy groups
in the prepolymer are effective in stabilizing PVC
against dehydrochlorination during processing and
use, in comparison to tribasic lead sulfate. Lead-based
stabilizers for poly(vinyl chloride) are mostly banned
and only allowed for a few applications. For example,
the replacement of lead-based stabilizers by epoxy
stabilizers will improve the environmental toxicity of
lead in water flowing through PVC pipes [329].
3.7 Special Formulations
3.7.1 Development of
Formulations
In practice, epoxy resins are composed of a wide vari-
ety of individual components. To obtain a composition
with the desired properties, a great deal of know-how
is required.
A solid knowledge of the structure-property rela-
tionships can serve as a valuable tool for the art of
formulation [330].
AND APPLICATIONS
On the other hand, there are methods that are helpful
in the development of formulations. In particular, sta-
tistical methods can save time. An overview of such
methods is given in the standard book of Box and
Hunter [331]. Instead, most studies on epoxy formu-
lation are done by the “one variable at a time” space
method. This means that only one parameter of inter-
est is changed while the other remaining parameters
are kept constant. This strategy provides admittedly
valuable information; however, it does not allow a
good insight into mutual interactions of formulation
parameters. The usefulness of statistical methods in
the field of formulation of epoxy adhesives has been
demonstrated in the literature [332].
3.7.2 Restoration Materials
A variety of epoxy resins are used for the consolida-
tion of stone monuments in an outdoor environment.
For these applications good weathering resistance and
sufficient penetration depth are mandatory.
A suitable epoxy monomer for restoration materials
is 3-glycidoxypropyltrimethoxysilane (GLYMO) and
amine curing agent is (3-aminopropyl)triethoxysi-
lane. This monomeric composition penetrates deep
enough to exceed the maximum moisture zone and
creeps beyond the damaged layers.
The alkoxysilane groups are hydrolytically unstable
and generate silanol groups which may crosslink with
one another, and form bonds to the hydroxyl groups
present in the stone, thus anchoring the organic poly-
mer onto the lithic matrix [333,334].
The curing kinetics of hybrid materials prepared
from diglycidyl ether of bisphenol A and GLYMO has
been investigated using poly(oxypropylene)diamine
as a hardener [335]. The total conversion of epoxy
groups was found to decrease with increasing content
of GLYMO. The experimental data were scattered,
which was attributed to an uncontrolled initial hydrol-
ysis of GLYMO caused by the varying air humidity
during the sample preparation.
3.7.3 Epoxy Polymer Concrete
The effects of solvents for the formulation of epoxy
polymer concrete has been investigated [336]. When a
mixture of acetone and toluene was used as solvent in
some cases the compressive strength and the flexural
strength could be increased.
3: EPOXY RESINS
3.7.4 Biodegradable
Epoxy-polyester Resins
Biodegradable epoxy-polyester resins consist of
polyesters with pendant epoxidized allyl groups
[244]. These polyesters are synthesized from succinic
anhydride and allyl glycidyl ether and butyl glycidyl
ether with benzyltrimethylammonium chloride as cat-
alyst.
The butyl glycidyl ether acts as a diluent for the
allyl functionalities, in order to reduce the amount of
pendant allyl groups in the chain. The epoxidation
of the polyesters is achieved by m-chloroperbenzoic
acid. The epoxy-polyester resins can be cured with
glutaric anhydride.
3.7.5 Swellable Epoxies
Hydrophilic polymers find applications in medicine
and agriculture, owing to their biocompatibility [337].
Crosslinked structures, prepared from sucrose and
1,4-butanediol diglycidyl ether (1,4-BDE), are hydro-
gels with water regain values of 30% [338]. The
crosslinking is achieved with triethylamine or sodium
hydroxide. Triethylamine gives rise to end capped
diethylamine groups. By this reaction the ethyl group
is left behind as ethyl ether in the sucrose.
The ring opening polymerization of epoxy end-
terminated PEO can serve to synthesize crosslinked
materials with an exceptional swelling behavior [339].
These gels have attracted interest for use as drug deliv-
ery platforms.
3.7.6 Membrane Materials
Reactive membrane materials can be prepared from 2-
hydroxyethyl methacrylate and glycidyl methacrylate
by radical photopolymerization.
