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Title: Synthesis of pH responsive aggregates of hyperbranched copolymer of

cetyltrimethylammonium functionalized poly (l,2,3 triazoacrylate) and poly (acrylic acid)

In many applications, hyperbranched polymers (HBPs) have replaced dendrimers (which are
difficult to produce and thus expensive) and conventional polymers (which lack many useful
properties). HBPs feature high solubility in various solvents, low solution viscosities, high
degree of functionality with more void space for encapsulation of macromolecules. Till date,
synthesis of HBPs from a multifunctional core material by polycondensation method is well
followed. However, much of the starting monomers for polycondensation processes are very
expensive and hence are not encouraged in commercial applications. Much cheaper free radical
techniques (FRP) may produce highly branched polymers if a balanced combination of a
branching agent and a chain transfer agent is used where gelation is prevented. However, HBPs
produced by FRP lack high degree of functionality which again restricts their applications in
many areas. In this regard, we tried to synthesize a pH responsive long alkyl chained triazole
functionalized HBP and characterized its solution properties so that it could be further used for
host-guest application.
Experimental Details & Discussions
In the first step, a branched copolymer of propargyl acrylate (PA) and acrylic acid (AA) was
prepared by FRP in presence of varied concentration of a branching agent (divinyl benzeneDVB) and a chain transfer agent (dodecane thiol-DDT). Typically, measured quantity of PA,
DVB and DDT were dissolved in DMF. Then AA and FRP initiator (AIBN) were added to the
resultant mixture and homogenized for 30 minutes under nitrogen blanket. Finally,
polymerization was carried out at 70C for 20 hrs (optimized condition which prevented gelation
and yielded maximum products). The final polymer masses were precipitated from water and
collected after centrifugation at 4000 r.p.m. The settled masses were freeze dried. In order to
remove other unreacted ingredients, the masses were further precipitated from diethyl ether and
vacuum dried. 1HNMR (d6-DMSO) (ppm): 1.5-1.6 (-CH2 of polymer backbone), 2.5 (DMSO
and HCC- of propargyl moiety), 5.5 (-CH 2 of pendant unreacted vinyl groups derived from
DVB residues where only one vinyl group has undergone polymerization, i.e. acting as
branching unit), 7-7.5 (aromatic hydrogens in DVB) and 12-13 (-COOH). FTIR (cm -1): 3289
(CH stretching), 2121 (-CC- stretching), 2845 & 2925 (symmetric & asymmetric stretching of

CH2), 1730 (C=O of ester stretching) and 1640 (-COOH stretching). In our study, we used
various compositions of starting materials to synthesize HBPs like P150/50/0/0 (PA-50 mmol, AA-50
mmol, DVB-0 mmol & DDT-0 mmol), P1 50/50/1.25/2.5, P150/50/2.5/2.5, P150/50/5.0/2.5, P130/70/2.5/2.5 and
P170/30/2.5/2.5. All P1-HBPs (0.1 g/ml) except P1 50/50/0/0 were soluble in CHCl3, DMF, DCM, -CH3,
t-BuOH, acetone, DMSO and alkaline medium. They exhibited low solution viscosities in DMF
in the range 0.4-0.9 dl/g unlike 4.4 dl/g of the linear analogue. Interestingly, GPC
characterization revealed HBPs had high Mnavg in the range 3x106 g/mol unlike 4x106 g/mol of
the linear analogue. GPC also confirmed hyper branching in all samples as they had broad PDI
(8-10) and low values of (~ 0.5-0.6). In the next step, we attempted to prepare pH responsive
aggregates from P1-HBPs. P1-HBPs contained free propargyl groups and thus could be used for
click reactions- a potential tool for functionalization.
We prepared cetyltrimethylammonium azide (CTAN3) from CTAB by a simple SN2 reaction with
NaN3 in DMF at 90C for 24 hrs. CTAN 3 is soluble in DMF and thus was isolated by ultra
filtration where NaN3 and CTAB precipitated out. The orange filtrate was precipitated to diethyl
ether and vacuum dried at 50C for an overnight. 1HNMR (d6-DMSO) (ppm): 2.5 (DMSO) &
3.4 (-CH2N3). FTIR (cm-1): 2915 & 2845 (asymmetric & symmetric stretching of CH 2 from
CTA group), 2099 (C-N3 stretching). ESI mass m/z: 284 [M+].
Finally alkyne rich P1-HBPs were functionalized with CTAN 3. In a typical process, P1-HBPs
and CTAN3 were dissolved in 1: 1 t-BuOH: H 2O medium. Then CuSO4.5H2O and sodium
ascorbate (NaAsc) were added to the mixture and purged under nitrogen for 30 minutes. Click
reaction was carried out at 60C for 48 hrs (click reaction on polymer is a slow process). Then
these functionalized HBPs (P2-HBPs) were isolated by centrifugation at 4000 r.p.m for 15
minutes and dialyzed against EDTA solution continuously for 2 days and then against D.D H 2O
for another 2 days. Finally the samples were freeze dried and grounded to fine green powder.
FTIR (cm-1): 1261 (N-N stretching of 1, 2, 3 triazole moiety). There was no characteristic FTIR
peak of alkyne or azide moieties in P2-HBPs. P2-HBPs (0.1 g/ml) were soluble only in DMF,
DMSO and alkaline medium. Limited solubility of P2-HBPs in various solvents might be due to
their functionalization with long alkyl chained triazoles. P2-HBPs underwent pH dependant
reversible self assembling. All samples of P2-HBPs except P2 50/50/0/0 showed a sharp jump in
hydrodynamic diameter (Dh) from 102 to 103 nm and in zeta potential value from -30 to +10
mScm-1 at a specific pH in the range 4-4.5 for different samples. This abrupt increase in D h value

between pH 4-4.5 reflects the transition from individual molecules to aggregates of respective
polymers. Interestingly, the transition in polymer architecture of P2-HBPs was reversible i.e the
aggregates dissociated into individual molecules when the pH of the medium exceeded 4.5.
However, P250/50/0/0 (linear grade) displayed high Dh value throughout the range of solution pH
(uncontrolled aggregation). Hence branching units in P2-HBPs definitely stabilized the
aggregates. The aggregation behavior of P2-HBPs was further studied using pyrene as the probe.
Intensity ratio, I3/I1 varied from 0.6 to 1.0 as the pH of the solution changed from 8.0 to 2.0
which indicated encapsulation of pyrene to hydrophobic environment of polymer aggregates,
which developed below certain pH. Even FESEM images showed that at high pH, P2-HBPs had
floral structures whereas at low pH they had compact globular structures (i.e in aggregate state).
In the first experiment, we were successful in designing pH responsive HBPs. We are further
trying to develop highly water soluble HBP stabilized AgNPs for quick and easy sensing of Hg 2+
for waste water treatment.