Progress in Organic Coatings 60 (2007) 328–334

Hyperbranched polyamine: A promising curing agent for a vegetable

oil-based poly(ester-amide) resin
Sibdas Singha Mahapatra, Niranjan Karak ∗
Department of Chemical Sciences, Tezpur University, Tezpur 784028, Assam, India
Received 15 March 2007; received in revised form 6 August 2007; accepted 6 August 2007

Abstract
A hyperbranched polyamine (HBPA) has been synthesized by a nucleophilic displacement polymerization of cyanuric chloride with an aromatic
diamine, 4,4 -(1,3-phenylene diisopropylidene) bis-aniline by using an A2 + B3 approach with high yield (>78%). The synthesized polyamine was
characterized by 1 H NMR, 13 C NMR and FT-IR spectroscopic studies, X-ray diffraction study, elemental and thermogravimetric analyses and by
measurement of solubility and solution viscosity. The polymer is soluble in polar solvents like DMAc, DMSO, DMF, THF, etc. but insoluble in
water and non-polar solvents. The flame retardancy as measured by limiting oxygen index (LOI) test of the polymer indicates its self-extinguishing
characteristic. This hyperbranched polyamine has been utilized as an effective curing agent for a Mesua ferrea L. seed oil-based poly(ester-amide)
resin. This hyperbranched polyamine alone as well as with conventional metal catalyzed peroxide system is found to effectively cure the above
resin at dose levels of 2.5–10 phr. The hyperbranched polyamine not only enhances the rate of crosslinking reaction but it also improves many
desirable performance characteristics especially the thermostability, flame retardancy, hardness, impact strength, chemical resistance, etc. of the
cured resin. Thus this study indicated that this hyperbranched polyamine acts as a promising curing agent for poly(ester-amide) resin.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Hyperbranched polyamine; A2 + B3 approach; Poly(ester-amide) resin; Vegetable oil; Coating performance; Flame retardancy

1. Introduction and unusual properties [4–7]. Hyperbranched polymers exhibit

Thermosetting resins need to be formulated with a few addi-
tives to crosslink and to obtain desirable level of performance
characteristics for their different applications [1]. Among these
additives, the crosslinking agents are the most important. A large
numbers of different crosslinking agents are available commer-
cially for this purpose. The resins based on vegetable oil are
conventionally cured by transition metal catalyzed peroxide sys-
tems such as Co-/Mn-octate/napthate with methyl ethyl ketone
peroxide (MEKP) in the presence of styrene as a reactive diluent
[2]. However, this system requires long time to achieve opti-
mum level of crosslinking, especially for the resins obtained
from non-drying vegetable oils [3]. Thus there is a need of an
effective crosslinking agent for this resin.
Non-linear highly branched polymers such as dendrimers
and hyperbranched polymers have received considerable atten-
tion in recent years due to their unique architectural features
∗ Corresponding author. Tel.: +91 3712 267327.
E-mail address: nkarak@tezu.ernet.in (N. Karak).
many useful properties like high solubility, low melt and solu-
tion viscosity, etc. in contrast to their linear analogs of same
molar mass. This is because of the highly functionalized glob-
ular and non-entangled structures of hyperbranched polymers
[8]. Further these polymers are being prepared by single step
processes and thus obtained in large scale at a reasonable cost,
which makes them more interesting for commercial applica-
tions [9,10]. They are generally synthesized from ABx (x ≥ 2)
type monomers but due to infrequent commercial availability of
this type of monomers, researchers incline to focus towards the
employment of polycondensation of A2 and B3 type monomers.
A few successful attempts have already been made for synthe-
sis of hyperbranched polyethers, polyamides, polyimide, etc.
[11–16] using this strategy. Due to the presence of large num-
ber of active surface functional groups, low viscosity and tailor
made compatibility; they may be utilized as excellent candidates
in crosslinking of many thermosetting polymers. A few reports
on effective curing of epoxy resins by hyperbranched polymers
have also been published [17,18].
An important vegetable oil based industrial resin, poly(ester-
amide) improves the film characteristics compared to the