Enzymes, such as cholesterol oxidase, can be
directly immobilized on the membrane by the reac-
tion of the amino groups of the enzyme and the
epoxide groups of the membrane. The immobilization
improves the pH stability of the enzyme as well as its
thermal stability. The immobilized enzyme activity
remains quite stable [340].
Poly(2-hydroxyethyl methacrylate) membranes
can be also activated by direct treatment with
epichlorohydrin. On such materials poly(L-lysine)
can be immobilized [341]. Such a membrane with
immobilized poly(L-lysine) can be utilized as an
adsorbent for DNA adsorption experiments.
129
Ultrafiltration membranes composed of activated
carbon in an epoxy resin matrix have been synthe-
sized [342].
Composite membranes with a final porosity of 60%
were prepared from a microporous powder activated
carbon, with different particle size distributions. The
membranes were characterized for their thermal sta-
bility, chemical composition, specific surface area,
and porosity. A specific surface area with an apparent
porosity of 50–58% and thermal stability up to 370 ◦ C
was found. At this temperature the decomposition of
the organic matrix starts [342].
3.7.7 Controlled-release
Formulations for Agriculture
In order to introduce pendant dichlorobenzaldehyde
functionalities as acetals, the epoxide functionalities
in linear and crosslinked poly(glycidyl methacrylate)
are hydrolyzed to diol groups. In the second step the
pendant diol groups in the polymers are acetalized by
dichlorobenzaldehyde [343]. Dichlorobenzaldehyde
is a bioactive agent that is slowly released under var-
ious conditions.
3.7.8 Shape Memory Composites
Medical applications have been the primary targets
for the development of shape memory polymers that
exhibit softness at body temperature, biocompatibil-
ity, high deformability, good shape recovery, and good
shape fixity [344]. Shape memory epoxies are partic-
ularly promising base materials for such applications.
The influence of the molecular structure design on
their shape memory properties has been studied. The
instantaneous shape memory behavior was found to
be similar for all the epoxies studied.
The performances strongly depend on the thermal
expansion or contraction, respectively, of the materi-
als during thermomechanical cycling. Materials with
low crosslinking density and thus with high chain flex-
ibility or mobility exhibit reduced performance [344].
Synthetic routes for adding attractive properties to
commonly used industrial and commodity resins have
been elucidated [345].
3.7.9 Electronic Packaging
Application
In flip-chip manufacturing, filled polymers serve as
underfilling. Underfilling is the plastic material which
130 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

is inserted in the gap between integrated circuit and the
substrate. The gap is approximately 50–75 µm wide.
The underfilling is used to couple the chip and the sub-
strate mechanically. It decreases the residual stress in
the solder joints caused by thermal expansion. The
materials used for underfilling should have good wet-
ting characteristics, significant adhesion, high con-
ductivity, and should not form voids. The preven-
tion of void formation is essential for thermal con-
ductivity. Low viscosity of the monomeric resin is
essential to achieve void-free underfillings. A resin
with a lower viscosity allows the addition of a greater
amount of filler. The viscosity of a benzoxazine
resin can be reduced by the incorporation of a low-
viscosity epoxy resin. The benzoxazine resin imparts
low water uptake, high char yield, and mechanical
strength. The epoxy resin reduces the viscosity of
the mixture and results in higher crosslinking den-
sity and improved thermal stability of the material.
A melt viscosity of about 0.3 Pa s at 100 ◦ C can be
achieved [350].
The effects of an epoxy resin on various arylamine-
based benzoxazine resins, such as aniline, m-
toluidine, and 3,5-xylidine, have been investigated
[351]. The processing windows have become more
extended by the addition of epoxy resins. The gel
points of the compositions can be predicted by an
Arrhenius equation. The glass transition temperatures
exhibit synergistic behavior. In addition, the mechan-
ical properties become somewhat better.
response in the molar range of 10−4 –10−1 Nd3+ . Zir-
conium antimonotungstate with the epoxy resin in a
ratio of 40:60% shows a best response in the molar
range of 10−5 –10−4 Nd3+ . Both electrodes have a
fast response time. The electrodes can be used in a pH
range of 3–9. The electrodes can be used as indica-
tor electrodes for the potentiometric titration of Nd3+
with EDTA [346].
Further, the response time of the tin tungstophos-
phate sensor is less than 5 s [347,348].
