M. Cai et al. / Reactive & Functional Polymers 70 (2010) 182–188
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monomer containing amide linkages, N,N0-bis(4-phenoxybenzoyl)-
m-phenylenediamine (BPBMPD). Novel aromatic poly(ether amide
amide ether ketone ketone)s (PEAAEKKs) were prepared by elec-
trophilic Friedel–Crafts solution copolycondensation of BPBMPD
with a mixture of terephthaloyl chloride (TPC) and isophthaloyl
chloride (IPC) in the presence of anhydrous aluminum chloride
and N-methylpyrrolidone (NMP) in 1,2-dichloroethane (DCE).
Crafts solution copolycondensation of BPBMPD with a mixture of
terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC) in
the presence of anhydrous aluminum chloride and NMP in DCE.
A typical preparative procedure for polymer I is described hereaf-
ter. Other polymers were also obtained in a similar manner.
To a 150 mL, three-necked, round-bottomed flask equipped
with a mechanical stirrer, a thermometer, nitrogen inlet and outlet
tubes, were added 6.14 g (46 mmol) of anhydrous AlCl3 and 20 mL
of DCE. The flask was cooled to 0 °C using an ice-water bath, then a
solution of 1.7 mL (18 mmol) of NMP in DCE (10 mL) was added
dropwise with stirring over a period of 10 min and the mixture
was stirred for 30 min and then cooled to –15 °C. Into the resulting
suspension were added 2.50 g (5 mmol) of BPBMPD and 1.015 g
(5 mmol) of TPC with stirring and the reaction mixture was
warmed to 20 °C over 2 h and the reaction was continued at this
temperature for 18 h. The reaction mixture was treated with
0.5 mL of diphenyl ether (DPE) as the end-capper for 1 h, quenched
with methanol (50 mL) at 0 °C and the precipitate was crushed,
washed with methanol and extracted with boiling methanol for
24 h and allowed to dry in air. The air-dried product was heated
at 100 °C overnight under vacuum to give the polymer I. Yield:
(94.4%). IR (KBr, cmꢀ1): 3064, 3427, 1657, 1592, 1497, 1418,
1240, 844. 1H NMR (DMSO-d6, d, ppm): d = 10.34 (s, 2H), 8.34 (s,
1H), 8.08 (d, J = 8.4 Hz, 4H), 7.90–7.87 (m, 8H), 7.49 (d, J = 8.0 Hz,
2H), 7.33–7.27 (m, 5H), 7.22 (d, J = 8.4 Hz, 4H).
2. Experimental
2.1. Materials
All reagents and solvents were of analytical grade and were
used without further purification unless stated otherwise. Tereph-
thaloyl chloride (TPC) and isophthaloyl chloride (IPC) (Shuanglin
Chemical Co., China) were purified by distillation under vacuum
prior to use. 1,2-dichloroethane (DCE, Shanghai Chemical Reagent),
N-methylpyrrolidone (NMP, Shanghai Chemical Reagent), N,N-
dimethylacetamide (DMAc, Shanghai Chemical Reagent), and
N,N-dimethylformamide (DMF, Shanghai Chemical Reagent) were
purified by distillation and dried by 0.4 nm molecular sieve. Alumi-
num chloride (Shanghai Chemical Reagent) was sublimed prior to
use. m-Phenylenediamine (Shanghai Chemical Reagent) and p-
phenoxybenzoic acid (Shanghai Chemical Reagent) were used as
received.
2.2. Synthesis of N,N0-bis(4-phenoxybenzoyl)-m-phenylenediamine
(BPBMPD)
2.4. Measurements
Elemental analysis was performed with Perkin-Elmer Model
2400 CHN analyzer. The FT-IR spectra of the monomers and poly-
mers in KBr pellets (2%) were recorded using a Nicolet FT-IR (510P)
spectrophotometer. 1H NMR (400 MHz) and 13C NMR (100 MHz)
spectra were obtained with a Bruker PC-A400 (400 MHz) spec-
trometer at an operating temperature of 25 °C using DMSO-d6 as
a solvent. Mass spectra were obtained on a Finnigan 4510 mass
spectrometer. Inherent viscosities were obtained with a concentra-
tion of 0.5 g/dL in NMP at 25 °C using an Ubbelhode suspended le-
vel viscometer. Differential scanning calorimetry (DSC)
measurements were performed on a Mettler Toledo DSC 821e
instrument at a heating rate of 10 °C/min under nitrogen. The
glass-transition temperature (Tg) was taken in DSC curve as the
center of the step transition in the second heating run. Thermo-
gravimetric analysis (TGA) was performed on a Netzch Sta 449c
thermal analyzer system at a heating rate of 10 °C/min in nitrogen.
The polymer thin films for stress–strain tests and X-ray diffraction
measurements were cast from NMP solutions onto glass plates,
and this was followed by evaporation of the solvent and drying
at 100 °C for 1 h, at 150 °C for 1 h, and at 200 °C in vacuo for 2 h.
The completeness of the solvent removal from the films was con-
firmed by TGA and DSC measurements. The mechanical properties
were measured at 25 °C using a Shimadzu AG-2000A tester at a
crosshead speed of 10 mm/min and an average of at least three
replicas was used. Wide angle X-ray diffraction (WAXD) was mea-
To
a 250 mL, round-bottomed flask were added 14.98 g
(0.07 mol) of 4-phenoxybenzoic acid, 50 mL of SOCl2, and 1 mL of
DMF. The mixture was stirred at reflux temperature for 4 h. After
removal of SOCl2 under reduced pressure, the residue was dis-
solved in 180 mL of DMAc under nitrogen, then 3.24 g (0.03 mol)
of m-phenylenediamine was added at 0 °C with stirring. The reac-
tion mixture was stirred at 0 °C for 1 h and at room temperature for
4 h, poured into water (100 mL). The solid product was filtered and
washed with water and ethanol, respectively. The crude product
was recrystallized from DMF and ethanol (VDMF/VEtOH = 1/2) and
dried under vacuum at 100 °C to afford 12.06 g of white crystals.
(Yield: 80%. m.p. 225–226 °C. MS (EI): m/z (%) = 500 (M+, 30),
197 (100). Elem. Anal. C32H24N2O4 Calcd. C 76.79, H 4.83, N 5.59;
Found. C 76.60, H 4.96, N 5.44. FTIR (KBr, cmꢀ1): 3335, 1642,
1590, 1538, 1496, 1408, 1248, 846. 1H NMR (DMSO-d6, d, ppm):
d = 10.32 (s, 2H), 8.27 (s, 1H), 7.98 (d, J = 8.8 Hz, 4H), 7.47–7.43
(m, 6H), 7.31 (t, J = 8.0 Hz, 1H), 7.22 (t, J = 7.6 Hz, 2H), 7.10 (d,
J = 8.0 Hz, 4H), 7.07 (d, J = 8.8 Hz, 4H). 13C NMR (DMSO-d6, d,
ppm): d = 164.77, 159.77, 155.39, 139.11, 130.30, 129.92, 129.26,
128.63, 124.44, 119.55, 117.32, 115.96, 112.75.
2.3. Polymer synthesis
Poly(ether amide amide ether ketone ketone)s (PEAAEKKs)
were prepared as shown in Scheme 2 by electrophilic Friedel–
sured with a Rigaku D/MAX-IIA X-ray diffractometer, using CuK
a
NH2
H2N
SOCl2
Reflux
O
O
CO2H
O
O
COCl
DMAc, 0-25 oC
O
C
(BPBMPD)
NH
HN
O
C
Scheme 1. Synthesis of BPBMPD.