0300-9440/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2007.08.004
 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334
conventional alkyd resins in terms of drying time, hardness,
chemical resistance, etc. [3,19,20]. However, poor flame retar-
dancy limits their uses in many applications like electronics, high
performance adhesives and coatings, etc. [21]. A considerable
attention has been paid, therefore, to control the flammability of
vegetable oil-based poly(ester-amide) resins. Most of the com-
mercially used flame retardants are either inorganic or halogen
based organic small molecular weight compounds. However,
both of them have some serious disadvantages like corrosion
of metal components and more importantly the generation of
toxic hydrogen halide gases during combustion process along
with low compatibility, leaching, migration, and volatility [22].
Again, sometimes to attain desirable level of flame retardancy,
large amount of additives is required to be incorporated in the
resin system, which may cause deterioration of many other prop-
erties due to physical dilution. However, use of nitrogenous
macromolecular flame retardant eliminates all the above draw-
backs. Again non-reactive flame retardants are only present as
so called ‘inert filler’, while reactive types are more effective
as they are chemically attached with the resin system [23]. In
the present investigation, it is therefore expected that the hyper-
branched reactive polyamine with thermostable s-triazine ring
may effectively function as crosslinking agent, reactive flame
retardant, heat stabilizer, viscosity reducer as well as improver
to chemical resistance in many chemical media.
The authors, therefore, wish to report here the synthesis, char-
acterization and application of a s-triazine based hyperbranched
polyamine as a promising curing agent for a vegetable oil-based
poly(ester-amide) resin.
2. Experimental
2.1. Materials
N,N -Dimethyl acetamide (DMAc, Merck, India) was
used after purification by vacuum distillation over calcium
oxide. 2,4,6-Trichloro s-triazine (CYC), diisopropyl ethylamine
(DIPEA, Merck, Germany), para toluene sulphonic acid (PTSA)
and tetrahydrofuran (THF, SD Fine Chem, India) were used
as received. 4,4 -(1,3-Phenylene diisopropylidene) bis-aniline
(PDA, Aldrich Chemie, Germany) was used after purification
from aqueous ethanol. Methyl ethyl ketone peroxide (MEKP)
and cobalt octate (Kumud Enterprise, Kharagpur) were used
without further purification. Styrene (Merck, India) was used
after purification by the conventional procedure. The phthalic
anhydride-based poly(ester-amide) resin was prepared accord-
ing to the procedure as described in the earlier paper [3].
2.2. Measurements
FT-IR spectra for the polymer systems were recorded in a
Nicolet (Impact 410, Madison, USA) FT-IR spectrophotome-
ter by using KBr pellet. 1 H NMR and 13 C NMR spectra of the
polymer were recorded with 400 MHz AMX (Michigan, USA)
NMR spectrometer by using d6 -DMSO as the solvent and TMS
as an internal standard. X-ray diffraction study was made on the
powder of the hyperbranched polyamine at room temperature
329
(ca. 27 ◦ C) on a Rigaku X-ray diffractometer (Miniflex, UK).
The inherent viscosity of the polymer was measured with 0.5%
(w/v) solution in DMAc at 27 ± 0.1 ◦ C by using an Ubbelohde
suspended level viscometer. Thermogravimetric (TG) analysis
and differential scanning calorimetry (DSC) were carried out in
Shimazdu TG 50 and DSC 60 thermal analyzers, respectively
using the nitrogen flow rate of 30 mL/min and at the heating rate
of 10 ◦ C/min. The flame retardancy test of all samples was car-
ried out by measurement of limiting oxygen index (LOI) value
by a flammability tester (S.C. Dey Co., Kolkata) as per the stan-
dard ASTM D 2863-77 procedure for self-supported samples.
The limiting oxygen index (LOI) value of the powder polymer
was determined by using modified version of the standard ASTM
D 2863-77. The density of the polymer was determined by pyc-
nometer in dry toluene at room temperature (ca. 27 ◦ C) by the
conventional liquid displacement method. The solubility of the
