Amidoamine: Synthesis, Disparity in Cure with Epoxy Resins
Between Bulk and Solvent Systems, and Structure–Property
Relationships of Its Epoxy-Based Coatings
Monoj Pramanik , Mark Early, Steven Wand, Diana Gottschalk, Sharathkumar K. Mendon,
James W. Rawlins
School of Polymers and High Performance Materials, The University of Southern Mississippi, Hattiesburg,
Mississippi 39406
Amidoamines are widely used as crosslinkers for epoxy
resins in protective coatings on metal substrates; how-
ever, their cure chemistry is not well elaborated in the
technical literature. During cure, the epoxy–amine and
epoxy–amide NH reactions could be accompanied by
epoxy–hydroxyl etherification, epoxy–epoxy homopolyme-
rization, and reaction between hydroxyls and amide moi-
ety to form in situ ester and amine. To understand the
epoxy–amidoamine cure chemistry and correlate it with
coating performance properties, amidoamines of known
structure are required. Therefore, amidoamines were syn-
thesized by reacting dimer fatty acids with diethylene tria-
mine. When these amidoamines were cured with epoxy
resins, discrepancies were observed between systems
cured at ambient and thermal conditions. The presence of
solvents were seen to greatly affect the rate of epoxy–
amidoamine cure at ambient, and before and after vitrifi-
cation. Near-IR and mid-IR spectroscopy studies indi-
cated that side reactions occurred to some extent during
cure. No reaction was noted between the amide NH moi-
ety and the epoxide group below 1508C whereas ester for-
mation was noted above 1208C. Solvent-based clear
epoxy–amidoamine coatings formulated at an epoxy:-
amine equivalent ratio 1.15 passed basic organic coatings
evaluation tests. POLYM. ENG. SCI., 00:000–000, 2018. V
C 2018
Society of Plastics Engineers
INTRODUCTION
Epoxy prepolymers are widely used in coatings and adhe-
sives because of their ease of processing, low shrinkage upon
curing, good thermal and mechanical stability, high resistance to
solvents, and promising anticorrosive properties [1–6]. Amine
curatives and reactive amidoamines are popular building blocks
for matrices in two component epoxy coatings [3, 7–15]. Such
amidoamines are synthesized by reacting fatty acids with amines
[16–19]. Coatings based on epoxy resins cured with dimer fatty
acid-based amidoamines offer the advantages of low cost, excel-
lent flexibility, and high hydrophobicity. Since the properties of
epoxy–amidoamine coatings depend on the extent of cure, it
Correspondence to: J. W. Rawlins; e-mail: james.rawlins@usm.edu
Additional Supporting Information may be found in the online version of
this article.
Contract grant sponsor: The United States Air Force through funding by the
Department of Defense (DoD); contract grant number: FA7000-13-2-0022
and FA7000-14-2-0011.
DOI 10.1002/pen.24858
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2018 Society of Plastics Engineers
V hydroxyl etherification and epoxy–epoxy homopolymerization
POLYMER ENGINEERING AND SCIENCE—2018
was necessary to study its cure kinetics to establish structure–
property relationships.
It is well established that amine moieties (-NH and -NH2) in
amidoamines react with epoxy moieties at ambient and elevated
temperatures. However, the reaction between NH of -
(C 5 O)NH moieties and epoxy groups at ambient or elevated
temperatures has hardly been studied. Cure kinetic study of
epoxy–amidoamine systems via differential scanning calorimetry
(DSC) only dispenses the overall extent of reaction without dif-
ferentiating between the individual component reactions [18,
20–27]. The evaluation of epoxy–amidoamine reactions via mid-
IR (600–4,000 cm21) spectroscopy [20, 28] has been compro-
mised by the fact that epoxy resins and amidoamines exhibit
overlapping bands in the mid-IR region. Prime and Sacher [20]
reported that the cure of epoxy–amidoamine blends were charac-
terized by the reaction between amine and epoxy moieties at
ambient temperature, and the formation of ester and amine moi-
eties via amide-alcohol reactions at elevated temperatures.
Zhong and Guo [28] studied cure kinetics of epoxy and nylon
blends via DSC and mid-IR spectroscopy, and reported that the
reaction between epoxy groups and the amide moiety of nylon,
and ester formation via amide-hydroxyl reaction occurred above
2008C. The extent of side reactions is important as it alters the
curing agent functionality and induces variations in crosslink
density as a function of the thermal cure profile.
When amidoamines react with epoxy resins in bulk at ambi-
ent conditions, progressive cure results in system solidification,
ultimately resulting in vitrification, that is, the progressive loss
of functional groups slows down the molecular motion and the
rate of crosslinking is typically reduced by three to four orders
of magnitude (cure is almost halted). In solvent-based epoxy–
amidoamine blends, the solvents usually impart enough mobility
for virtually all the groups to react before complete solvent
evaporation (i.e., elongated open times without vitrification),
and almost complete epoxy conversion is noted at ambient
conditions.
Epoxy–amine blend cure involves four reactions: epoxy–pri-
mary amine, epoxy–secondary amine, epoxy–hydroxyl etherifi-
cation, and epoxy–epoxy homopolymerization, that are governed
by their energy barriers of 55–60, 71, 104, and 170 kJ/
mol, respectively (some variation in energy barriers is likely
depending on the physical state and chemical structures of
monomers) [29, 30]. Noting that near-IR (4,000–8,000 cm21)
spectra of epoxy–amine systems are characterized by distinct
bands for epoxide, primary amine, phenyl, and combined pri-
mary–secondary amine and hydroxyl groups, we monitored the
cure kinetics of epoxy–amine blends and showed that epoxy–
 FIG. 1. (A) Basic structure of chemicals used, (B) sketch for synthesis of amidoamine-I, and (C) sketch for synthe-
sis of amidoamine-II.
occur under specific cure conditions [31]. In epoxy–amidoamine
blends, epoxy–amide NH reactions are also likely to occur.
In this study, it was essential to discern between the individ-
ual epoxy–amidoamine chemical reactions in bulk and in sol-
vent, and to correlate the extent of cure and structure–property
relationships while assessing the solvent effect on reactions and
reaction rates. To understand the epoxy–amidoamine cure chem-
istry and correlate it with coating performance properties, ami-
doamines of known structure and ability to form standard
organic coatings are required. Dimer fatty acid-based amido-
