Macromolecular Research, Vol. 18, No. 4, pp 324-330 (2010) www.springer.

com/13233
DOI 10.1007/s13233-010-0416-1

Improvement of the Thermal Latency for Epoxy-Phenolic Resins by Novel

Amphiphatic Imidazole Catalysts

Fung Fuh Wong*

Graduate Institute of Pharmaceutical Chemistry, China Medical University, No. 91, Hsueh-Shih Rd., Taichung,
Taiwan 40402, R.O.C.

Chun Min Lin1, Kun-Lung Chen2,3, and Yun-Hwei Shen2

1
Department of Chemistry and 2Department of Resources Engineering, National Cheng Kung University,
No. 1, Ta Hsueh Rd., Tainan, Taiwan 70101, R.O.C.
3
Sustainable Environment Research Center, National Cheng Kung University, No. 500, Sec. 3, An-ming Rd.,
Tainan City, Taiwan 709, R. O. C.

Jiann-Jyh Huang
Development Center for Biotechnology, No. 101, Lane 169, Kangning St., Xizhi City, Taipei County, Taiwan 221, R.O.C.

Received May 26, 2009; Revised November 30, 2009; Accepted November 30, 2009

Abstract: Novel amphiphatic imidazole compounds were evaluated as thermal latent catalysts for the polymeriza-
tion of diglycidyl ether of bisphenol A (DGEBA). Amphiphatic compounds 5-9, two commercially available catalysts
1 and 2, and compounds 3 and 4 were used to cure epoxy resin systems for an investigation of their thermal latency
and storage stability. The results from the cure activation energy and viscosity-storage time of the catalysts, the order
of thermally latent activity was 3-phenylpropanoic acid (4) > 2-amino-3-phenylpropinoic acid (5) > 2-amino-3-(imi-
dazole-4-yl)-propionic acid (H-His-OH, 8) > N-tert-butoxycarbonyl-histidine (9) > imidazole-4-acrylic acid (6) >
3-(imidazole-4-yl)propionic acid (7) > 1-cyanoethyl-2-ethyl-4-methyl-imidazole (2) > 2-ethyl-4-methylimidazole
(1) > histamine (3). From the results, the amphiphatic imidazole catalysts 5-9 showed better thermal latency than
commercialized catalysts 1 and 2, basic catalyst 3 and acidic catalyst 4. Concerning the glass transition temperature
(Tg), the use of amphiphatic imidazole catalysts 5-9 provided complete or near complete curing systems at temper-
atures ranging from 152-163 oC, which were similar to two commercially available catalysts (151-152 oC, 1 and 2)
and histamine (159 oC, 3). On the other hand, the Tg for compounds 4 and 5 could not be detected at 30-300 oC from
the temperature scans because of their weak nucleophilicity and low cross-linking reactivity.
Keywords: amphiphatic catalysts, thermal latent catalysts, epoxy-phenolic resins, polymerization, thermosets.

Introduction filter loadings.8-10 Nevertheless, the biphenyl type epoxy resins

Epoxy resins are thermosetting polymers widely used as
molding and sealing materials for electronic packaging in
the electronics industry. Their excellent insulating charac-
teristics, good adhesive properties, outstanding chemical
resistance, retention of properties under severe operating
conditions, low moisture adsorption, and absence of by-products
causing void formation or acting as plasticizers attract atten-
tions in the fields of industry and research.1-7 As an epoxy
resin, high molecular weight biphenyl type epoxy resins are
highly reliable electronic molding compounds (EMC) with
good adhesion and high toughness, and can be used as high
*Corresponding Author. E-mail: wongfungfuh@yahoo.com.tw
of low molecular weight show low storage stability at room
temperature. To improve the pot life at room temperature,
latent catalysts are thus developed.6
Catalysts are used in most molding compound formula-
tions to reduce the in-mold time and extremely important
for adhesives, paints, coating, molding resins, insulation
materials, and matrices for composite materials. However,
un-modified catalysts are less stable and the curing process
occurs fast at room temperature. Thermal11 and cationic
latent12 catalysts are two classes of catalysts developed to
promote the pot-life of epoxy resin systems. Many cationic
latent catalysts were published in recent year and their reac-
tivity were enhanced by the couterions including BF4-, PF6-,
AsF6- and SbF6-.13 During the curing polymerization, how-