polymer was observed in different solvents up to 7 days at room
temperature, using 0.01 g sample in 1.0 mL solvent. The chlo-
rine content of the polymer was determined by the standard
Schoniger oxygen combustion method. The film thickness of
cured films was determined by Pentest, coating thickness gauge
meter (Sheen Instrument Ltd., Model 1117, UK). The coating
performance of the cured films was evaluated by determination
of pencil hardness using pencils of different grades ranging from
6B to 6H, impact resistance by falling weight (ball) method and
adhesion (cross-cut) by using commercial cello tape.
2.3. Synthesis of polymer (HBPA)
To a 250 mL three-necked round bottom flask 5.88 g
(0.017 mol) of PDA, 1.46 g (0.0113 mol) of DIPEA and 40 mL
of DMAc were taken under N2 purge. In the clear solution of the
above mixture, 2.10 g (0.0113 mol) of CYC solution in 40 mL
DMAc was added dropwise for about 1 h at 0–5 ◦ C with constant
stirring. After completion of the addition, the reaction mixture
was stirred for another 1 h under the same condition. Then the
temperature was raised to 40–45 ◦ C. At this temperature, again
1.46 g of DIPEA was added in the reaction mixture and stirring
was continued for another 2 h. Then the temperature was again
raised to 85–90 ◦ C and further 1.46 g of DIPEA was added. The
reaction was continued for another 6 h under the same condition.
Then it was cooled and poured slowly with constant stirring in
1 L of ice cold water. The precipitate formed was collected by fil-
tration and washed several times at first with methanol followed
by acetone to remove the unreacted reagents. The product was
dried under vacuum at temperature of 45–50 ◦ C for 3 days to
obtain dry powder of the polymer.
2.4. Curing of poly(ester-amide) resin
A homogenous mixture of poly(ester-amide) resin with
30 phr (parts per hundred gram of resin) of styrene as the reac-
tive diluent, 4 phr of MEKP as the initiator and 2 phr of cobalt
octate as the accelerator without, and with 5.0, 7.5 and 10.0 phr
of hyperbranched polyamine as 10% solution in THF along with
0.01 phr of PTSA was prepared separately in a glass beaker
at room temperature by hand stirring for 5–7 min. Samples
330 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334
Scheme 1. Synthesis of hyperbranched polyamine.
containing the resin with only hyperbranched polyamine in
the presence of 0.01 phr PTSA at dose levels of 2.5, 5 and
10 phr were also prepared. Then the mixtures were uniformly
coated on mild steel plates (150 mm × 50 mm × 1.60 mm),
tin plates (150 mm × 50 mm × 0.40 mm) and glass plates
(75 mm × 25 mm × 1.75 mm) and allowed to cure at specified
temperatures for the different time period.
3. Results and discussion
3.1. Synthesis of hyperbranched polyamine (HBPA)
The s-triazine based hyperbranched polyamine was synthe-
sized considering both high thermostability and good solubility
by using an A2 + B3 approach (Scheme 1). The A2 monomer
is 4,4 -(1,3-phenylenediisopropylidene) bis-aniline and the B3
monomer is cyanuric chloride (CYC) for this reaction. As the
nucleophilic aromatic amine substitution reaction of CYC is
highly selective [24], so polymerization reaction was carried out
at three different temperatures, i.e. at 0–5 ◦ C for 2 h, at 40–45 ◦ C
for 2 h and at 85–90 ◦ C for 6 h. Gelation was avoided by using the
judicious choice of reaction conditions such as appropriate ratio,
concentration and slow addition of the monomers. The reaction
succeeded by using 3:2 mole ratio of A2 and B3 monomers
and slow addition of a very dilute solution (<10%, w/v) of B3
monomer into the A2 monomer of same dilution in DMAc sol-
vent. The reaction was further facilitated by using diisopropyl
ethylamine, an effective base to scavenge the HCl gas, which
was generated during the substitution reaction. These reaction
conditions not only offered the product without gel but also the
yield was very high (>78%).
3.2. Characterization of HBPA
The physical properties like density and color of the poly-
mer were found to be 1.18 g/cm3 and light brown, respectively.
 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334 331