amines were synthesized with the intent to study: (i) reactivity
of the amine (-NH2 and -NH) and amide -NH moieties of the
amidoamine with epoxy groups at ambient and at elevated tem-
peratures, (2) the effect of solvent on epoxy–amidoamine cure,
(3) occurrence of reactions other than epoxy–amine and epoxy–
amide NH reactions during cure, (4) chances of in situ forma-
tion of ester and amine due to non-curative reactions between
amide and hydroxyl moieties, and (5) properties of epoxy–ami-
doamine cured coatings to establish structure–property relation-
ships. Cure of epoxy resins with amidoamine was studied in
bulk and in solvent, at ambient and elevated temperatures. As a
control, the cure kinetics of the reaction between the epoxy resin
and N-methyl acetamide was studied to verify the occurrence of
epoxy–amide reaction at selected temperatures. Solvent-based
clear coatings were formulated using the epoxy resin and amido-
amine, and evaluated for their performance properties. The
effect of partly pre-reacting the amidoamine moiety was also
evaluated in coatings.
EXPERIMENTAL
Materials
Unidyme 14, a liquid dimer fatty acid (reported acid value
194.70 mg KOH/g) was donated by Arizona Chemicals. From
the acid value, the equivalent weight of the dimer fatty acid was
calculated to be 288.14 g/equiv. Diethylene triamine (DETA,
98% pure) and 1,3-bis(aminomethyl)cyclohexane (BAC, 98%
pure) were purchased from Acros Organics and TCI America,
respectively. Deuterated chloroform (CDCl3, 99.8% pure) was
2 POLYMER ENGINEERING AND SCIENCE—2018
procured from Acros Organics. Diglycidyl ether bisphenol-A
(DGEBA)-based liquid epoxy prepolymer, Epon 828 [reported
epoxy equivalent weight (EEW) 185–192 g/equiv.] was donated
by Hexion (Momentive). Epoxy terminated polysulfide based
liquid epoxy prepolymer, Thioplast EPS 70 (reported EEW
310 g/equiv.) was supplied by Akzo Nobel. Benzyl alcohol
(BzOH) and 1-methoxy-2-propanol (PGME) were purchased
from Fisher Scientific. Figure 1A shows the basic chemical
structures of dimer fatty acid, DETA, BAC, and epoxy prepoly-
mers. All the chemicals were used as received unless mentioned
otherwise.
Amidoamine Synthesis
DETA (476.76 g) was weighed into a 2 L, four-neck round
bottom flask set up with a water condenser, thermocouple,
mechanical stirrer with Teflon blade, Dean Stark water trap, and
nitrogen in overhead space. The flask was heated to 508C under
stirring. Dimer fatty acid (1,250.24 g) was added dropwise into
the flask while heating the flask to 808C (to reduce viscosity
and maintain flow). The reaction temperature was raised gradu-
ally to 1008C (0.5 h), 1258C (0.5 h), 1508C (1 h), and 1808C
(4 h). Based on its equivalent weight and assuming the presence
of only dimers, the molar mass of dimer fatty acid was calcu-
lated to be 576.27 g. Amidoamines-I and -II were synthesized
by reacting DETA and BAC, respectively, with the dimer fatty
acid at an amine:acid molar ratio of 2.13. Figure 1B and C
shows the amidoamine synthesis scheme with structures of the
expected trimers of amidoamines-I and -II, though higher
molecular weight products may also be formed. Amidoamine-II
was synthesized to verify the reproducibility of the adopted syn-
thetic method.
Preparation of Coatings and Free Films
All coating formulations were based upon amidoamine-I with
an epoxy:amine ratio of 1.15:1. Coating C1 was prepared by
mixing 33.96 g (0.1799 equiv.) Epon 828, 18.0 g (0.1565
equiv.) amidoamine-I, and 22.27 g solvent blend (1:1 by weight
of BzOH and PGME) in a 100 g FlackTek cup. The cup
DOI 10.1002/pen
 TABLE 1. Composition of near-IR samples.
Amount (g) of
Near-IR sample Epon 828
1.0-bulk 6.00
1.0%–70% solid 6.00
1.15-bulk 6.00
1.15%–70% solid 6.00
contents were mixed at 1800 rpm for 4 min in a centrifugal
speed mixer (FlackTek, Inc.). Coating C2 was prepared by pre-
reacting amidoamine-I with 10 equiv.% Epon 828 overnight at
ambient in the same solvent blend as used in C1, before adding
the remaining Epon 828 (to maintain the 1.15:1 epoxy:amine
ratio). The coatings were applied on two different steel panel
types (S36 and QD), Leneta chart, and polypropylene sheets.
The coatings were cured at ambient for 16 h and at 808C for
4 h. The coated steel panels (S36) were characterized by wet
and dry crosshatch adhesion (ASTM D 3359), and solvent resis-
tance via methyl ethyl ketone (MEK) double rubs (ASTM
D5402). Pull-off stress, mandrel flexibility, and impact resis-
tance tests were conducted on coated QD panels. Gloss meas-
urements were taken on the coated Leneta chart. Coatings from
the polypropylene sheet were peeled off and analyzed for resid-
ual solvent via thermogravimetric analysis (TGA) and dynamic
mechanical properties (storage modulus and glass transition tem-
perature, Tg).
Characterization
Fourier Transform Infrared Spectroscopy. Fourier transform
infrared (FTIR) spectroscopy was conducted using a Nicolet
6700 FTIR spectrometer over a frequency range of 650–
4,000 cm21. Liquid samples were smeared on to NaCl disks to
obtain their mid-IR spectra while attenuated total reflectance
spectroscopy was employed to acquire mid-IR spectra of partial/
fully cured solid films.
Nuclear Magnetic Resonance Spectroscopy. Carbon nuclear
magnetic resonance (NMR) spectra were obtained from 30 wt%
solutions in CDCl3 using a Varian mercury NMR spectrometer
operating at a frequency of 75.5 MHz. All chemical shifts (indi-
cated as d ppm) were referenced either automatically by the
software (VNMR 6.1C) or manually using the resonance fre-
quency of CDCl3.
Equivalent Weight Determination. Prior to use, the EEW of
Epon 828 and EPS 70 were determined via ASTM D1652. For
this, the epoxy sample was solubilized in methylene chloride.
Tetraethyl ammonium bromide solution in acetic acid was added
to the epoxy solution before titrating against perchloric acid
solution in acetic acid using crystal violet indicator (end point
marked by color change from blue to green). EEW values of
Epon 828 and EPS 70 were determined to be 188.75 and
325.39 g/equiv, respectively.
The amine value (total, secondary, and tertiary amines) of
the synthesized amidoamines was determined following ASTM
D 2074 using bromophenol blue indicator (end point marked by
color change from blue to bright yellow). Total amine value
DOI 10.1002/pen
Amount (g) of Amount (g) of solvent
amidoamine-I (1:1 blend of BzOH and PGME)
3.66 0.00
3.66 4.14
3.18 0.00
3.18 3.93
was determined from the isopropanol solution of amidoamine.
Chloroform solution of amidoamine was agitated at ambient