Quinhydrone and spectral graphite powders with an
epoxy resin and a polyethylene polyamine as binder
have been tested for use as a solid indicator electrode
[352]. The design is intended for measurements of the
pH. The graphite-quinhydrone indicator electrode is
mechanically renewed before a measurement series
starts. The pH dependence of the potential in the pH
range of 2–7 is linear and close to the theoretical
model. In contrast to a traditional quinhydrone elec-
trode, the results are reproducible and linearly depend
on the pH.
A composite electrode, based on multiwalled car-
bon nanotubes and an epoxy resin, was tested as the
working electrode in an automated flow system. The
composition is made from 10% carbon nanotubes and
90% epoxy resin. A highly sensitive device for the
detection of free Cl2 in water at 0.02–4 mg l−1 with a
response time of 60 s could be fabricated [353]. The
system was validated both for tap water and swim-
ming pool water.

3.7.10 Ion-selective Electrodes 3.7.11 Solid Polymer Electrolytes

A series of ion-selective electrodes have been pre-
pared using epoxy resins as binders. The analytes and
base materials are summarized in Table 3.15.
Nd3+ -selective electrodes were prepared by tin
antimonotungstate and zirconium antimonotungstate
as electroactive materials and an epoxy resin as the
binding material [346]. Tin antimonotungstate with
the epoxy resin in a ratio of 50:50% shows a best
The interest in solid polymer electrolytes arises from
the possibility of applications of polymer ionic con-
ductors in energy storage systems, electrochromic
windows, and fuel cells or sensors operating from sub-
ambient to moderate temperatures [354].
Hosts for solid polymer electrolytes are PEO,
segmented poly(urethane)s with poly(ethylene
oxide)/poly(dimethyl siloxane) [355] and with

Table 3.15 Ion-selective Electrodes

Analyte Electrode References

Nd3+ Tin antimonotungstate [346]
Nd3+ Zirconium antimonotungstate [346]
Nd3+ Tin tungstophosphate [347,348]
Dy3+ Zirconium antimonomolybdate [349]
3: EPOXY RESINS
poly(ethylene oxide)/perfluoropolyether [356]
blocks, respectively, as well as crosslinked epoxy-
siloxane polymer complexes [357,358]. The copoly-
mers are immersed in a liquid electrolyte (1 M
LiClO4 in propylene carbonate) to form gel-type
electrolytes.
Solvent-free solid polymer electrolytes are based
on polyether epoxy crosslinked with poly(propylene
oxide) polyamines [359]. The crosslinked polyether
networks are doped with LiClO4 . The network is pre-
pared by mixing epoxy monomer, the curing agent
dissolved in acetone, and LiClO4 . To obtain films the
mixture is poured on plates and cured at elevated tem-
peratures. The electric conductivity of the polymer
electrolyte is dependent on interactions between ions
and the host polymer.
3.7.12 Optical Resins
3.7.12.1 Lenses
In comparison to glasses, plastics have low den-
sity, i.e., comparative low weight, are fragmentation-
resistant and can be easily dyed. Therefore, optical
materials made from organic polymers are attractive
for optical elements such as lenses of eyeglasses and
cameras. However, the refractive index of the stan-
dard resins is relatively small. Therefore, there is a
need to use materials with high refractive index and
low chromatic aberration.
The introduction of sulfur into the monomers raises
the refractive index. Sulfur-containing resins have a
high refractive index, low dispersion, and a good heat
stability [23,233]. Components for epoxy resin with
high refractive index are obtained from BEPTPhS and
epichlorohydrin.
A sulfur-containing curing agent is captotriethy-
lamine, which can be obtained from triethanolamine.
Besides sulfur-containing epoxies, with tailor-made
polyphosphazenes, refractive indices ranging from
1.60 to 1.75 can be achieved [360].
3.7.12.2 LEDs
Epoxy carbazole compositions show photolumi-
nescence. In particular, 5-(9-carbazolyl)methyl-1,3-
oxothiolane-2-thione has been used for formula-
tions. These products may be used for LEDs.
A co-crosslinking of the epoxy resin and the car-
bazole occurs. The absorption spectra in the UV range
131
O
HO C CH
CH OH
1,3-Bis-(4-hydroxy-phenyl)-propenone
Figure 3.23 4,4 -Dihydroxychalcone.
and the photoluminescence are characteristic for car-
bazole compounds. The epoxy resin may act as a scat-
tering matrix for the carbazolyl substituents [361].
