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
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) 328–334 329
conventional alkyd resins in terms of drying time, hardness, (ca. 27 ◦ C) on a Rigaku X-ray diffractometer (Miniflex, UK).
chemical resistance, etc. [3,19,20]. However, poor flame retar- The inherent viscosity of the polymer was measured with 0.5%
dancy limits their uses in many applications like electronics, high (w/v) solution in DMAc at 27 ± 0.1 ◦ C by using an Ubbelohde
performance adhesives and coatings, etc. [21]. A considerable suspended level viscometer. Thermogravimetric (TG) analysis
attention has been paid, therefore, to control the flammability of and differential scanning calorimetry (DSC) were carried out in
vegetable oil-based poly(ester-amide) resins. Most of the com- Shimazdu TG 50 and DSC 60 thermal analyzers, respectively
mercially used flame retardants are either inorganic or halogen using the nitrogen flow rate of 30 mL/min and at the heating rate
based organic small molecular weight compounds. However, of 10 ◦ C/min. The flame retardancy test of all samples was car-
both of them have some serious disadvantages like corrosion ried out by measurement of limiting oxygen index (LOI) value
of metal components and more importantly the generation of by a flammability tester (S.C. Dey Co., Kolkata) as per the stan-
toxic hydrogen halide gases during combustion process along dard ASTM D 2863-77 procedure for self-supported samples.
with low compatibility, leaching, migration, and volatility [22]. The limiting oxygen index (LOI) value of the powder polymer
Again, sometimes to attain desirable level of flame retardancy, was determined by using modified version of the standard ASTM
large amount of additives is required to be incorporated in the D 2863-77. The density of the polymer was determined by pyc-
resin system, which may cause deterioration of many other prop- nometer in dry toluene at room temperature (ca. 27 ◦ C) by the
erties due to physical dilution. However, use of nitrogenous conventional liquid displacement method. The solubility of the
macromolecular flame retardant eliminates all the above draw- polymer was observed in different solvents up to 7 days at room
backs. Again non-reactive flame retardants are only present as temperature, using 0.01 g sample in 1.0 mL solvent. The chlo-
so called ‘inert filler’, while reactive types are more effective rine content of the polymer was determined by the standard
as they are chemically attached with the resin system [23]. In Schoniger oxygen combustion method. The film thickness of
the present investigation, it is therefore expected that the hyper- cured films was determined by Pentest, coating thickness gauge
branched reactive polyamine with thermostable s-triazine ring meter (Sheen Instrument Ltd., Model 1117, UK). The coating
may effectively function as crosslinking agent, reactive flame performance of the cured films was evaluated by determination
retardant, heat stabilizer, viscosity reducer as well as improver of pencil hardness using pencils of different grades ranging from
to chemical resistance in many chemical media. 6B to 6H, impact resistance by falling weight (ball) method and
The authors, therefore, wish to report here the synthesis, char- adhesion (cross-cut) by using commercial cello tape.
acterization and application of a s-triazine based hyperbranched
polyamine as a promising curing agent for a vegetable oil-based 2.3. Synthesis of polymer (HBPA)
poly(ester-amide) resin.
To a 250 mL three-necked round bottom flask 5.88 g
2. Experimental (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
2.1. Materials 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
N,N -Dimethyl acetamide (DMAc, Merck, India) was stirring. After completion of the addition, the reaction mixture
used after purification by vacuum distillation over calcium was stirred for another 1 h under the same condition. Then the
oxide. 2,4,6-Trichloro s-triazine (CYC), diisopropyl ethylamine temperature was raised to 40–45 ◦ C. At this temperature, again
(DIPEA, Merck, Germany), para toluene sulphonic acid (PTSA) 1.46 g of DIPEA was added in the reaction mixture and stirring
and tetrahydrofuran (THF, SD Fine Chem, India) were used was continued for another 2 h. Then the temperature was again
as received. 4,4 -(1,3-Phenylene diisopropylidene) bis-aniline raised to 85–90 ◦ C and further 1.46 g of DIPEA was added. The
(PDA, Aldrich Chemie, Germany) was used after purification reaction was continued for another 6 h under the same condition.
from aqueous ethanol. Methyl ethyl ketone peroxide (MEKP) Then it was cooled and poured slowly with constant stirring in
and cobalt octate (Kumud Enterprise, Kharagpur) were used 1 L of ice cold water. The precipitate formed was collected by fil-
without further purification. Styrene (Merck, India) was used tration and washed several times at first with methanol followed
after purification by the conventional procedure. The phthalic by acetone to remove the unreacted reagents. The product was
anhydride-based poly(ester-amide) resin was prepared accord- dried under vacuum at temperature of 45–50 ◦ C for 3 days to
ing to the procedure as described in the earlier paper [3]. obtain dry powder of the polymer.