with salicylaldehyde and titrated with hydrochloric acid to esti-
mate secondary amine and tertiary amine content. A chloroform
solution of amidoamine was treated with phenyl isothiocyanate
and titrated with hydrochloric acid to determine the tertiary
amine content. Subtracting the amine value of the third titration
from the amine value obtained from the second titration yielded
the secondary amine value. Primary amine value was calculated
by subtracting the secondary and tertiary amine values from the
total amine value. Amine hydrogen equivalent weight (AHEW)
of amidoamines was calculated using primary and secondary
amine value. N-methyl acetamide was employed as a control
amide and titrated against 0.05 N hydrochloric acid to determine
its amine values. Its zero amine value validated the absence of
interference from the amide nitrogen during titration with hydro-
chloric acid. AHEW values of amidoamines-I and -II were
determined to be 115 and 188 g/equiv respectively.
Near Infrared Spectroscopy. Near-infrared (near-IR) spectra
were obtained using an Antaris II, FT-NIR analyzer (Thermo
Scientific).
A drop of the sample (DETA, BAC, dimer fatty acid, N-
methyl acetamide, or amidoamine) was placed on a microscope
glass slide and its spectrum was recorded in the near-IR region
of 4,000–8,000 cm21 (32 scans, resolution 4 cm21) via the inte-
grating sphere in combination with the OMNIC version
8 software.
The epoxy–amidoamine reaction in bulk and in solution was
monitored on the same near-IR equipment. A known amount (as
shown in Table 1) of liquid epoxy prepolymer and amidoamine-
I (in bulk and in solution) were mixed at 1,800 rpm in a centrif-
ugal Speed Mixer (FlackTek, Inc.), and placed on a single side
depressed glass slide to conduct cure kinetics via near-IR using
Results Operation software. The collected spectra were proc-
essed for baseline correction and normalization against the inter-
nal standard near-IR peak.
Differential Scanning Calorimetry. DSC analysis was con-
ducted on a DSC Q 2000 (TA Instruments) and the data were
processed via Universal Analysis 2000 software to determine
the cure and activation energy of the epoxy–amidoamine reac-
tion. 6.00 g Epon 828 and 3.66 g amidoamine-I were mixed at
1,800 rpm in the centrifugal Speed Mixer, and about 15 mg
sample was employed for the analysis at heating rates of 2.5, 5,
7.5, and 108C/min under nitrogen. 6.00 g EPS 70 and 2.12 g
amidoamine-I were also mixed and analyzed similarly via DSC
to determine the reactivity amidoamine-I with the sulfide-based
epoxy resin.
POLYMER ENGINEERING AND SCIENCE—2018 3
 FIG. 2. 13C NMR spectra of BAC, DETA, dimer fatty acid, N-methyl acetamide, amidoamines-I, and -II. [Color
figure can be viewed at wileyonlinelibrary.com]
Dynamic Mechanical Analysis. Dynamic mechanical analysis
(DMA) was performed on a DMA Q800 (TA Instruments, Inc.).
Free films (0.08-mm thick, 5-mm wide) were analyzed at a fre-
quency of 1.0 Hz using a heating rate of 28C/min with the set
of strain control in tension mode. The DMA dataset for each
sample represents the average of three specimens. Storage (E’)
and loss moduli (E’’) as well as tan d were monitored for each
sample. The tan d maxima were characterized as the mechanical
Tg of the sample. The molecular weight between crosslinks (Mc)
was determined from the storage modulus in the rubbery plateau
region. Storage modulus (E’) is inversely proportional to the
chain length between entanglement molecular weight (Mc) as:
3qrRT
Mc 5
E0Tg150
where q is a front factor usually taken as 1.0 and followed for
our calculations, r is density (g/cm3) acquired using thermome-
chanical analysis (TMA) at Tg1508C, R is universal gas constant
[8.314 J/(mol K)] and E’Tg150 is the storage modulus (MPa) at
Tg1508C.
Adhesion Test. Coatings on steel panels (S 36) were character-
ized by wet and dry crosshatch adhesion on a scale of 0B–5B as
per ASTM D3359. Six parallel cross cuts were made on a
coated panel using a sharp knife. Adhesion test tape was taped
over the cross cut area and peeled off sharply. For wet adhesion
test, the cross cut area was moistened with a paper towel wet
with deionized (DI) water for 10 min prior to taping it. Support-
ing Information Fig. S1 clarifies the 0B–5B scale for adhesion.
Pull-off stress tests were performed using a MTS Insight
instrument equipped with a load cell of 2.5 kN following
ASTM D4541-02. The test was conducted at a crosshead speed
of 0.5 mm/min. Each dataset represents the average of nine
specimens for each sample. The adaptors for the load frame
used in pull-off testing were customized to hold a coated panel
on the bottom with an Elcometer 20 mm stud on the top. Prior
4 POLYMER ENGINEERING AND SCIENCE—2018
to application, studs were prepared by abrading the surface first
with 60 grit sand paper and then with Scotch Brite pads. Before
adhering the studs to the panel, the coating was also abraded
with Scotch Brite. Studs were adhered to the coating surface
with Scotch Weld D460 and applied by hand. The adhesive was
cured for 24 h prior to testing. Supporting Information Fig. S2A
shows the specimen and arrangement for pull-off adhesion test.
Solvent Resistance Test. Solvent resistance of coatings applied
to S36 panels was evaluated following ASTM D 5402 using
MEK as the solvent. Protective organic coatings are expected to
pass 200 MEK double rubs without any detectable visual dam-
age. A MEK double rub test set up is shown in Supporting
Information Fig. S2B.
(1)
Mandrel Bend Flexibility Test. Resistance to cracking or flexi-
bility of cured epoxy–amidoamine coatings on S36 panels was
tested following ASTM D 522. The mandrel bend flexibility test
setup is shown in Supporting Information Fig. S2C.
Impact Resistance Test. Impact resistance of coatings on QD
panels was tested following ASTM D 2794.
Gloss Measurement. Coating specular gloss at 208, 608, and
858 was measured on coated Leneta charts using a BYK gloss
meter following ASTM D 523.
Water Sorption Measurement of Free Films. Free films of
coatings C1 and C2 were used to measure water sorption prop-
erties. Using a circular hollow punch, samples (13-mm diame-
ter) were cut from the films and weighed. The samples were
submerged in scintillation vials filled with DI water and held at
ambient. Over the course of two weeks, the disks were removed
periodically; patted dry with paper towels, and its mass was
recorded before being placed back in the vial. The test was con-
ducted in triplicate. The change in mass due to swelling was
calculated from the Equation as:
DOI 10.1002/pen