The Polymer Society of Korea 324

 Improvement of the Thermal Latency for Epoxy-Phenolic Resins by Novel Amphiphatic Imidazole Catalysts
Scheme I.
ever, the acidic species (HBF4, HPF6, HAsF6 and HSbF6)
would be released to damage the electronic products.
Many pure thermal latent catalysts14 were developed and
reported as epoxy curing agents in the recent research
because they can provide polymers of better heat resistance,
lower tensile elongation, a higher modulus and a wider
range of cure temperature than amine-cured system.15,16 The
modified imidazoles have attracted much attention as latent
catalysts for the reason that they can maintain the long pot-
life and improve the physical properties, as well as the cure
reaction at high temperature. Much work has been carried
out on reducing the activity of imidazoles. The approaches
involve the preparation of metal Lewis acid–imidazole
complex (e.g. metals acetylacetone–imidazole complex),17
the formation of 1,3-disubstituted imidazolium salts18 and 1-
substituted imidazole derivatives,19 and the modification by
blending with the organic carboxylic acids (e.g. benzoic
acid, isophthalic acid, and trimellitate).20
In this paper, we reported first use of amphiphatic imida-
zole compounds 6-9 as the thermal latent catalysts, with a
structural feature containing an acidic carboxylic acid,
amino-acid and/or a basic imidazole, for the polymerization
of diglycidyl ether of bisphenol A (DGEBA). Their struc-
tures were shown in Scheme I. Amphiphatic catalysts 5-9
were weak acid, and thus, the nucleophilic imidazolyl and
amino group was de-activated, making them unable to attack
the oxirane of the polymer at room temperature. At elevated
temperature (100-175 oC), the ring-opening reaction of epoxy
resin (DGEBA) could be initiated by protonation and attacked
with the nucleophilic part of the catalyst to underwent prop-
agation and polymerization. Finally, the polymerization was
terminated by the protonation of alkoxide from the catalyst.
These new catalysts showed high conversions, and might be
suitable for being used as thermal latent catalysts.
Experimental
Chemical Materials. Commercial available starting materi-
als were used as purchased. Diglycidylether of bisphenol
A (DGEBA, NPEK-114M) was purchased form Nan Ya
Plastics Co. 3-(2-Ethyl-4-methyl-imidazol-1-yl)-propionitrile
(2E4MZ-CN, 2) and 2-ethyl-4-methylimidazole (2E4MZ,
1) were purchased form Shikoku Chemical Co. Histamine
(3), 3-phenylpropanoic acid (4), and imidazole-4-acrylic acid
(6) were purchased from Acoros Chemical Co. 2-Amino-3-
Macromol. Res., Vol. 18, No. 4, 2010
phenylpropanoic acid (5) and 2-amino-3-(imidazole-4-yl)-
propionic acid (8) were purchased from Novabiochem Co.
3-(Imidazole-4-yl)-propionic acid (7) and N-tert-butoxycar-
bonylhistidine (9) were prepared by reported procedure.21,22
Synthesis of 3-(imidazol-4-yl)propionic Acid (7).21 A
solution of urocanic acid (3.30 g, 24.0 mmol) and 10% Pd/C
(170 mg) in hot acetic acid (80 mL) was hydrogenated in a
Parr apparatus at room temperature for 12 h. After the reaction
was completed, the reaction mixture was filtered through
Celite and the filtrate was concentrated under reduced pres-
sure to remove acetic acid. The residue was recrystallized
from ethanol/ether to obtain compound 7 as white solids in
96% yield (3.15 g , 23.0 mmol): mp 206-208 oC; 1H NMR
(D2O, 300 MHz) d 2.35 (t, 2 H, J = 9.0 Hz, -CH2), 2.75 (t, 2
H, J = 9.0 Hz, -CH2), 6.99 (s, 1 H), 8.33 (s, 1 H); 13C NMR
(D2O, 75 MHz) δ 20.64, 35.54, 114.89, 132.45, 133.12,
180.54; IR (neat) 3139 (b), 1572 (s, C=O), 1346 (m), 1253
(m), 1073 (m), 855 (m), 733 (m) cm-1; MS m/z (relative
intensity) 141 (M+, 20), 139 (11), 138 (29), 137 (52), 136
(54), 120 (9), 107 (12), 89 (9), 77 (8), 63 (3), 51 (3); Anal.
Calcd for C6H8N2O2: C, 51.42; H, 5.75; N, 19.99. Found: C,
51.13; H, 5.87; N, 19.55.
Synthesis of N-tert-Butoxycarbonylhistidine (9).22 To a
solution of 2-amino-3-(imidazole-4-yl)-propionic acid (8,
4.25 g, 27.0 mmol) in dry acetonitrile (100 mL) was added
tert-butyloxycarbonyl azidoformate (4.58 g, 32.1 mmol)
and triethylamine (22 mL). The reaction mixture was heated
at 50 oC for 24 h. After the reaction was completed, the resi-
due was extracted with hexane (50 mL × 2) and EtOAc (50
mL × 3). The combined organic layers were concentrated
under reduced pressure and re-dissolved in water (50 mL).
The aqueous solution was adjusted to pH 3 with 1.0 N HCl
(aq) and refrigerated overnight to provide colorless granules.
The granules was collected and recrystallized from metha-
nol/water to give compound 9 as white solids in 70% yield
(4.92 g, 19.2 mmol): mp 199-201 oC; 1H NMR (D2O, 300
MHz) δ 1.17 (s, 9 H, -CH3), 2.81 (dd, J = 4.7, 7.5 Hz, 1 H),
3.06 (dd, J = 2.1, 8.7 Hz, 1 H), 4.02 (m, 1 H, CH), 7.09 (s, 1
H), 8.41 (s, 1 H); 13C NMR (D2O, 75 MHz) δ 27.34, 27.78,