A heat curable silicone/epoxy resin composition
for high-brightness LEDs or solar cells has been
described [362]. The composition contains a heat cur-
able silicone resin, triazine-based derivative epoxy
resin and an acid anhydride [362].
The triazine-based epoxy resin contains an isocya-
nurate ring and exhibits particularly superior light
resistance and electrical insulation. Specific examples
of such epoxy compounds are tris(2,3-epoxypropyl)
isocyanurate and tris(α-methylglycidyl) isocyanu-
rate. The acid anhydride acts as a curing agent. In order
to impart improved light resistance, the acid anhydride
is preferably non-aromatic, and without double bonds.
Examples of such acid anhydrides include hexa-
hydrophthalic anhydride, methylhexahydrophthalic
anhydride, trialkyltetrahydrophthalic anhydrides,
and hydrogenated methylnadic anhydride [362] (see
Figure 3.23).
For curing the silicone resin of a component, special
accelerators are required. A wide variety of possible
compounds have been mentioned; however, most pre-
ferred in the present case are zinc benzoate and org-
anotitanium chelate compounds [362].
3.7.12.3 Solar Cells
The effect of the composition on the overheating pro-
tection properties of thermotropic systems for solar
thermal collectors was estimated [363]. Optical prop-
erties, switching temperatures, and the switching pro-
cess were assessed by optical spectroscopy. Thermal
transitions of the thermotropic layers and the addi-
tives used were determined by differential scanning
calorimetry. The thermotropic layers showed a hemi-
spheric solar transmittance between 76% and 87%
in the clear state. Above the switching threshold this
transmittance changed to 62–85%. The layers exhib-
ited switching temperatures of 33–80 ◦ C.
132 REACTIVE POLYMERS FUNDAMENTALS
Nanoscaled poly(pyrrole) particles were synthe-
sized using I2 as dopant and oxidant. These materi-
als were subsequently used for a poly(pyrrole) epoxy
resin counter electrode for construction of dye sensi-
tized solar cells. An open-circuit voltage of 0.525 V
was found and the short circuit was 0.90 mA cm−2 .
The introduction of this counter electrode decreases
the demand of fluorine-doped tin oxide coated glass
substrate [364].
3.7.12.4 Liquid Crystal Displays
In liquid crystal displays (LCDs), control of the align-
ment of the LC molecules is one of the most impor-
tant issues with respect to the quality of LCDs. The
rubbing method does not satisfy the recent demands
for alignment quality. The photoalignment method
reduces contaminations that lower the contrast ratio
and electrostatic build-up that can cause failure of
thin-film transistors [365].
Nematic liquid crystalline materials can be aligned
homogeneously on a photoreactive polymer film
when exposed to linearly polarized light. Thermal sta-
bility and photostability of the alignment layer are
crucial parameters and the alignment layer must be
transparent in the visible region for a display device.
Certain photocrosslinkable polymer systems meet
these demands. Derivatives of cinnamic ester
and cinnamic acid are suitable candidates for
phototransformations. In particular, the anisotropic
[2 + 2] cycloaddition of the cinnamate moiety can
induce an irreversible alignment of a low-molecular-
weight liquid crystal. Polymers with the chalcone
group in the side chain react in a similar way.
A chalcone-epoxy compound can be synthesized
from 4,4 -dihydroxychalcone (cf. Figure 3.23) and
epichlorohydrin in the same way as with bisphenol
A. In this photoreactive epoxy oligomer, the photo-
sensitive unsaturated carbonyl moieties are located in
the main chain. For the polymerization of the epoxy
groups, triaryl sulfonium hexafluoroantimonate is a
suitable photoinitiator.
The photodimerization of the chalcone precedes the
photopolymerization of the epoxy groups. Under con-
tinuous irradiation, the anisotropic photocrosslinked
chain molecules can be frozen by the photopolymer-
ization of the epoxy groups at both ends of the com-
pound. Without a photoinitiator, the end groups of the
oligomer are not fixed. Therefore, there are two kinds
of photochemical reactions that enhance the photosta-
bility of the induced optical anisotropy [24].
AND APPLICATIONS
A UV curable sealant was synthesized from an
epoxy resin with acrylic acid in the presence of cat-
alyst N,N-dimethylbenzylamine. The material can be
solidified by irradiation with UV light at 365 nm for
8 s. It has been demonstrated that the sealant can be
used for LCDs [366].