FIG. 3. (A) Mid-IR, and (B) near-IR spectra of BAC, DETA, dimer fatty
acid, N-methyl acetamide, amidoamines-I and -II. [Color figure can be
viewed at wileyonlinelibrary.com]
ðmt 2md Þ
Water Sorption ð%Þ5 3100 (2)
md
where mt is the mass of the free film sample at time t and md is
the mass of the dry sample.
RESULTS AND DISCUSSION
Amidoamines-I and -II Synthesis
Figure 2 shows the 13C NMR spectra of DETA, BAC, dimer
fatty acid, amidoamines-I, -II, and N-methyl acetamide. The 13C
NMR spectrum of dimer fatty acid shows peaks at d 180, 34,
31.89–22.65, and 14.06 ppm due to the existence of -COOH, -
CH2-COOH, -CH2- in chain, and terminal -CH3, respectively
(basic structure displayed in Fig. 1A). Carbon peaks at d 41 and
51.79 ppm were observed in the DETA spectrum consisting of -
CH2-NH2, and -CH2-NH-CH2-, respectively. The disappearance
of the carboxylic carbon peak from the dimer fatty acid and the
appearance of two new carbon peaks at d 173 and 167 ppm in
the spectrum of amidoamine-I were attributed to the secondary
amide carbonyl (-CO-NH-) and tertiary amide carbonyl (-CO-
N(CH2)2-), respectively (basic structure shown in Fig. 1B). This,
in turn, confirmed the amide formation from dimer fatty acid
and DETA. Shifting of the peak at d 34 (-CH2-COOH) to d 36
ppm (-CH2-CO-NH-) also supported amide formation. The reac-
tion between fatty acid and BAC was conducted using the same
procedure to test the reproducibility of the synthetic method.
Carbon NMR spectrum of BAC exhibited 10 carbon peaks even
though only 5 peaks were expected, and were attributed to its
cis and trans isomers. Peaks at d 47.75 and 45.15 ppm are
attributed to carbons attached to NH2 (-CH2-NH2). Similar to
amidoamine-I, the 13C NMR spectrum of amidoamine-II exhib-
ited a peak at d 172.89 ppm (-CO-NH-) along with the loss of
the d 180 ppm (-COOH) peak. Amidoamine-II also showed a
peak at d 36.12 from the carbon attached to the amide carbonyl
(-CH2-CO-NH-) due to peak shifting from d 34 (-CH2-COOH).
Amidoamine-I showed two carbonyl peaks (d 173, 167 ppm) as
it consists of secondary amide and tertiary amide whereas
DOI 10.1002/pen
amidoamine-II exhibited only one carbonyl peak (at d 172.89
ppm) from its secondary amide. 13C NMR spectrum of the con-
trol amide, N-methyl acetamide, is shown in Fig. 2. Overall,
these results indicated the reproducibility of the amidoamine
synthesis.
Figure 3A displays the mid-IR spectra of BAC, DETA, dimer
fatty acid, N-methyl acetamide, amidoamines-I, and -II. The
dimer fatty acid showed mid-IR bands at 2,924, 2,854, 1,707,
1,461, 1,238, 939, and 723 due to C-H asymmetric stretching,
C-H symmetric stretching, C 5 O stretching of -COOH, CH2
bending (in-plane), CH2 bending (out-of-plane), O-H deforma-
tion (out-of-plane) of COOH, and CH2 bending (out-of-plane),
respectively [32]. In addition, a broad mid-IR band 3,400–
2,500 cm21 is attributed to the existence of O-H stretching of -
COOH. DETA and BAC exhibited mid-IR bands at 3,600–
3,200, 2,985–2,775, 1,600, 1465 due to NH2 stretching, C-H
stretching, NH2 bending, and CH2 bending, respectively. The
mid-IR spectrum of amidoamines-I and -II showed the disap-
pearance of the dimer carboxylic acid C 5 O stretching
(1,707 cm21) and appearance of a new peak at 1,643 cm21
(amide C 5 O stretching), which indicated amide formation.
Since amidoamines-I and -II comprise of secondary amide (-
CO-NH-) and -NH2 or NH moieties, mid-IR bands correspond-
ing to amide N–H stretching and N-H bending, amine NH
stretching and bending were expected. Amide N-H stretching
and amine N-H stretching in amidoamines overlapped in the
wavenumber region 3,100–3,600 cm21 (Fig. 3A). Amide N-H
bending and amine N-H bending in amidoamines also appeared
to overlap with each other (Fig. 3A).
Near-IR spectroscopy was conducted to observe the coexis-
tence of amide NH and amine NH. Near-IR spectra of DETA,
BAC, dimer fatty acid, amidoamines-I, -II, and N-methyl acet-
amide are shown in Fig. 3B. The secondary amide moiety in
amidoamines-I and -II is similar to the secondary amide moiety
of N-methyl acetamide. The near-IR spectrum of N-methyl acet-
amide shows a near-IR band at 4,903 cm21 that is attributed
to combination of C 5 O stretching and NH stretching (
1,646 1 3,287 cm21), and combination of NH stretching and
NH bending ( 3,287 1 1,553 cm21) of the (-CO-NH-) group.
The first overtone of amide NH stretching of N-methyl acet-
amide is therefore expected to be seen at 6,575 cm21. A very
weak and baseline noise level peak was observed at
6,570 cm21 in the near-IR spectrum of N-methylacetamide
due to first overtone of amide NH stretching. In the near-IR
spectra of DETA and BAC, bands were noted at 4,933 and
6,500 cm21 due to combination of NH2 stretching and bend-
ing, and first overtone of NH2 stretching, respectively [31]. The
near-IR spectra of both amidoamines-I and -II exhibited a peak
at 4,933 cm21, which is attributed to a combination of amine
NH stretching and bending, and combination of amide NH
stretching and bending. Thus, the peak at 4,933 cm21 in the
near-IR spectra of amidoamines cannot be used to establish the
presence of amine with amide. An intense peak was also noticed
at 6,500 cm21 in the near-IR spectra of amidoamines-I and -
II, which established the presence of an amine moiety.
The presence of amine moiety in amidoamine was further
confirmed by amine titration using 0.05 N hydrochloric acid sol-
utions in isopropanol. Titration of amidoamines-I and -II with
hydrochloric acid solution only protonates amine nitrogens as
similar titration with N-methyl acetamide resulted in zero amine
POLYMER ENGINEERING AND SCIENCE—2018 5