54.86, 80.93, 116.60, 129.80, 132.85, 156.92, 176.99; IR
(neat) 3127 (m, NH), 1701 (s, C=O), 1598 (m), 1370 (m),
1165 (m), 1053 (m), 1028 (m), 864 (m), 804 (m) cm-1; MS
m/z (relative intensity) 256 (M+, 100), 200 (40), 156 (17),
155 (11), 154 (29), 137 (14), 136 (17), 110 (17), 107 (5), 89
(4), 57 (5); Anal. Calcd for C11H17N3O4: C, 51.76; H, 6.71;
N, 16.46. Found: C, 51.47; H, 6.77; N, 16.19.
Measurement of Pot-life.
Sample Preparation: The catalyst level was set to 2% w/
w to DGEBA. The viscosity and epoxide equivalent weight
of DGEBA was 2,100-2,500 cp and 188-199 g/equiv, respec-
tively. The samples were mixed by use of a high shear
blender and degassed in vacuum oven. All samples were
stored in glass vials at room temperature between viscosity
measurements. The glass vials were rotated by a rotator at
325
 F. F. Wong et al.
~10 rpm all the time to keep the filler from settling.
Measurement of Viscosity: The viscosities of the sam-
ples were measured periodically for 600 h by use of a vis-
cometer (Brook Field Instruments, model DV-II+) with
parallel plate geometry and spindle (model SC4-21). The
gap was set to 250 µm and the test was performed at 25 oC.
The test method is listed as follows:
(1) Pre-shear at 10 S-1 for 30 sec.
(2) Stepped ramp of shear rate at 0.1-20 S-1 by 25 points,
with tolerance ≤ 5% (up curve);
(3) Stepped ramp of shear rate from 20 to 0.1 S-1 by 25
points, with tolerance no ≤ 5% (down curve).
(4) The viscosity for each sample was calculated from the
down curve.
Differential Thermometry Analysis (TG/DTA). All scan-
ning TG/DTA studies of were performed with Perkin Ele-
mer Instruments Pyris Diamond at heating rate of 10 oC/min
under N2. High purity indium and zinc were used to cali-
brate the calorimeter. TG/DTA studies of the cure of DGEBA
with the each catalyst (1-9) at a concentration of 1, 2, 3, and
5% w/w are performed from 30-300 oC at heating rate of
10 oC/min under N2.
Glass Transition Temperature (Tg) Measurement. The
glass transition temperature (Tg) studies are performed by
using a dynamic differential scanning calorimeter (DSC,
Shimadzu Instruments DSC-60), which is calibrated with
indium. The samples were placed in aluminum sealed pans
and were performed under a flow (30 mL/min) of dry N2.
Temperature scans were performed from 30-300 oC at heat-
ing rate of 10 oC/min. The amount of sample was limited to
12-15 mg to minimize the experimental errors. The glass
transition temperature (Tg) of the cure of DGEBA (DGEBA,
NPEK-114M, 188-199 g/eq) with the catalyst 1-9 at a con-
centration of 2 wt% are measured and determined by a sec-
ond run; the thermogram presents no residual heat. The
Scheme II. Proposed mechanism of adduct formation for the cure diglycidylether of bisphenol A, (DGEBA, NPEK-114M) with the
organic Lewis acid-base hybrid catalysts (4-9).
326
epoxy (DGEBA) with two of commercially available cata-
lysts (1 and 2) and a base catalyst (3) and two acidic catalysts
(4 and 5) were also done for comparison purpose.
Result and Discussion
Measurement of the pH Value of Catalysts 1-9 in Water
and the Curing Mechanism Study. Since the polymeriza-
tion of DGEBA were reported to be initiated by the protonation
of the oxirane followed by ring opening by the nucleophiles
from the catalysts (see Scheme II),11,14,23-25 the pH value of
the catalyst would contribute to the efficiency of the poly-
merization. In aqueous solution, the simple imidazole cata-
lysts 1-3 were basic and the pH values ranged from 9.6 to
10.1. Catalysts 4 were simply a carboxylic acid, demon-
strated as a moderate acid with pH 3.2. The pH values of
amphiphatic catalysts 5-9, which contained carboxylic acid,
amino-acid, and/or imidazole, were weaker acids with pH
values of 4.4-5.8 (see Table I). Catalyst 8 was found to be
almost neutral (pH = 6.8) and compound 9 was an acid due
to the N-Boc decreased the basicity. After the proton trans-
fer from the catalyst to the oxirane of DGEBA, the nucleo-
philic moiety in the catalyst could be nitrogen atom on the
imidazoly or amino groups, or the carboxylate form a loss
of a proton (see Scheme II).26 The nucleophiles would attack
the protonated oxirane to propagate the polymerization at
elevated temperatures.
Measurement of Pot-life.27 Figure 1 illustrated the vis-
cosity–shear rate relationship of DGEBA containing 2 wt%
of catalysts 1-9 at room temperature under nitrogen system.
The viscosity of DGEBA treated with imidazole derivatives
1-3 significantly increased from ~2,000 to ~10,000 cp in
100 h, indicating that compounds 1-3 exhibited poor latency
properties at room temperature. For DGEBA treated with
carboxylic acid 4 and amphiphatic compound 5-9, however,
Macromol. Res., Vol. 18, No. 4, 2010
 Improvement of the Thermal Latency for Epoxy-Phenolic Resins by Novel Amphiphatic Imidazole Catalysts