Fig. 2. 13 C NMR spectrum of hyperbranched polyamine.

Fig. 1. 1 H NMR spectrum of hyperbranched polyamine.
The polymer is amorphous in nature as indicated by XRD
study. The low dilute solution viscosity value (inherent viscos-
ity = 0.14 dL/g) of this polymer may be due to low molecular
weight as well as globular type structure [6,25].
The FT-IR spectrum of the polymer indicates the presence of
aromatic amine linkage, N–H stretching at 3170–3360 cm−1 and
bending at 1578–1596 cm−1 for primary and 1488–1515 cm−1
for secondary amines, respectively. The marginal shift of these
absorption values may be due to the presence of H-bonding
[26]. The presence of the above peaks in the polymer con-
firmed the occurrence of nucleophilic displacement reaction
with formation of secondary amine bond. The other important
linkages such as C N of triazine moiety at 1406–1409 cm−1
and aromatic C–Cl at 1016 cm−1 were also observed. The struc-
ture of the polymer was further supported by NMR studies.
The 1 H NMR spectrum (Fig. 1) of the polymer indicates the
presence of important protons. The peaks at δ = 10.81 ppm,
δ = 9.12 ppm and δ = 8.86 ppm are due to >N–H protons attached
with the terminal triazine unit (triazine with two unsubstituted
chlorine atoms), with the linear unit (triazine with one unsub-
stituted chlorine atom) and with the dendritic unit (triazine
with no chlorine atom), respectively for this hyperbranched
polyamine (Scheme 1). The other important peaks such as
–NH2 protons at δ = 3.60 ppm, isopropylediene –CH3 protons
at δ = 1.49–1.54 ppm and protons for aromatic moieties at
δ = 6.45–7.57 ppm as multiplet were also observed in the spec-
trum. The 13 C NMR spectrum (Fig. 2) further supports the
structure of the polymer. All the important peaks such as those
due to carbon atoms present in the dendritic triazine units at
δ = 164.31 ppm, carbons attached with secondary >N–H groups
at δ = 150.44–134.27 ppm, carbon atoms at ortho and meta to
isopropyl groups at δ = 127.22–121.67 ppm and carbon atoms of
isopropylediene moiety at δ = 42.07–30.12 ppm were observed
in this spectrum [26]. The elemental analysis data (Table 1) also
support the structure of the polymer as shown in Scheme 1.
The variation of the elemental analysis values from the ideal
dendritic structure (calculated) is quite obvious as the hyper-
branched structure has more structural defects as substitution
Table 1
Elemental analysis data of the hyperbranched polyamine
Polymer % of element
C H N Cla
HBPA
Calculatedb 78.18 6.59 14.21 0.0
Found 76.02 6.37 13.68 3.0
a Estimated by Schoniger oxygen combustion method.
b Calculated using ideal dendritic structure with no chlorine atom.
was not completed and is complex in nature. Thus it is very dif-
ficult to assign the exact structure of the hyperbranched polymer.
3.2.1. Degree of branching
The determination of degree of branching (DB) of the hyper-
branched polymers is very important and is usually calculated
by using Frechet’s equation as follows [27] from 1 H NMR spec-
trum:
D+T
DB =
D+T+L
where D, T, and L refer to the number of dendritic, terminal
and linear units in the structure of the polymer, respectively
(Scheme 1). The value of DB for the polymer is found to be
0.52. This value indicates that the polymer exhibits near to ideal
hyperbranched structure.
3.3. Properties of hyperbranched polyamine
The polymer was soluble only in highly polar solvents such
as DMAc, DMF, DMSO, NMP, THF, etc. partly soluble in ace-
tone, methanol, etc. but insoluble in hydrocarbon solvents, water,
common chlorinated organic solvents, etc. This solubility con-
firmed that the polymer is not a crosslinked gel product. Further it
has been found that the solubility is further enhanced by addition
of a slight amount of dilute HCl, which may be due to reduction
of inter molecular attraction among the chain molecules.
The amorphous nature of hyperbranched polymer was fur-
ther proved by DSC study, as no melting or crystallization peak
was observed in the thermogram. However, the study indicates
332 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334
that the polymer has high Tg at about 236 ◦ C. Thermogravimet-
ric (TG) analysis of the polymer indicates that the polymer is
thermostable up to 280 ◦ C without any decomposition, and 50%
decomposition occurred at 550 ◦ C. The char residue at 800 ◦ C
is 44%, which indicates that the polymer formed a high amount
of non-combustible product after decomposition. This result
indicates that the polymer may show self-extinguishing char-
acteristic. This is confirmed by the measurement of LOI value
(LOI = 37). These results motivate that the polymer can be used
as a flame retardant in other base polymers. The high thermosta-
bility and self-extinguishing characteristics of this polymer are
due to the presence of thermostable triazine unit, aromatic
moiety and non-flammable special elements like nitrogen and