FIG. 4. Possible reactions that may occur during cure of epoxy resin with
amidoamine.
value. Titration indicated AHEW values of 115.05 and 187.99 g/
equiv of amidoamines-I and -II, respectively. Amidoamine-I was
further used to study epoxy–amidoamine cure kinetics and to for-
mulate epoxy–amidoamine clear coatings.
Reactivity of Amidoamine-I with Liquid Epoxy Resin
Figure 4 summarizes possible reactions most likely to occur
during cure of epoxy resins with amidoamines at ambient and
FIG. 5. DSC curves of curing of (A) stoichiometric mixture of Epon 828 and amidoamine-I, and (B) stoichiometric
mixture of EPS 70 and amidoamine-I, (C) Kissinger plot, and (D) Ozawa plot.
6 POLYMER ENGINEERING AND SCIENCE—2018
elevated temperatures. It is well established that primary amine
moieties in liquid amidoamines react with epoxide moieties in
liquid epoxy resins at ambient condition (first reaction in Fig.
4). Secondary amine moieties formed in situ and or pre-existing
in amidoamine also react with epoxy in liquid state at ambient
(second reaction in Fig. 4). The third and fourth reactions shown
in Fig. 4 are usually not prominent in stoichiometrically formu-
lated bulk epoxy–amidoamine systems. These two reactions
(third and fourth) may occur if: (1) the epoxy–amine blend con-
tains excess epoxy, (2) the in situ formed or externally added
tertiary amine moiety exerts a strong catalytic effect, (3) sol-
vents are present, and/or (4) cure occurs at elevated tempera-
tures [31]. The fifth reaction shown in Fig. 4 (amide NH with
epoxide) expectedly requires elevated temperatures to occur as
the amide nitrogen is rendered poorly nucleophilic by its prox-
imity to the carbonyl moiety. Amide NH has been reported to
react with epoxide above 2008C in an epoxy–nylon blend [28].
In coating formulations, an excess of epoxy is usually main-
tained to avoid the presence of unreacted amines after applica-
tion and cure. In addition, solvents used in coatings usually
contain functionalities such as hydroxyl, carbonyl, hydroxyl-
ether, and/or esters. It is clear that at least two of the above
mentioned features (i.e., excess epoxy and solvent) exist in
solvent-based epoxy–amine coating formulations that can pro-
mote the occurrence of Reactions 3 and 4.
Amidoamine-I was blended individually with Epon 828 and
EPS 70 at stoichiometric proportion in bulk and evaluated via
DSC (Fig. 5A and B). Initial temperature (Ti) or onset tempera-
ture of reaction exotherm was observed to be 228C at a heat-
ing rate of 2.58C/min, indicating that amidoamine is reactive at
ambient condition with both the liquid epoxy prepolymers.
DOI 10.1002/pen
 FIG. 6. Near-IR spectra of Epon 828 and amidoamine-I blend during cure at ambient/16 h 1 808C/ 2 h 1 1208C/1
h 1 1608C/2 h 1 2008C/2 h in bulk at (A) stoichiometric and (B) 1.15 epoxy: amine ratio systems, and near-IR spec-
tra during cure at ambient/16 h 1 808C/2–4 h of blend of Epon 828 and amidoamine-I at 70% solids (50:50 PGME
and BzOH) (C) stoichiometric and (D) 1.15 epoxy:amine ratio. [Color figure can be viewed at wileyonlinelibrary.
com]