Table I. The pH Values of Catalysts 1-9 in Aqueous Solution

Catalyst Functional Groups pHa
1 Imidazolyl group 9.6
2 Imidazolyl group 10.1
3 Amino and imidazolyl groups 10.0
4 Carboxylic acid group 3.2
5 Amino-acid group 5.8
6 Carboxylic acid and imidazolyl groups 4.4
7 Carboxylic acid and imidazolyl groups 5.3
8 Amino-acid and imidazolyl groups 6.8
9 Protecting amino-acid and imidazolyl groups 4.5
a
The black testing is performed in water and the pH is 6.4. Figure 2. Diagram of ln(ϕ/Tm2) versus (1/Tm) for the determina-
tion of Ea of DGEBA with catalyst 1-9.

Table II. Cure Activation Energy (Ea) Obtained by the Kissinger

Equation

Kinetic Heating Rate (oC/min) Ea

Catalyst Slope
Factors 5 10 15 20 (kJ/mol)

1/Tm 2.45 2.36 2.32 2.28

1 2
-7.25 60.3
ln (ϕ/T ) -10.41 -9.79 -9.42 -9.17
m

1/Tm 2.31 2.24 2.20 2.15

2 -8.03 65.4
ln (ϕ/Tm2) -10.53 -9.89 -9.53 -9.28
1/Tm 2.44 2.36 2.31 2.26
3 2
-6.84 56.8
ln (ϕ/T ) -10.41 -9.79 -9.43 -9.18
m

1/Tm 1.90 1.87 1.84 1.82

Figure 1. Diagram of the viscosity of DGEBA treated with catalysts 4 -14.78 123
1-9 against storage time at 10 S-1 shear rate (N/C: DGEBA alone).
2
ln (ϕ/T ) -10.91 -10.25 -9.89 -9.62
m