3.7.12.5 Holography
Materials for high-resolution holograms, which can
be used on holographic optical elements such
as heads-up display, consist of a bisphenol-type
epoxy resin and a radically polymerizable aliphatic
monomer. A diaryliodonium salt and 3-ketocoumarin
are used as a complex initiator. The formation of
the image is based on the radical polymerization
of the monomer initiated by a holographic expo-
sure, followed by the cationic polymerization of the
epoxy resin by UV exposure after post-exposure bak-
ing [367].
3.7.12.6 Nonlinear Optical Polymers
Second-order nonlinear optical (NLO) polymeric
materials are of interest because of their potential
applications in integrated optical devices, such as
waveguide electro-optic modulators, switches, and
optical frequency doubling devices. The interest in
these polymeric materials is mainly due to their large
optical nonlinearities, low dielectric constants, and
ease of production. For practical use, the poled poly-
mers must possess large second-order optical nonlin-
earities which should be sufficiently stable at ambient
temperature for a long period of time.
A high crosslinking density and stiffness make
interpenetrating networks attractive for such applica-
tions. The possibility of introduction of chromophores
that impart the nonlinear optical properties is
essential.
An example of an NLO active interpenetrat-
ing polymer network is an epoxy prepolymer and a
phenoxy-silicon polymer. 4,4 -Nitrophenylazoaniline
(Disperse Orange 3) functionalized with crosslink-
able acryloyl groups is incorporated into the
epoxy prepolymer. The epoxy prepolymer forms a
network through acryloyl groups which are reac-
tive at high temperatures without the aid of any
catalyst or initiator. The phenoxy-silicon poly-
mer is based on an alkoxysilane dye made of
3-glycidoxypropyltrimethoxysilane and Disperse
Orange 3, and 1,1,1-tris(4-hydroxyphenyl)-ethane,
3: EPOXY RESINS
as a multifunctional phenol. The two networks
are formed simultaneously and separately at
200 ◦ C [368].
Interpenetrating polymer networks based on
crosslinked poly(urethane)/epoxy-based polymer can
be obtained by simultaneously crosslinking phenol-
capped isocyanates with 2-hydroxypropyl acrylate
and curing epoxy prepolymers. To each of these
components phenylazo-benzothiazole chromophore
groups are linked. The crosslinked poly(urethane)
and the epoxy-based polymer show glass transition
temperatures of 140–178 ◦ C, respectively, whereas
the interpenetrating network shows two Tg values
at 142 and 170 ◦ C. Thin, transparent poled films of
the crosslinked polymers can be prepared by spin-
coating, followed by thermal curing and corona poling
at 160 ◦ C. The polymers exhibit long-term stability of
the dipole alignment at 120 ◦ C [369].
3.7.13 Reactive Solvents
Polymers can be processed more easily by using sol-
vents. The disadvantage is the necessary removal
of the solvent. This might be tedious and a time-
consuming step. Also, environmental hazards may
arise. Reactive solvents are those that polymerize after
the molding process. In this case, no removal is nec-
essary. Accordingly, intractable polymers can be pro-
cessed by the utilization of reactive solvents. The
polymers are dissolved in a liquid curable resin. Then
the homogeneous solution is transferred into a mold.
The curing of the reactive solvent takes place in the
mold.
In the course of curing, the molecular weight of the
resin increases. A phase separation and phase inver-
sion are likely to take place. The dissolved polymer
should become the continuous matrix, and the reac-
tive solvent is dispersed as particles in the matrix. So
the final properties of the system are dominated by the
properties of the thermoplastic phase.
The main advantage of this procedure is a lower
processing temperature because of decrease in vis-
cosity. There is no need to remove the solvent which
is bound to the polymer.
3.7.13.1 Poly(butylene terephthalate)
Although poly(butylene terephthalate) can be rela-
tively easily processed, a further improvement of the
processing is required when a difficult flow length or
mold geometry has to be mastered [370].
133
3.7.13.2 Poly(phenylene ether)
Poly(2,6-dimethyl-1,4-phenylene ether) can be dis-
solved at elevated temperatures in an epoxy resin and
the solution can be easily transferred into a mold or
into a fabric [371].
During the curing of epoxy resin, a phase separation
and a phase inversion occur. The originally dissolved
poly(phenylene ether) (PPE) then becomes the con-
tinuous phase. The dispersed epoxy particles become
an integral part of the system and act as fillers or as
toughening agents, depending on the type of epoxy
resin. An important parameter for the final physical
and mechanical properties is the size of the dispersed
particles.