chlorine in the structure [28].
3.4. Curing study of the poly(ester-amide) resin
The resin was not cured at room temperature or even at
high temperature without curing agent. However, the same
was cured by using a combination of curing agents such as
styrene, MEKP and cobalt octate at 175 ◦ C for 4 h. But when
hyperbranched polyamine in the presence of PTSA was used
with the above system, it has been found that the curing time
decreases with the increase of dose of hyperbranched polymer
(Table 2). Further, using hyperbranched polyamine alone as the
curing agent, it can be cured at 175 ◦ C for 7–4 h at dose level
of 2.5–10 phr. This is due to the presence of large numbers
of free reactive surface amino groups in the structure of the
hyperbranched polyamine, which may react with the ester, free
acid, hydroxyl groups, unsaturation moiety, etc. of the polyester
resin. The higher dose than 10 phr was not studied because of
commercial point of view as well as due to the fact that the
cured resin became rather brittle even at dose level of 10 phr of
hyperbranched polymer. This may be due the presence of rigid
structure of the hyperbranched polymer.
3.5. Coating performance of the poly(ester-amide) resin
The performance of the poly(ester-amide) resin was stud-
ied by the measurement of drying time, pencil hardness, impact
resistance, adhesive strength, thermal stability, flame retardancy
(LOI) and chemical resistance in different chemical media for
the resins with conventional drying system compared to conven-
tional drier system with 5 phr of hyperbranched polyamine. The
miscibility of the hyperbranched polymer with the resin system
Table 2
Drying time of poly(ester-amide) resin
Resin code Curing system (phr)
PEA-CV 30:4:2::styrene:MEKP:Co-octate
PEA-CV-2.5PA 30:4:2:2.5::styrene:MEKP:Co-octate:HBPA
PEA-CV-5PA 30:4:2:5::styrene:MEKP:Co-octate:HBPA
PEA-CV-7.5PA 30:4:2:7.5::styrene:MEKP:Co-octate:HBPA
PEA-2.5PA 2.5::HBPA
PEA-5PA 5::HBPA
PEA-10PA 10::HBPA
Table 3
Coating properties of poly(ester-amide) resin
Property PEA-CV PEA-CV-5PA
Drying time (h) 4.0 3.0
Pencil hardness 2H pass 3H pass
Adhesion (%) 100 100
Impact resistance (cm) 10–12 14–15
Specific gravity 0.89 0.91
Swelling (%) 12.87 4.76
LOI 21 25
Char residue (%) 4.6 11.2
was studied by SEM (Fig. 3) and it has been observed that there
is no distinct phase separation in both the cases.
3.5.1. Physical properties
The drying of resin means the conversion from the liquid
state to solid state by crosslinking reaction, which forms a three-
dimensional network structure. In this case the crosslinking is
mainly from radical reaction of resin initiated by peroxide or
aerial oxidation by absorbing oxygen from the atmosphere at
high temperature in the presence of conventional drier system
(PEA-CV). As the oil is non-drying, so the resin requires a long
time to dry [3]. Whereas in case of drying of resin with hyper-
branched polyamine (PEA-CV-5PA) the time required is less
(Table 3), which is due to the various crosslinking reactions as
mentioned above (Section 3.4) along with the radical reaction.
The pencil hardness (Table 3) value for the PEA-CV-5PA is
higher than the PEA-CV due to higher crosslinking density, the
presence of rigid aromatic moieties and greater H-bonding in the
former than the latter. Swelling test and FT-IR study also sup-
ports this fact. The FT-IR spectrum of PEA-CV-5PA indicates
the presence of broad band for extended H-bonded >C O groups
at 1695 cm−1 . The adhesion characteristic for both the resin sys-
tems is very good, which is due to the presence of different
polar groups. A little improvement in falling ball impact resis-
tance in case of PEA-CV-5PA compared with PEA-CV indicates
that hyperbranched polyamine can also act as impact modifier.
This result is also supported by other results [29]. These results
indicated that PEA-CV-5PA is better material than PEA-CV for
surface coating applications.
3.5.2. Flame retardancy study
As already stated in the introduction the polymeric nature
and hyperbranched architecture make these types of polymers
very much compatible with the other polymeric systems, so it
is expected and also found from SEM studies that HBPA and
poly(ester-amide) resin formed a miscible system (Fig. 3). This
result also indicates that the hyperbranched polyamine has good
Time (h) compatibilizing capability for other components in base resin
system.
4
3.5 It has already been reported [28] and found in this study that
3 triazine based polymers have very good flame retardant behavior
2.5 for their excellent char forming effect. This is mainly due to
7 the presence of tertiary nitrogen in their ring structure. They
6
also have other advantages like low toxicity, no corrosion, low
4
smoke, good compatibility, etc. The LOI value may be used
 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334 333