1/Tm 2.07 2.01 1.99 1.97

the viscosity of DGEBA retained almost constant at ~2,000 5 2
-13.26 110
ln (ϕ/T ) -10.75 -10.11 -9.73 -9.46
m
cp. These results concluded that the acidic catalyst 4 and
mild acidic amphiphatic catalyst 5-9 demonstrated superior 1/Tm 2.22 2.17 2.13 2.11
6 -11.14 92.6
latency properties than commercial available imidazole cat- ln (ϕ/Tm2) -10.60 -9.96 -9.59 -9.33
alysts 1-3 at room temperature. 1/Tm 2.32 2.26 2.22 2.19
The Cure Activation Energy (Ea). The cure behaviors of 7 2
-10.18 84.6
ln (ϕ/T ) -10.52 -9.88 -9.50 -9.24
m
DGEBA resin with catalysts 1-9 (2% w/w) were studied
with TG/DTA in the dynamic scanning mode at different 1/Tm 1.98 1.93 1.91 1.88
8 -12.60 104
heating rates. The cure activation energy (Ea) of the overall 2
ln (ϕ/T ) -10.83 -10.19 -9.81 -9.55
m
process was determined by the Kissinger method:12d,28,29 1/Tm 2.27 2.22 2.19 2.16
ϕ Ea AR 9 2
-11.22 93.3
ln -----2- = --------- + ln ------- (1) ln (ϕ/T ) -10.56 -9.91 -9.53 -9.27
m
Tm RT m Ea
From Table II, we found the Ea values for DGEBA with catalysts 1-9
Where, ϕ is the heating rate; Tm is the temperature of the were in the range of 56.8-123 kJ/mol. The Ea values, which reflected
the relative controlled polymerization, were in the order of 4 (123 kJ/mol)
maximum exothermic peak; A is the pre-exponential factor; > 5 (110 kJ/mol) > 8 (104 kJ/mol) > 9 (93.3 kJ/mol) > 6 (92.6 kJ/mol)
and R is the gas constant (8.314 J/g·mole·K). > 7 (84.6 kJ/mol) > 2 (65.4 kJ/mol) > 1 (60.3 kJ/mol) > 3 (56.8 kJ/
Ea can be obtained from the slope from the graph of ln (ϕ/ mol). Their tendency is consistent with the viscosity measurement.
Tm2) versus (1/Tm) on the basis of the eq. (1). The parameter and
experiment for curing DGEBA by catalysts 1-9 from TG/DTA culated and listed in Table II.
were obtained and plotted in Figure 2 in accordance with Differential Thermometry Analysis (TG/DTA). Results
eq. (1). The activation energy Ea for each process were cal- from TG/DTA analysis for the curing of DGEBA by use of