The size of the dispersed phase is governed by
the competition between the coalescence of dis-
persed droplets, and the vitrification or gelation rate,
respectively, induced by the curing process. For the
coalescence, the viscosity of the system plays an
important role which is dependent on the curing
temperature. The viscosity can be further controlled
by adding another thermoplastic material such as
poly(styrene).
Blends of poly(phenylene ether) and an epoxy resin
cured with dicyandiamide materials show a two-phase
morphology. To improve the uniformity and miscibil-
ity, triallyl isocyanurate (TAIC) can be used as an in
situ compatibilizer [372]. Also, the fracture toughness
of the modified systems is improved by adding TAIC.
3.7.14 Encapsulated Systems
Photopolymerizable liquid encapsulants (PLE) for
microelectronic devices may offer important advan-
tages over traditional transfer molding compounds.
A PLE is comprised of an epoxy novolak-based
vinylester resin, fused silica filler, a photoinitiator, a
silane coupling agent, and optionally of a thermal ini-
tiator [373].
Boron trichloride amine was encapsulated in a thiol-
acrylate shell. Particle sizes from 10 to 150 µm were
obtained. The microparticles were used in a silica con-
taining bisphenol A diglycidyl ether epoxy resin in
order to improve the thixotropic properties [374].
3.7.15 Functionalized Polymers
The epoxy group can be used to functionalize various
polymers, to achieve certain desired properties.
134 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

3.7.15.1 Tougheners in e-EPDM reacts with the polyamide 6 to form a

Vinylester-urethane hybrid resins (VEUH) can be
toughened by functionalized polymers [375]. Suit-
able basic materials for toughening are nitrile rubber,
hyperbranched polyesters, and core/shell rubber parti-
cles. These materials can be functionalized with vinyl
groups, carboxyl groups, and epoxy groups.
Toughness is improved in VEUH when the func-
tional groups of the modifiers react with the secondary
hydroxyl groups of a bismethacryloxy vinylester
resin and with the isocyanate groups of the polyiso-
cyanate compound. Functionalized epoxy and vinyl
hyperbranched polymers are less efficient as tough-
ness modifiers in comparison to functionalized liq-
uid nitrile rubber. They show no adverse effect on the
mechanical properties.
3.7.16 Epoxy Resins as
Compatibilizers
Most polymers are not miscible with one another.
This lack of miscibility results in poor properties
of polymeric blends. However, the properties can
be improved by adding compatibilizers. Due to the
inherent reactivity of the epoxy group, an interfacial
chemical bonding can be achieved which results in
small particle sizes of the blend. This enhances the
properties of the blends. Some compatibilizers based
on epoxy compounds are shown in Table 3.16.
3.7.16.1 Polyamide Blends
Blends of polyamide 6 and epoxidized ethylene
propylene diene (e-EPDM) can improve the tough-
ness of polyamide 6. The particle size of e-EPDM
is much smaller than that of unepoxidized ethylene
propylene diene monomer (u-EPDM) rubber in a
polyamide 6 matrix. It is believed that the epoxy group
graft copolymer. Thus an interfacial compatibiliza-
tion takes place [376].
Styrene/glycidyl methacrylate (SG) copolymers
are miscible with syndiotactic poly(styrene) (s-PS).
In blends of PA6 with syndiotactic poly(styrene),
the epoxide units in the SG phase are capable of
reacting with the PA6 end groups. Copolymers of
styrene/glycidyl methacrylate are effective in reduc-
ing the s-PS domain size and improving the interfacial
adhesion. The best compatibilization is found with a
content of 5% GMA in the SG copolymer. Both the
strength and modulus of the blend are improved by
the addition of the SG copolymers. However, a loss in
toughness is observed at loadings of copolymer. The
addition of SG copolymer to the blend has little influ-
ence on the crystallization behavior of the polyamide
component. The crystallinity of s-PS is reduced [377].
Blends of nylon 6 with ABS copolymers and
with SAN can be prepared using glycidyl methacry-
late/methyl methacrylate (GMA/MMA) copolymers
as compatibilizing agents [378].