Fig. 3. SEM micrograms for PEA-CV (a) and PEA-CV-5PA (b).

as an indicator to evaluate flame retardancy of a polymer. The Table 4

hydrocarbon-based polymers with high hydrogen/carbon ratio Chemical resistance of cured poly(ester-amide) resin
like vegetable oil based resins are highly susceptible to flame. Medium Weight loss (%)
Thus the flame-retardant behavior of these resin systems was PEA-CV PEA-CV-5PA
examined by the LOI test. The results are tabulated in Table 3. It
has been observed that the LOI value of poly(ester-amide) resin Distilled water −0.01 0.01
10 wt% aqueous NaCl 0.01 0.00
without flame retardant additive is lower than that with 5 phr of 5 wt% aqueous HCl 0.02 0.01
hyperbranched polyamine. This increment of LOI value is due 3 wt% aqueous NaOH 0.20 0.12
to flame retardant characteristic of HBPA as it has nitrogen and
chlorine as the special elements in its structure.

3.5.3. Thermal study 3.5.4. Chemical resistance

From the thermogravimetric (TG) analysis of the resin sys-
tems it has been found that the thermostability of the resin was
enhanced a little by the presence of hyperbranched polyamine
(Fig. 4). The char residue with the HBPA is much higher than
that without hyperbranched polymer at 600 ◦ C (Table 3). These
findings suggest that hyperbranched polyamine not only pro-
motes some amounts of char formation (where heterocyclic
moiety is mainly responsible) in the solid polymers, but it also
helps the thermostability of the resin, which is due to chemical
crosslinking, formation of H-bonding, enhanced compatibility,
etc.
The results for the cured resin systems (Table 4) indicate
that they have excellent chemical resistance in all tested media
except dilute aqueous NaOH solution. In alkali solution the loss
of adhesion was observed in both the cases, though the loss of
weight in case of PEA-CV is little higher than PEA-CV-5PA
system. This small improvement of alkali resistance may be due
to the higher crosslinking density, the presence of rigid aromatic
moieties and greater H-bonding in the former than the latter.
4. Conclusion

From this study it can be concluded that a flame retardant

hyperbranched polyamine was synthesized successfully by an
A2 + B3 approach. The synthesized polymer was characterized
fully by different analytical and spectroscopic techniques. This
hyperbranched polymer was used successfully as a promising
multipurpose curing agent for Mesua ferrea L. seed oil-based
poly(ester-amide) resin. The performance characteristics like
rate of curing, hardness, impact resistance, thermostability,
flame retardancy, chemical resistance, etc. of the resin are
improved by the addition of the hyperbranched polyamine at
relatively low dose level.