Macromol. Res., Vol. 18, No. 4, 2010 327

 F. F. Wong et al.

catalysts 1-9 at four concentrations were summarized in amounts of catalysts 1-9 were increased. That might due the
Table III, which showed the exotherm onset, exotherm enhancement of the reaction rate by more catalysts.25 Total
peak, and total heat for the polymerization. We found that heat output revealed that all the polymerizations were exo-
the peaks shifted towards lower temperatures when the thermic, and that for the curing by typical imidazoles (1-3,
1-5 wt%) were 8-719 J/g. For weak acidic catalyst 4 and 5
Table III. The Exotherm Onset, Main Peak, and Total Heat of lacking of strong nucleophilic moiety, the lower total heats
DGEBA with Catalysts (1-9) at a Concentration of 1, 2, 3, and 5 wt% were found (10-61 J/g, 1-5 wt%, see Table III). For com-
pounds 6-9 possessing strong nucleophilic imidazole moi-
Catalyst Concentration Exotherm Exotherm Total Heat
(wt%) Onset (oC) Peak (oC) (J/g) ety, the higher exothermic heats were generated (27-677 J/g,
1-5 wt%, see the molding study Figure 3). Total heats of
1 135 164 42
compound 1-4 in the Table III were consistent with the liter-
2 120 151 259 ature reported data.17,18,24,30 The total heat output is impor-
1
3 116 150 406 tant to evaluate the feasibility for the curing system, for the
5 106 149 719 reason that too little total heat output indicates that no poly-
1 163 186 8 merization take place. However, too high total heat output
revealed that the reaction may not be scaled up to industrial
2 154 176 71
2 scale with a satisfactory safety level.18
3 151 169 185 We found that the curing of DGEBA by the catalyst 1-8
5 145 166 499 showed only one exotherm peak varying with different cata-
1 152 177 41 lyst concentration in TG/DTA (see Figure 3). For DGEBA
2 125 157 233
with catalyst 9, a small peak next to the main exotherm peak
3 in higher temperature was observed (see Figure 4). The area
3 118 155 436
and height of the shoulder peak is increasing with the con-
5 110 151 524 centration of catalyst 9. The formation of shoulder exothermic
1 157 263 17 peak might originate from the cleavage of t-Boc protecting group
2 156 261 36 by nucleophiles (e.g. amino, imidazolyl, or oxygen anion).
4 Measurement of Glass Transition Temperature (Tg)
3 155 259 41
and Conversion. The glass transition temperature (Tg) is an
5 153 256 61 important single parameters to determine the applications
1 192 226 10 and properties of polymer materials.31 The Tg values of
2 189 223 23 DGEBA cured with catalyst depend on the amount and
5 property of the catalysts,32 the epoxide equivalent weight of
3 188 223 38
DGEBA, and the blending agents (i.e. hardener, and filter).31
5 186 223 44
For DGEBA cured with imidazole 1-3, the Tg value indi-
1 178 191 27 cated the complete or near complete curing systems in the
2 177 190 47 temperature range of 151-159 oC. The results were consis-
6
3 175 189 66 tent with the published data.19,30
5 173 188 100 When weak acidic catalysts 4 and 5 were applied in cur-
1 158 173 65
2 156 171 141
7
3 154 170 164
5 155 170 294
1 222 246 145
2 221 245 281
8
3 216 245 414
5 207 245 677
1 160 179 29
2 158 176 71
9
3 157 173 110
5 156 172 141 Figure 3. Scanning TG/DTA of the cure of DGEBA at 10 oC/min
o
The heating rate was 10 C/min. with 3-(imidazole-4-yl)propionic acid (7, 1-5 wt%).