Increasing the heating rate to 108C/min shifted the Ti and peak 249 6 7.09 and 213 6 9.94 J/g, respectively. A stoichiometric
temperature (Tp) to higher values as expected and reported in blend of Epon 828 and amidoamine-I comprises of 6.58 milie-
literature [33, 34]. The exothermic heat of reaction (DH) of quiv reactive moieties per gram, while the EPS 70–amidoamine-
Epon 828 and EPS 70 with amidoamine-I was determined to be I stoichiometric blend contains 4.54 miliequiv of reactive

FIG. 7. (A) DSC curves when heated (2.58C/min in N2 atmosphere) to 1508C, (B) near-IR spectra during cure at
ambient/15 h 1 808C/6 h 1 1208C/1 h of stoichiometric blend of Epon 828 and N-methyl acetamide. [Color figure
can be viewed at wileyonlinelibrary.com]

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2018 7

 FIG. 8. Mid-IR spectra of Epon 828 and amidoamine-I blend in bulk during cure at ambient/16 h, 1 808C/
1 h, 1 808C/ 2 h, 1 1208C/1 h, 1 1608C/1 h, 1 1608C/2 h, 1 2008C/1 h 1 2008C/2 h (A) stoichiometric and (B) 1.15
epoxy amine ratio, and mid-IR spectra of clear coating C1 (A) and C2 (B) when heated at 808C/4 h, 11208C/
1 h, 1 1608C/1 h, 1 1608C/2 h, 1 2008C/1 h 1 2008C/2 h. [Color figure can be viewed at wileyonlinelibrary.com]
moieties per gram. The difference in DH values shows the dilu-
tion effect on the EPS 70–amidoamine-I blend system relative
to the Epon 828–amidoamine-I system. Activation energy for
Epon 828 and amidoamine-I, and EPS and amidoamine-I sys-
tems were determined using Kissinger and Ozawa models
(shown in Supporting Information) [34]. Kissinger and Ozawa
plots (Fig. 5C and D) indicated activation energies of  58 and
 53 kJ/mol for Epon 828 and amidoamine-I, and EPS 70 and
amidoamine-I systems, respectively. By comparison, 2-
methylpentanediamine, a liquid aliphatic amine crosslinker that
is reactive with epoxy prepolymers at ambient conditions, has
an activation energy of  56 kJ/mol as determined in our labo-
ratory by the same method [31]. This indicates that the activa-
tion energy of amidoamine-I with liquid epoxy prepolymers is
consistent with that of reactive liquid amines and epoxy
prepolymers.
Near-IR Spectra during Cure of Liquid Epoxy Resin with
Amidoamine-I
Cure of Epon 828 and amidoamine-I in bulk at stoichiomet-
ric proportion and 1.15:1 epoxy amine ratio at ambient as well
as at elevated temperatures was monitored via near-IR spectros-
copy (Fig. 6A and B). The epoxy band at 4,530 cm21, phenyl
band at 4,622 cm21, primary amine band at 4,933 cm21, and
combined band of primary and secondary amine at 6,500 cm21
are of specific interest and are highlighted in the figure. Each
acquired spectrum was normalized against an internal standard
peak (phenyl band) at 4,622 cm21. As expected, the intensities
of the epoxy band at 4,530 cm21, primary amine band at
4,933 cm21, and combined band of primary and secondary
amine at 6,500 cm21 were observed to decrease consistently
with time as a result of reaction between epoxy and amine func-
tional groups, regardless of stoichiometry. The epoxy peak
(4,530 cm21) in the stoichiometric blend (Fig. 6A) disappeared
completely after 16 h at ambient 1 808C for 2 h 1 1208C for 2
h 1 1608C for 2 h 1 2008C for 2 h, indicating complete reaction
8 POLYMER ENGINEERING AND SCIENCE—2018
of epoxy functional groups. On the other hand, the secondary
amine peak (6,500 cm21 in Fig. 6A) did not disappear
completely, indicating the presence of residual amine content
even after all the epoxy groups had reacted. When the epoxy:-
amine ratio was increased to 1.15, the residual secondary amine
peak (Fig. 6B) was still evident despite the complete consump-
tion of epoxy moieties. This indicates that side reactions (third
and fourth reactions shown in Fig. 4) occurred during cure at
elevated temperatures in both the stoichiometric and 1.15 epoxy
amine ratio systems. To verify occurrence of epoxy–hydroxyl
reaction, a triethanolamine–Epon 828 blend was evaluated via
non-isothermal DSC and near-IR (Supporting Information Fig.
S3). Both these techniques confirmed the occurrence of epoxy–
hydroxyl reaction.
If Reactions 3–5 (Fig. 4) occur singularly or together during
cure of epoxy amidoamine systems, then it could explain the
presence of detectable amounts of residual secondary amine.
Zhong and Guo [28] reported that amide NH reacts with epox-
ide above 2008C in an epoxy–nylon blend. One could therefore
expect that both the stoichiometric and 1.15 epoxy:amine ratio
systems did not involve Reaction 5 (Fig. 4) during cure up to
2008C in bulk. To further verify whether the amide NH reacts
with epoxide, the N-methyl acetamide and Epon 828 stoichio-
metric blend in bulk were evaluated via DSC and near-IR (Fig.
7). The lack of any exotherm in the non-isothermal DSC curve
(Fig. 7A) validates that the amide NH of amidoamine-I does not
react with epoxide at  1508C. Near-IR spectra (Fig. 7B) during
cure at ambient for 15 h 1 808C/6 h 1 1208C/1 h also exhibited
unchanged epoxide and amide NH peak intensity, again indicat-
ing that the amide NH remained unreactive with the epoxide up
to 1208C.
Apart from first five reactions (first to fifth), sixth ones may
occur during cure of epoxy and amidoamine blend at elevated
temperature (Fig. 4). This reaction between hydroxyl groups and
amide moieties to form in situ ester and amine has been
reported to occur in an epoxy–nylon blend heated above 2008C
[28]. For this, mid-IR spectra were collected at the end of each
DOI 10.1002/pen
 FIG. 9. Epoxy conversions of Epon 828 and amidoamine-I blends in bulk and 70% solids, stoichiometric (1.0) and
1.15 epoxy–amine ratio during cure at ambient and elevated temperatures. 1.0 and 1.15 blends in bulk cured at ambi-
ent/16 h 1 808C/2 h 1 1208C/1 h 1 1608C/2h 1 2008C/2 h. 1.0 and 1.15 blends in 70% solids (50:50 PGME and
BzOH) cured at ambient/16 h 1 808C/2–4 h.
step of temperature rise during cure of Epon 828 and
amidoamine-I systems (both stoichiometric and 1.15 epoxy:-
amine ratio blends) in bulk (Fig. 8A and B). At 2008C, a promi-
nent mid-IR band (low intensity) was observed at 1,729 cm21
in both the systems, indicating ester formation. Further evalua-
tion of the spectra in the region of 1,675–1,825 cm21 indicated
that the ester peak started growing at 1608C. Therefore, the
occurrence of Reactions 3–5, and in situ occurrence of Reaction
6 (Fig. 4) during cure at elevated temperature of Epon 828 and
amidoamine-I blend in bulk are the likely cause of secondary
amine retention despite complete conversion of epoxy groups.
To discern cure characteristics of solvent-based epoxy amido-
amine systems, Epon 828–amidoamine-I blends (stoichiometric
and 1.15:1 epoxy:amine) in BzOH and PGME (50:50) solvent
mixture at 70% solids were monitored at ambient and 808C. The
near-IR spectra of this system are displayed in Fig. 6C and D. As
was noted in bulk, the intensities of the epoxy peak, primary
amine peak and combined band of primary and secondary amine
peak decreased consistently over time via reaction between epoxy
and amine groups during cure at ambient and post-cure at 808C.
Complete reaction of both epoxy and amine moieties was noted
in the 1.15:1 epoxy:amine ratio blend after ambient cure for 16
h 1 808C/1 h (Fig. 6D). The stoichiometric blend exhibited com-
plete reaction of epoxy groups after 16 h at ambient 1 808C/1 h
with detectable presence of residual secondary amine (Fig. 6C).
Figure 7A and B confirmed that amide NH does not react with
epoxide up to 1508C. Figure 8C and D (mid-IR spectra) also indi-
cated that in situ ester and amine formation did not occur when
Epon 828 and amidoamine was heated to < 1608C. This denotes
that to a certain extent, some side reactions (Reactions 3 and 4 in
Fig. 4) occur along with the main epoxy–amine reaction in
solvent-based Epon 828–amidoamine-I systems.
Epoxy Conversion during Cure of Liquid Epoxy Resin with
Amidoamine-I
Figure 9 displays the epoxy conversions of Epon 828 and
amidoamine-I blends in bulk and solvent, stoichiometric (1.0),
DOI 10.1002/pen
and 1.15 epoxy amine ratio during cure at ambient and elevated
temperatures. Conversions were calculated from normalized
near-IR spectra displayed in Fig. 6 using the following
Equation.
 
