JOURNAL OF
POLYMER SCIENCE
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ARTICLE
The nitroaromatic compounds used in this study are nitro-
benzene (NB), nitrotoluene (NT), dinitrobenzene (DNB), dini-
trotoluene (DNT), nitro benzoic acid (NBA), 3-nitro
benzaldehyde (3-NBA), Trinitrotoluene (TNT), 4-nitrophenol
(NP), and picric acid (PA), especially picric acid, are very
powerful explosives. They must be handled with care and
also used in very small quantities.
Preparation of PVM (9)
Compound (8) was taken in dry DCM under nitrogen atmo-
sphere, 1.2 equivalent of EDC.HCl, and 1 equivalent of DMAP
was added. After 10 min, 2-hydroxyethylmetha acrylate was
added through syringe very slowly. The mass was stirred at
room temperature for about 12 h, then quenched with
excess of water and extracted twice with DCM, and washed
with water and brine solution. Crude mass was purified by
column chromatography. Product eluted at 9:1 hexane:ethyl
acetate.
Preparation of Methyl 3,5-Bis(3,4,5-
Tris(Dodecyloxy)Styryl)Benzoate (7)
Methyl-3,5-dibromo benzoate (223 mg, 0.76 mmol) and
3,4,5-tris(dodecyloxy)stilbene (1 g, 1.521 mmol) were dis-
solved in dry DMF/toluene under inert atmosphere. Tetrabu-
tylammonium bromide (490 mg, 1.521 mmol), triethylamine
(630 mg, 4.563 mmol), and palladium acetate (34 mg. 0.152
mmol) were added into the reaction mixture. Then the reac-
tion mixture was heated to 908 C for about 12 h. After check-
ing the TLC, the mixture was cooled to room temperature
and it was poured into the water, extracted with ethyl ace-
tate (23 50mL) and washed with brine solution, dried, and
evaporated. The crude mass was purified by silica gel (60–
120 mesh) column chromatography, using 2% ethyl acetate
in hexane as an eluent.
1H NMR (300 MHz, CDCl3) d: 8.04(s, 2H), 7.77(s, 1H), 7.15–
7.10(d, 2H), 7.03–6.98(d, 2H), 6.74(s, 4H), 6.18(d, 1H),
5.61(d, 1H), 4.62–4.56(m, 4H), 4.05–3.96(m, 12H), 1.97(s,
3H), 1.85–1.76(m,12H), 1.49–1.26(m, 96H), 0.89–0.85(t,
J 5 10Hz, 18H); MS (MALDI-TOF): m/z calcd. for
C101H170O10: 1544.4610; found 1544.4796.
Preparation of PVP
The monomer of PVM, initiator, CuBr, and PMDETA (molar
ratio: 100/2/3/10) were accurately weighed and placed into
a precleaned and dried glass tube (schlenk tube), and tolu-
ene: benzene (1:1) was added. The polymerization mixture
was degassed with freeze-evacuate thaw cycle for three
times. The tube was sealed and then heated to 90 8C with
stirring for 72 h under argon. Afterwards, the reaction mix-
ture was diluted with excess amount of THF, passed through
a short column on basic aluminum oxide to remove Cu-
complex. The excess of THF was evaporated under reduced
pressure, and the product was precipitated from a large
amount of cold methanol, filtered, and dried under vacuum
to constant weight. Polymer was obtained as white solid
with 70% of yield. Mw: 92,647, Mn: 53,808, Mw/Mn: 1.72.
Yield is 0.8
g
(36%). mp: 46 8C.FT-IR (KBr): tC 5 O
1H NMR (300 MHz, CDCl3): d:
1731 cm21, tC 5 C 1648cm21
.