328 Macromol. Res., Vol. 18, No. 4, 2010

 Improvement of the Thermal Latency for Epoxy-Phenolic Resins by Novel Amphiphatic Imidazole Catalysts
Figure 4. Scanning TG/DTA of the cure of DGEBA at 10 °C/
min with N-tert-butoxycarbonyl-histidine (9, 1-5 wt%).
ing DGEBA, the Tg value could not be detected between
30-300 oC at the heating rate of 10 oC/min. Application of
the same conditions for the cure of DGEBA by amphiphatic
catalysts 6-9, the Tg values could be obtained, which ranged
from 152 to 163 oC (see Table IV and Figure 5). The cata-
lyst imidazole-4-acrylic acid (6), containing an α,β-unsatur-
ated double bond moiety, were able to participate the
polymerization and thus increased the crosslinking density
of the polymer.33 As a result, the Tg values and the thermal
stabilities were enhanced in this curing system by use of 6.
The conversions of the DGEBA by catalysts 1-9 (calcu-
lated from TGA, see Table IV) were plotted against the cur-
ing temperature as shown in Figure 6. Except for catalyst 4,
the conversions of all catalysts rapidly rose at specific and
narrow temperature ranges (see Figure 6). In the cases of
DGEBA with N-H contained imidazole 1 and 3, the conver-
sion rapidly increased at 140-165 oC and decreased gradu-
ally at 180-185 oC, whereas the conversion of DGEBA with
Table IV. The Glass Transition Temperature (Tg) Studies of
DGEBA with Catalysts (1-9) at a Concentration of 2 wt%
Catalyst Glass Transition Temperature (Tg, oC)a Conversion (%)b
1 151 >99
2 152 >99
3 159 >99
4 Non detatable >99
5 Non detatable >99
6 163 >99
7 153 >99
8 152 >99
9 153 >99
a
The glass transition temperature was obtained from second run of
DSC at the heating rate 10 oC/min. bThe conversion was determined
by scan of TG/DTA.
Macromol. Res., Vol. 18, No. 4, 2010
Figure 5. Second run for the DSC thermogram of DGEBA with
catalysts 1-9 curing systems at a concentration of 2 wt% showing
the Tg values.
fully blocked imidazole 2 increased drastically at >165 oC.
This might come from the hinderance of N1-substitutition.
3-Phenylpropanoic acid (4) is a weak acid and its conver-
sion for DGEBA is slowly activated from 185 to 290 oC. As
a result, compound 4 is not an efficient catalyst in this
epoxy system.
For amphiphatic catalyst 6 and 7, the conversion rapidly
increased at around 164 and 178 oC, and decreased gradu-
ally at around 191 and 211 oC, respectively. In the case of
DGEBA with amino-acid group catalysts 5 and 8, the con-
version took place at around 203 and 231 oC, which was
higher than imidazole–carboxylic acid 6 and 7. We thus
concluded that the amphiphatic catalysts 5-9 reported herein
showed better latent thermal properties in the epoxy system
down to temperature below 130 oC.
The Water-Absorption Properties. For the study the water-
absorption of the polymers, DGEBA resin and amphiphatic
catalyst 8 or 9 (2 wt%) were mixed and cured at 150 oC for
7-8 h. The polymers were chopped into specimens of 3×7×
50 mm in size and exposed to humid environments (72 h at
85 oC/85% R.H.). The resulting moisture absorptions were
Figure 6. Conversion curves of DGEBA cured by each catalyst
(1-9) as a function of the curing temperature.
329
 F. F. Wong et al.
obtained from weight difference and found to be lower than
1%. When the specimens in same size were cook in the
boiling water for 48 h, the average water-absorptions were
also lower than 0.7 wt%.
Conclusions
In this work, we successfully developed a series of amphiphatic
compounds 5-9 with basic imidazolyl and/or amino-acid
and carboxylic acid in the same molecule as the curing
agents to initiate the polymerization in the molding temper-
ature (100-175 oC). Due to the intramolecular or intermolec-
ular acid-base neutralization, the reactivity of amino and
imidazolyl moieties was reduced in the curing epoxy resins
to provide the good latent properties. Based on the studies
of the viscosity and Ea measurement, the activity order of
the thermally latent catalytic systems was estimated to be 4
> 5 > 8 > 9 > 6 > 7 > 2 > 1 > 3. As a result, the thermal latent
properties of amphiphatic catalysts 5-9 were better than the
commercial latent catalysts 1, 2, and 3, and efficient in ther-
mal curing DGEBA resin. Since most of the cationic latent
catalysts would be released the acidic by-product including
HBF4, HPF6, HAsF6 and HSbF6 to damage the electronic
products, the new-developed amphiphatic catalysts might pro-