A0 2At
Conversion ð%Þ5 3100 (3)
A0
where A0 and At are areas under the peaks at 0 h (first spectra
acquired immediately after mixing) and any time t during cure,
respectively. The area under the near-IR peak at 4,530 cm21
was used to calculate epoxy conversion. Epoxy conversion
increased rapidly up to 5 h but slowed down thereafter as vitrifi-
cation restricted the mobility of the reactive functional groups.
It was noticed that the initial rate of epoxy conversion in
solvent-based systems is higher than the rate of epoxy conver-
sions in bulk, regardless of stoichiometry. Higher initial rate of
epoxy group conversions in solvent-based systems is attributed
to higher mobility of functional groups as well as the accelerat-
ing influence of the solvent hydroxyl groups on the epoxy–
amine reaction via hydrogen bonding with the epoxy ring oxy-
gen. In addition, visual heterogeneity was noted in the bulk
sample whereas the solvent-based system was visually transpar-
ent and homogeneous. These combined effects led to epoxy con-
version values of 77.81% and 68.53% in stoichiometric and 1.15
epoxy:amine ratio systems respectively, whereas corresponding
values for the bulk condition were 51.27% and 48.90%, respec-
tively after 5 h at ambient. After 16 h at ambient, the stoichiomet-
rically formulated solvent-based system exhibited 98.32% epoxy
conversion while the stoichiometric bulk system was limited to
64.15% epoxy conversion. This indicates that the epoxy conver-
sion rate of solvent-based stoichiometric system in the vitrified
state was higher than the epoxy conversion rate in vitrified state
of stoichiometric bulk system. In other words, residual solvent did
affect the epoxy conversion in vitrified state.
Post-curing of the solvent-based stoichiometric system at
808C for 2 h led to epoxy conversion values of >99%. On the
POLYMER ENGINEERING AND SCIENCE—2018 9
 TABLE 2. Properties of clear coatings.
Residual solvent 20/60/85 gloss on Dry/wet
Coatings (wt%) by TGA Leneta chart adhesion
C1 8.30 66/88/93 5B/5B
C2 7.00 79/93/97 5B/5B
other hand, post-cure of the stoichiometric bulk system at 808C/
2 h resulted in 71.48% epoxy conversion, which increased to
>99% after post-curing at 1208C/1 h 1 1608C/2 h 1 2008C/2 h.
Post-cure of the 1.15 epoxy:amine ratio bulk system at 808C/2 h
resulted in 66.09% epoxy conversion, that is, lower than the
stoichiometric bulk system, due to its higher epoxy content. The
epoxy conversion increased to > 99% upon further post-curing
at 1208C/1 h 1 1608C/2 h 1 2008C/2 h. As mentioned earlier,
both the stoichiometric and excess epoxy (1.15) bulk systems
had residual secondary amine even after full conversion of
epoxy moieties at elevated temperature (Fig. 6A and B). The
solvent-based stoichiometric system contained trace amounts of
residual secondary amine after full conversion of epoxy at 808C
(Fig. 6C). The solvent-based system formulated at 1.15:1
epoxy:amine ratio proceeded to 91.60% epoxy conversion in
16 h at ambient, that is, lower than the stoichiometric solvent-
based system. The theoretical epoxy conversion drops to
86.96% if only amine moieties of amidoamine-I are considered
to react with epoxy. This means that side reactions (Reactions 3
and 4 in Fig. 4) also occurred along with cure reactions (Reac-
tions 1 and 2 in Fig. 4) during cure at ambient. Post-curing of
the 1.15:1 solvent-based system at 808C/2 h led to > 99% epoxy
conversion with complete reaction of amine moiety (Figs. 6D
and 9). Side reactions, that is, epoxy–epoxy homopolymerization
and epoxy–hydroxyl etherification, occur depending on cure
condition and efficiency of in situ formed tertiary amine in the
system. This reasoning also favors having excess epoxy in coat-
ing formulations.
The solvent-based 1.15 epoxy:amine ratio system exhibited
complete amine consumption before the epoxy moiety, and
complete epoxy conversion after cure for 16 h at ambient and
post-cure at 808C/2 h. Figure 8C and D displays mid-IR spectra
of coatings C1 and C2 at ambient, 80, 120, 160, and 2008C. A
prominent ester peak at 1,729 cm21 was noticed in coatings C1
and C2 when heated at 2008C, which started growing at 1608C.
Thus, ester formation in situ occurred in this epoxy–
amidoamine-I system at 1608C. Figure 8C and D indicates the
lack of ester groups upon post-heating of coatings C1 and C2 to
1208C. Literature reports and the reaction shown in Fig. 4 sug-
gest that ester formation is accompanied by in situ formation of
amine as well. Near-IR (Supporting Information Fig. S4) analy-
sis of coatings C1 and C2 at the same temperatures used for
mid-IR analysis (Fig. 8C and D) did not show any amine peak
at 6,500 cm21; so any amine that may have formed was prob-
ably in the undetectable range.
Clear Coatings Properties
Table 2 shows the properties of clear coatings C1 and C2.
Despite post-curing at 808C for 4 h, coatings C1 and C2 con-
tained 7–8 wt% residual solvent (boiling points of BzOH and
PGME are 205 and  1188C, respectively). Both coatings
10 POLYMER ENGINEERING AND SCIENCE—2018
Mandrel MEK double Impact resistance Pull-off
flexibility rubs in-lb (J) stress (MPa)
Passed >200 145 (16.38) 1.33 6 0.66
Passed >200 160 (18.08) 0.64 6 0.28
displayed excellent crosshatch dry and wet adhesion (on S36
panels), excellent flexibility via the mandrel bend test, and very
good solvent resistance (>200 MEK double rubs). Impact resis-
tance of C1 and C2 coatings were determined to pass 145 in-lb
(16.38 J) and 160 in-lb (18.08 J), respectively. Pull-off stress
values of coatings C1 and C2 were 1.33 and 0.64 MPa, respec-
tively (standard deviation in measurement was 50%). Meis
et al. [8] reported pull-off stress of 2.8–8.6 MPa of stoichiomet-
rically balanced epoxy–amine coatings on pretreated aluminum
alloy 2024-T3 metals. High standard deviation ( 50%) in pull-
off stress tests of several epoxy–amine coatings was also
reported by Meis et al. Pull-off adhesion values in the range of
1–3.75 MPa were reported by Almeida et al. [35] for several
epoxy–polyamide coatings on Sa 2.5 blast clean steel substrates.
The lower pull-off stress of coatings C1 and C2 compared with
the values reported in literature is attributed to the use of
untreated, smooth QD panels that limits the physical interaction
between substrate and coating. Overall, there was very little dif-
ference between coatings C1 and C2 in terms of gloss, dry/wet
cross-cut adhesion, flexibility, impact resistance, solvent resis-
tance, and pull-off stress.
Figure 10A and Table 3 display the dynamic mechanical
properties (in terms of storage modulus, Tg, and full width at
half height of tan d curve). Coatings C1 and C2 showed no
practical difference in Tg in the second cycle. The breadth of
the tan d (first cycle) curves suggests the presence of residual
solvent in both coatings. The Tg in first cycle was centered
around 70 and 758C for C1 and C2, respectively, and the dispar-
ity between the two coatings is professed to be because of the
differences in their residual solvent content. The noticeably
higher storage modulus (2 MPa) in the rubbery region of the
second cycle cannot be due to residual cure as near-IR cure
kinetics and near-IR spectra of these clear coatings suggested
that no residual cure was left in coatings C1 and C2. Post-
heating of cured coatings (C1 and C2) to 2008C resulted in in
situ formation of trace amounts of ester (Fig. 8C and D) while
near-IR of the same samples did not show detectable amounts
of amine (Supporting Information Fig. S4). It is thus understand-
able that the extent of reaction between amide and hydroxyl
groups to generate ester and amine is nominal when C1 and C2
were heated to 2008C. This in turn indicated that this traceable
amount of reaction between amide and hydroxyls can cause
only little change in the rubbery region storage modulus in sec-
ond cycle, which may very well fall within the standard devia-
tion range.
Molecular weight between crosslinks (Mc) of coatings C1
and C2 was determined from rubbery plateau storage modulus
using Eq. 1. The theoretical Mc of a stoichiometrically balanced
Epon 828 and amidoamine-I system was calculated to be 623 g/
mol, and the experimental Mc values of both C1 and C2 coat-
ings were reasonably close to the expected value. In addition,
DOI 10.1002/pen
 FIG. 10. (A) Plot of storage modulus (E’) and tan d versus temperature C1 and C2 via dynamic mechanical analy-
sis, (B) water sorption (wt%) versus time of coatings C1 and C2 at ambient. [Color figure can be viewed at wileyon-
linelibrary.com]