8.07(s, 1H), 8.01(s, 1H), 7.79(s, 1H), 7.10–7.05(d, J 5 16.3
Hz, 2H), 6.93–6.88(d, J 5 16.2 Hz, 2H), 6.71(s, 4H), 4.03–
3.97(m, 12H), 3.94(s, 3H), 1.87–1.70(m,12H), 1.48–1.26(m,
96H), 0.89–0.85(t, J 5 10 Hz, 18H). 13C NMR(75 MHz, CDCl3)
d: 166.0, 153.7, 140.1, 139.2, 133.4,132.5,131.9, 131.8, 126.4,
125.3, 123.1, 105.7, 73.9, 69.5, 52.8, 32.3, 32.5, 30.77, 30.1,
30.1, 30.1, 30.1, 30.0, 30.0, 29.8, 29.8, 29.8, 26.5, 23.1, 23.1,
14.5.
1H NMR (300 MHz, CDCl3) d: 8.02(Ar, H), 7.78(Ar, H), 7.15–
7.10(-CH 5 CH-), 7.04–6.99(-CH 5 CH-), 6.75(Ar, H), 4.55(-
CH2-CH2), 4.35(-CH2-CH2), 4.03–3.97(-OCH2-), 1.81(-CH2),
1.62(-CH3, acrylate), 1.26((-CH2)9), 0.88–0.85(-CH3). ANAL.
FOUND: C 82.11, H 6.97, O 10.93.
Preparation of 3,5-Bis (3,4,5-Tris(Dodecyloxy)Styryl)
Benzoic Acid (8)
Methyl-3,5-bis (3,4,5-tris(dodecyloxy)styryl)benzoate (0.7 g,
0.484 mmol) was dissolved in THF (10 mL) and KOH(54 mg,
0.968 mmol) solution were added into the reaction mixture.
The reaction mixture was refluxed for about 3 h. After com-
pletion of the reaction time, the reaction mixture was cooled
to room temperature and the solvent was evaporated, resi-
due was diluted with water and extracted with ether, and
aqueous layer was separated and acidified with 1.5N HCl
solution and extracted with ethyl acetate. The organic layer
was separated and washed with brine solution, dried over
Na2SO4 and evaporated.
RESULTS AND DISCUSSION
Synthesis
The synthetic pathway for the PVM is shown in Scheme 2.
The compound 520 was synthezised by earlier procedure
and it was treated with 3,5-dibromo methylbenzoate in the
presence of Pd catalysts (Heck reaction) to obtain product 7.
The formation of compound 7 was confirmed by the appear-
ance of tC 5 O stretching frequency at 1731 cm21 and also
the tC 5 C stretching frequency at 1648 cm21. Furthermore,
the ester compound was hydrolyzed with lithium hydroxide
(LiOH) to give acid 8. The compound 8 was confirmed by
1H-NMR spectrum. The acid compound was treated with 2-
hydroxyethyl methacrylate by using EDC. HCl gives the
monomer with moderate yield. The monomer 9 further
undergoes ATRP to give blue light emitting PVP with very
good yield. The PVP shows rod like morphology in the
aggregated states which was confirmed by SEM analysis
(Scheme 1). All the intermediates and final compounds were
Yield is 0.6
g ,
(90%). IR(KBr) (t21): 1577 cm21 1H
NMR(300 MHz, CDCl3) d: 8.13(s, 1H), 8.08(s, 1H), 7.85(s,
1H), 7.12–7.07(d, J 5 16.3 Hz, 2H), 6.95–6.91(d, J 5 16.2 Hz,
2H), 6.72(s, 4H), 4.04–3.96(m,12H), 1.87–1.71(m, 12H),
1.49–1.266(m, 96H), 0.90–0.85(t, J 5 12Hz, 18H); 13C
NMR(75 MHz, CDCl3) d: 166.3, 154.0, 140.4, 139.5,132.7,
132.6,132.2,126.6, 125.5, 123.4, 106.0, 74.2, 69.8, 32.6, 32.6,
31.0, 30.4, 30.4, 30.4, 30.3, 30.3, 30.3, 30.1, 30.0, 30.0, 26.8,
23.3, 23.3, 14.7.
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2016, 00, 000–000
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