FT-IR spectra for the polymer systems were recorded in a A homogenous mixture of poly(ester-amide) resin with
Nicolet (Impact 410, Madison, USA) FT-IR spectrophotome- 30 phr (parts per hundred gram of resin) of styrene as the reac-
ter by using KBr pellet. 1 H NMR and 13 C NMR spectra of the tive diluent, 4 phr of MEKP as the initiator and 2 phr of cobalt
polymer were recorded with 400 MHz AMX (Michigan, USA) octate as the accelerator without, and with 5.0, 7.5 and 10.0 phr
NMR spectrometer by using d6 -DMSO as the solvent and TMS of hyperbranched polyamine as 10% solution in THF along with
as an internal standard. X-ray diffraction study was made on the 0.01 phr of PTSA was prepared separately in a glass beaker
powder of the hyperbranched polyamine at room temperature 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
containing the resin with only hyperbranched polyamine in highly selective [24], so polymerization reaction was carried out
the presence of 0.01 phr PTSA at dose levels of 2.5, 5 and at three different temperatures, i.e. at 0–5 ◦ C for 2 h, at 40–45 ◦ C
10 phr were also prepared. Then the mixtures were uniformly for 2 h and at 85–90 ◦ C for 6 h. Gelation was avoided by using the
coated on mild steel plates (150 mm × 50 mm × 1.60 mm), judicious choice of reaction conditions such as appropriate ratio,
tin plates (150 mm × 50 mm × 0.40 mm) and glass plates concentration and slow addition of the monomers. The reaction
(75 mm × 25 mm × 1.75 mm) and allowed to cure at specified succeeded by using 3:2 mole ratio of A2 and B3 monomers
temperatures for the different time period. 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
3. Results and discussion ethylamine, an effective base to scavenge the HCl gas, which
was generated during the substitution reaction. These reaction
3.1. Synthesis of hyperbranched polyamine (HBPA) conditions not only offered the product without gel but also the
yield was very high (>78%).
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 3.2. Characterization of HBPA
is 4,4 -(1,3-phenylenediisopropylidene) bis-aniline and the B3
monomer is cyanuric chloride (CYC) for this reaction. As the The physical properties like density and color of the poly-
nucleophilic aromatic amine substitution reaction of CYC is 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
Table 1
Fig. 1. 1 H NMR spectrum of hyperbranched polyamine. Elemental analysis data of the hyperbranched polyamine
Polymer % of element
The polymer is amorphous in nature as indicated by XRD
study. The low dilute solution viscosity value (inherent viscos- C H N Cla
ity = 0.14 dL/g) of this polymer may be due to low molecular HBPA
weight as well as globular type structure [6,25]. Calculatedb 78.18 6.59 14.21 0.0
The FT-IR spectrum of the polymer indicates the presence of Found 76.02 6.37 13.68 3.0
aromatic amine linkage, N–H stretching at 3170–3360 cm−1 and a Estimated by Schoniger oxygen combustion method.
bending at 1578–1596 cm−1 for primary and 1488–1515 cm−1 b Calculated using ideal dendritic structure with no chlorine atom.
for secondary amines, respectively. The marginal shift of these
absorption values may be due to the presence of H-bonding was not completed and is complex in nature. Thus it is very dif-
[26]. The presence of the above peaks in the polymer con- ficult to assign the exact structure of the hyperbranched polymer.
firmed the occurrence of nucleophilic displacement reaction
with formation of secondary amine bond. The other important 3.2.1. Degree of branching
linkages such as C N of triazine moiety at 1406–1409 cm−1 The determination of degree of branching (DB) of the hyper-
and aromatic C–Cl at 1016 cm−1 were also observed. The struc- branched polymers is very important and is usually calculated
ture of the polymer was further supported by NMR studies. by using Frechet’s equation as follows [27] from 1 H NMR spec-
The 1 H NMR spectrum (Fig. 1) of the polymer indicates the trum:
presence of important protons. The peaks at δ = 10.81 ppm,
D+T
δ = 9.12 ppm and δ = 8.86 ppm are due to >N–H protons attached DB =
with the terminal triazine unit (triazine with two unsubstituted D+T+L
chlorine atoms), with the linear unit (triazine with one unsub- where D, T, and L refer to the number of dendritic, terminal
stituted chlorine atom) and with the dendritic unit (triazine and linear units in the structure of the polymer, respectively
with no chlorine atom), respectively for this hyperbranched (Scheme 1). The value of DB for the polymer is found to be
polyamine (Scheme 1). The other important peaks such as 0.52. This value indicates that the polymer exhibits near to ideal
–NH2 protons at δ = 3.60 ppm, isopropylediene –CH3 protons hyperbranched structure.
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- 3.3. Properties of hyperbranched polyamine
trum. The 13 C NMR spectrum (Fig. 2) further supports the
structure of the polymer. All the important peaks such as those The polymer was soluble only in highly polar solvents such
due to carbon atoms present in the dendritic triazine units at as DMAc, DMF, DMSO, NMP, THF, etc. partly soluble in ace-
δ = 164.31 ppm, carbons attached with secondary >N–H groups tone, methanol, etc. but insoluble in hydrocarbon solvents, water,
at δ = 150.44–134.27 ppm, carbon atoms at ortho and meta to common chlorinated organic solvents, etc. This solubility con-
isopropyl groups at δ = 127.22–121.67 ppm and carbon atoms of firmed that the polymer is not a crosslinked gel product. Further it
isopropylediene moiety at δ = 42.07–30.12 ppm were observed has been found that the solubility is further enhanced by addition
in this spectrum [26]. The elemental analysis data (Table 1) also of a slight amount of dilute HCl, which may be due to reduction
support the structure of the polymer as shown in Scheme 1. of inter molecular attraction among the chain molecules.
The variation of the elemental analysis values from the ideal The amorphous nature of hyperbranched polymer was fur-
dendritic structure (calculated) is quite obvious as the hyper- ther proved by DSC study, as no melting or crystallization peak
branched structure has more structural defects as substitution was observed in the thermogram. However, the study indicates
332 S.S. Mahapatra, N. Karak / Progress in Organic Coatings 60 (2007) 328–334
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