the nominal difference of Mc between the first and second
cycles of both coatings C1 and C2 suggested that the chemical
changes (observed via mid-IR of post heated samples) between
cycles have negligible effect on the coatings network. Compari-
son of storage moduli across the glassy state in first and second
cycles indicated anti-plasticization at sub-ambient temperatures,
either due to residual solvent occupying the free volume within
the polymer without swelling and resulting in a net decrease of
free volume or being involved in strong intermolecular interac-
tions with polymer chains that provided molecular level rein-
forcement against glassy state (sub-Tg) motions [36–38]. The
intermolecular interactions between solvent molecules and poly-
mer chains are favored by the hydroxyl groups of residual
PGME and BzOH. Anti-plasticization lowers the Tg but
increases the resistance to deformation at sub-Tg temperatures.
Figure 10B shows water sorption data of coatings C1 and C2
measured via immersion technique. Several researchers have
investigated the water sorption properties of bulk epoxy thermo-
sets [39–41] and fully formulated epoxy-based coatings [8, 42],
and found a range of water sorption and transport behaviors that
were influenced by a multitude of factors such as polymer
chemistry, substrate, pigments, and residual solvents. In general,
DGEBA-based epoxy resins exhibit total water uptake of 0.5–5
wt%. The free films studied here exhibited similar behaviors
with values of 0.75 and < 1.5 wt% for coatings C1 and C2,
respectively. Water sorption of coating C1 decreased after
achieving equilibrium, probably due to leaching of residual sol-
vent from the film. Polymer hydroplasticization followed by
water sorption would allow for greater mobility of polymer
chains, which would result in solvent being released into the
water and a decrease in overall sample mass. A morphological
difference between the two systems could also be responsible
for the water sorption differences with more or less densely
crosslinked regions allowing for greater polymer–water
interactions.
During cure of an epoxy–amidoamine system, we can expect
epoxy–amine, epoxy–hydroxyl etherification, epoxy–epoxy
homopolymerization, epoxy–amide NH, and hydroxyl–amide
esterification reactions. Epoxy–amine reactions occurred at
ambient as well as at elevated temperatures in case of Epon 828
and amidoamine-I blend as has been reported by others. The
amide NH in N-methyl acetamide did not react with epoxide up
to 1508C, suggesting that the amide NH in amidoamine-I was
also unlikely to react with Epon 828 under similar conditions.

TABLE 3. DMA properties of clear coatings obtained from Fig. 10A.

E’ at Tg1508C Peak width at half

E’ at 8C (GPa) Tg (8C) (MPa) height (PWHH) Mc (g/mol)

First Second First Second First Second First Second First Second
Coatings cycle cycle cycle cycle cycle cycle cycle cycle cycle cycle

C1 2.35 2.75 67.80 100 16.59 18.74 38 18 654 624

C2 2.37 2.46 77.31 102 16.26 18.17 37 17 667 642

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2018 11

Ester formation was observed in situ via amide–hydroxyl reac-
tion in the Epon 828–amidoamine-I blend at  1608C. The good
coating performance properties (solvent resistance, adhesion,
flexibility, minimum water sorption, etc.) validated the choice
of amidoamine selected to understand cure chemistry of epoxy–
amidoamine systems.
CONCLUSIONS
A dimer fatty acid-based amidoamine was synthesized with
DETA without using catalyst. The synthetic procedure was repro-
ducible as it has been verified by reacting same dimer fatty acid
with BAC. Amidoamine-I was reactive at ambient with DGEBA-
based liquid epoxy resin (Epon 828) as well as sulfide-based
epoxy resin. Near-IR and DSC analysis of Epon 828 and N-methyl
acetamide stoichiometric blend indicated that the amide NH moi-
ety in amidoamine-I does not react with DGEBA-based liquid
epoxy at  1508C. Epoxy conversion was quantified for bulk and
solvent-based epoxy and amidoamine-I systems with 1:1 and
1.15:1 epoxy:amine equivalent ratios to understand differences in
vitrification, stoichiometry, and thermal limited reaction progress.
Epoxy group conversion reached 64.15% and 59.86% in 16 h at
ambient for blends of Epon 828 and amidoamine-I in bulk at
epoxy–amine ratios of 1.0 and 1.15 respectively, whereas in
solvent-based systems, the corresponding epoxy conversion was
98.32% and 91.60%, respectively. When the stoichiometric blend
of amidoamine-I and Epon 828 in bulk was post-cured at 2008C,
partial conversion of the secondary amine moieties and complete
conversion of epoxy functional groups was observed. The same
system with an epoxy:amine ratio of 1.15:1 also exhibited incom-
plete consumption of secondary amine when post-cured to 2008C.
Cure monitoring via near-IR experiments indicated that the pres-
ence of residual amine moieties was due to the occurrence of
hydroxyl–etherification and epoxy–epoxy homopolymerization
during cure of Epon 828–amidoamine-I blend in bulk at elevated
temperatures. Residual secondary amine moieties were detected
via near-IR spectroscopy in the stoichiometric solvent-based ami-
doamine-I–Epon 828 blend when cured at ambient for 16 h fol-
lowed by 4 h at 808C. Increasing the epoxy:amine ratio to 1.15:1
in the solvent-based system resulted in complete consumption of
amine moiety after 16 h at ambient. The solvent-based epoxy–ami-
doamine blend also experienced hydroxyl–etherification and
epoxy–epoxy homopolymerization as epoxy conversion proceeded
to 91.60% at ambient after 16 h, which is beyond the theoretical
limit (86.96%) for 1.15:1 epoxy–amine ratio. Ester formation was
detected via mid-IR when the amidoamine-I–Epon 828 blend was
heated to  1608C in both the bulk and solvent systems. Solvent-
based clear coatings of amidoamine-I and Epon 828 resulted in
excellent wet and dry crosshatch adhesion, pull-off stress, solvent
resistance, and flexibility. In addition, Tg (determined via DMA)
and water absorption of solvent-based Epon 828 and amidoamine-
I coatings are in the range of widely used and reported epoxy–ami-
doamine coatings.
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