Acknowledgement

Fig. 4. TG thermograms for I = HBPA, II = PEA-CV, III = PEA-5PA and The authors express their gratitude to CSIR, New Delhi for
IV = PEA-CV-5PA. the financial support (No. 01(1868/03/EMR-II)) of this project.
334 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334

References [16] J. Fang, H. Kita, K. Okomoto, Macromolecules 33 (2000) 4639.

[17] D. Ratna, G.P. Simon, Polymer 42 (2001) 8833.
[1] J.A. Brydson, Plastics Materials, 4th ed., Butterworths, London, 1982. [18] J.H. Oh, J. Jang, S.-H. Lee, Polymer 42 (2001) 8339.
[2] N. Dutta, N. Karak, Prog. Org. Coat. 49 (2004) 146. [19] J. Economy, J. Macromol. Sci. Chem. A 21 (1984) 1705.
[3] S.S. Mahapatra, N. Karak, Prog. Org. Coat. 51 (2004) 103. [20] T.K. Rao, V.M. Mannari, D.A. Raval, J. Sci. Ind. Res. 55 (1996) 971.
[4] B. Voit, J. Polym. Sci. 33 (2000) 1720. [21] F. Miyashiro, Electronics Packaging Technology Road Map for the Year
[5] M. Jikei, M. Kakimoto, Prog. Polym. Sci. 26 (2001) 1233. 2010, Japan Institute of Electronic Packaging, Japan, 1999.
[6] D.A. Tomalia, J.M.J. Frechet, J. Polym. Sci. Part A: Polym. Chem. 40 [22] H. Horacek, R. Grabner, Polym. Degrad. Stab. 54 (1996) 205.
(2002) 2719. [23] D. Price, K. Pyrah, T.R. Hull, G.J. Milnes, J.R. Ebdon, B.J. Hunt, P. Joseph,
[7] C. Gao, Y. Yan, Prog. Polym. Sci. 29 (2004) 183. Polym. Degrad. Stab. 77 (2002) 227.
[8] J. Hao, M. Jikei, M. Kakimoto, Macromolecules 35 (2002) 5372. [24] J.T. Thurston, J.R. Dudley, D.W. Kaiser, I. Hechenbleikner, F.C. Schaefer,
[9] H.J. Lee, Y.S. Perk, J.L. Jin, Bull. Korean Chem. Soc. 23 (2002) 1201. D. Holm-Hansen, J. Am. Chem. Soc. 73 (1952) 2981.
[10] M. Seiler, D. Kohter, W. Arlt, Sep. Purif. Technol. 29 (2002) 245. [25] C.R. Yates, W. Hayes, Eur. Polym. J. 40 (2004) 1257.
[11] T. Emrick, H.T. Chang, J.M.J. Frechet, Macromolecules 32 (1999) 6380. [26] R.M. Silverstein, G.C. Bassler, T.C. Morril, Spectrometric Identification of
[12] O. Monticelli, A. Mariani, B. Voit, H. Komber, R. Mendichi, V. Pitto, D. Organic Compounds, 6th ed., Wiley, New York, 1998.
Tabuani, S. Russo, High Perform. Polym. 13 (2001) 45. [27] C.J. Hawker, R. Lee, J.M.J. Frechet, J. Am. Chem. Soc. 113 (1991)
[13] J. Borah, N. Karak, Polym. Int. 53 (2004) 2026. 4583.
[14] M. Jikei, S.H. Chon, M. Kakimoto, S. Kawauchi, T. Imase, J. Watanabe [28] X.-P. Hu, Y.-L. Li, Y.-Z. Wang, Macromol. Mater. Eng. 289 (2004) 208.
Macromolecules 32 (1999) 2061. [29] O. Gryshchuk, N. Jost, J. Karger-Kocsis, J. Appl. Polym. Sci. 84 (2002)
[15] H. Chen, J. Yin, J. Polym. Sci. Part A: Polym. Chem. 40 (2002) 3804. 672.