Known compatibilizers for blends of low den-
sity poly(ethylene) and PA6 are ethylene-co-
acrylic acid (EAA), maleic anhydride functionalized
polyethylenes, and an ethylene/glycidyl methacrylate
copolymer (EGMA). The effectiveness of EGMA as
a reactive compatibilizer is comparable to that of the
EAA copolymers. However, the effectiveness is lower
than that of poly(ethylene) functionalized with maleic
anhydride. A possible reason is the reaction of the pen-
dant epoxy groups with the amide groups that attach
the polyamide molecules together and hinder the dis-
persion in this way [379].
In blends of poly(propylene) and polyamide 6,
poly(ethylene) functionalized with maleic anhy-
dride showed better compatibilization than glycidyl
methacrylate. The compatibilizing effect of the

Table 3.16 Compatibilizers Based on Epoxy Compounds for Various Polymers

Polymer 1 Polymer 2 Compatibilizer

PA6 PS Styrene/glycidyl methacrylate copolymers
PA6 ABS Glycidyl methacrylate/methyl methacrylate copolymers (GMA/MMA)
PA6 PP Poly(ethylene) functionalized with maleic anhydride
PBT PPE Low-molecular-weight epoxy compounds
PBT SAN Terpolymers of methyl methacrylate, GMA, and ethyl acrylate

PA6, polyamide 6; PS, poly(styrene); PBT, poly(butylene terephthalate); ABS, acrylonitrile butadiene styrene (ABS), copoly-
mers; PP, poly(propylene); SPE, poly(phenylene ether); SAN, poly(styrene-co-acrylonitrile).
3: EPOXY RESINS
PP-MA for the PP/Ny6 blends was more effec-
tive than poly(propylene) functionalized with glycidyl
methacrylate [380].
Glycidyl methacrylate copolymers are miscible
with SAN. The epoxide unit can react with the
polyamide end groups. The compatibilizer can form
graft copolymers at the PA/SAN interface during melt
processing. Incorporation of the compatibilizer does
not significantly improve the impact properties of
PA/ABS blends.
The direct mixing of polyamide and
poly(propylene) leads to incompatible blends
with poor properties. Poly(propylene) functional-
ized with glycidyl methacrylate can be used as a
compatibilizer in the blends of PP and nylon 6 [381].
3.7.16.2 Poly(butylene terephthalate)
Poly(butylene terephthalate) (PBT) and PPE
can be compatibilized by low-molecular-weight
epoxy compounds [382]. Terpolymers of methyl
methacrylate, GMA, and ethyl acrylate are
effective reactive compatibilizers for blends
of PBT with SAN or ABS materials [383].
During melt processing, the carboxyl end groups of
PBT react with epoxide groups of GMA to form a
graft copolymer.
In blends of poly(butylene terephthalate) with an
E/EA, which show the general features of uncompat-
ibilized polymer blends, such as a lack of interfacial
adhesion and a relatively coarse unstabilized mor-
phology, no evidence of transesterification reaction
was found. In contrast, blends containing both virgin
and modified E/MA/GMA terpolymers show complex
behavior. Two competitive reactions take place during
the melt blending:
1. Compatibilization due to interfacial reactions
between PBT chain ends and terpolymer
epoxide groups, resulting in the formation of
E/MA/GMA/PBT graft copolymer, and
2. Rapid crosslinking of the rubber phase due to the
simultaneous presence of hydroxyl and epoxide
groups on E/MA/GMA chains.
The competition reactions between compatibiliza-
tion and crosslinking are dependent on the type of
terpolymer, since the modified E/MA/GMA contains
hydroxyl groups before mixing. The in situ compati-
bilization reaction of the pendant epoxy groups with
135
PBT causes the formation of E/MA/GMA hydroxyl
groups [384].
The concentration of carboxyl groups at the PBT
chain ends influences the rate of compatibilization
but not the final morphology. The lower the concentra-
tion, the slower the morphology development. Ternary
blends of PBT/(E-MA-GMA/E-MA) exhibit a very
fine morphology. Here the development of the mor-
phology is mildly influenced by the crosslinking rate
of the rubber phase caused by the shear rate in the
mixing chamber [385].
3.7.17 Surface Metallization
Established methods for the metallization of a poly-
mer surface are [386]:
1. electroless plating,
2. vacuum deposition or metal spraying, and
3. coating using a metallic paint.
A more recent method has been described that uti-
lizes the reduction of metal ions incorporated directly
in the polymer. It has been shown that cobalt or nickel
ions integrated in an epoxy network could be reduced
to the pure metal by dipping the film in an aqueous
NaBH4 solution [243].
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