vide an alternative pathway in the manufacturing of DGEBA.
In the model system, the Tg values of the polymers formed
by use of amphiphatic catalysts 5-9 were >150 oC, which
are better or similar the that by commercial available cata-
lysts 1 and 2. Moreover, compound 5-9 are quite stable at
room temperature. The prolongation the pot-life of DGEBA
resin could thus be achieved by use of these amphiphatic
catalysts to enhance the storage stability and good handling
of these polymers.
Acknowledgments. We are grateful to the National Sci-
ence Council of Republic of China for financial support
(NSC95-2221-E-006-398).
References
(1) S.-J. Park, J.-G. Kang, and S.-H. Kwon, J. Polym. Sci. Part B:
Polym. Phys., 42, 3841 (2004).
(2) A. L. Silva and J. C. Bordado, Catal. Rev., 46, 31 (2004).
(3) R. H. Lin, C.-L. Chen, L.-H. Kao, and P.-R. Yang, J. Appl.
Polym. Sci., 82, 3539 (2001).
(4) S.-J. Park, T.-J. Kim, and J.-R. Lee, J. Polym. Sci. Part B:
Polym. Phys., 38, 2114 (2000).
(5) S. Murai, Y. Nakano, and S. Hayase, J. Appl. Polym. Sci., 80,
181 (2001).
(6) W. G. Kim, H. G. Yoon, and J. Y. Lee, J. Appl. Polym. Sci., 81,
2711 (2001).
(7) C. A. May, in Epoxy Resins: Chemistry and technology, 2nd
Ed., Marcel Dekker, New York, 1988.
(8) S. Han, H. G. Yoon, W. G. Kim, and T. J. Moon, J. Polym. Sci.
Part A: Polym. Chem., 37, 713 (1999).
330
(9) S. Han, W. G. Kim, H. G. Yoon, and T. J. Moon, J. Polym. Sci.
Part A: Polym. Chem., 36, 773 (1998).
(10) S. Han, W. G. Kim, H. G. Yoon, and T. Moon, J. Bull. Kor.
Chem. Soc., 18, 1199 (1997).
(11) (a) C. P. Wong, in Polymers for Electronic and Photonic Appli-
cations, Academic Press, Inc., New York, 1993, p. 300; (b) J.
H. Ryu, K. C. Choi, and G. W. Kim, J. Appl. Polym. Sci., 96,
2287 (2005).
(12) (a) Y. C. Kim, S.-J. Park, and J.-R. Lee, Polym. J., 29, 759
(1997); (b) S.-J. Park, T.-J. Kim, and H.-Y. Kim, Polym. Int.,
51, 386 (2002); (c) Y. Goh, T. Iijima, and M. Tomoi, J.
Polym. Sci. Part A: Polym. Chem., 40, 2689 (2002); (d) S.-J.
Park and G.-Y. Heo, Macromol. Chem. Phys., 206, 1134
(2005); (e) S. Nakano and T. Endo, J. Polym. Sci. Part A: Polym.
Chem., 34, 475 (1996); (f) J. K. Lee, Y. Choi, J.-R. Lee, and J.
Park, Macromol. Res., 10, 34 (2002).
(13) J. A. Mcgowen and L. J. Mathias, Polym. Compos., 18, 348
(1997).
(14) (a) W. R. Ashcroft, in Chemistry and Technology of Epoxy
Resins, B. Ellis, Ed., Blackie Acadamic and Professional,
London, 1993, p. 58; (b) Y.-C. Chen and W.-Y. Chiu, Polymer,
42, 5439 (2001); (c) M. S. Heise and G. C. Martin, J. Appl.
Polym. Sci., 39, 721 (1990).
(15) M. Ito, H. Hata, and K. Kamagata, J. Appl. Polym. Sci., 33,
1843 (1987).
(16) R. J. Jackson, A. M. Pigneri, and E. C. Gaigoci, SAMPE J.,
23, 16 (1987).
(17) (a) J. M. Barton, G. J. Buist, I. Hamerton, B. J. Howlin, J. R.
Jones, and S. Liu, J. Mater. Chem., 4, 379 (1994); (b) G. J.
Buist, I. Hamerton, B. J. Howlin, J. R. Jones, S. Liu, and J.
M. Barton, J. Mater. Chem., 4, 1793 (1994); (c) J. D. B.
Smith, J. Appl. Polym. Sci., 26, 979 (1981).
(18) F. Ricciardi, W. A. Romanchick, and M. M. Joullié, J. Polym.
Sci., Polym. Lett. Ed., 21, 633 (1983).
(19) F. F. Wong, K.-L. Chen, C. M. Lin, and M.-Y. Yeh, J. Appl.
Polym. Sci., 104, 3292 (2007).
(20) M. Wang, Y. Yu, X. Wu, and S. Li, Polymer, 45, 1253 (2004).
(21) J. Altman, M. Shoef, M. Wilchek, and A. Warshawsky, J.
Chem. Soc. Perkin Trans., 1, 59 (1984).
(22) H. Kimoto and L. A. Cohen, J. Org. Chem., 45, 3831 (1980).
(23) (a) J. M. Barton and P. M. Shepherd, Makromol. Chem., 176,
919 (1975); (b) M. S. Heise and G. C. Martin, J. Appl. Polym.
Sci., 39, 721 (1990).
(24) T. J. Dearlove, J. Appl. Polym. Sci., 14, 1615 (1970).
(25) J. Berger and F. Lohse, J. Appl. Polym. Sci., 30, 531 (1985).
(26) S. K. Ooi, W. D. Cook, G. P. Simon, and C. H. Such, Polymer,
41, 3639 (2000).
(27) S. Wang and C. P. Wong, 1999 International Symposium on
Advanced Packaging Materials, p. 317 (1999).
(28) H. E. Kissinger, Anal. Chem., 29, 1702 (1957).
(29) S.-J. Park, M.-K. Seo, J.-R. Lee, and D.-R. Lee, J. Polym. Sci.
Part A: Polym. Chem., 39, 187 (2001).
(30) M. S. Heise and G. C. Martin, Macromolecules, 22, 99 (1989).
(31) L. Núñez, M. R. Núñez, M. Villanueva, A. Castro, and B.
Rial, J. Appl. Polym. Sci., 85, 366 (2002).
(32) N. Galego and F. González, Polym. Int., 40, 213 (1996).
(33) S. Wu, J. D. Jorgensen, A. D. Skaja, J. P. Williams, and M. D.
Soucek, Prog. Org. Coat., 36, 21 (1999).
Macromol. Res., Vol. 18, No. 4, 2010