7722 Kimura et al.
Macromolecules, Vol. 36, No. 20, 2003
with a mechanical stirrer and a gas inlet tube were placed
0.30 g of ACA (1.46 mmol) and 20 mL of LPF (1.5% w/v). The
reaction mixture was heated under a slow stream of nitrogen
up to 320 °C with stirring. The stirring was stopped when ACA
was completely dissolved. The temperature was maintained
at 320 °C for 6 h. The precipitated products were collected by
vacuum filtration at 320 °C and washed with n-hexane and
acetone. Product characteristics were as follows. FT-IR (KBr)
(cm-1): 2920 (aromatic CH), 1725 (ester CdO), 1633 (vinyl Cd
C). Anal. Calcd for C9H6O2: C, 73.97; H, 4.14; O, 21.89.
Found: C, 74.94; H, 4.21; O, 20.85.
Syn th esis of P h en yl (E)-4-[(E)-Cin n a m oyloxy]cin n a -
m a te (P CC). Into a 50 mL flask equipped with a dropping
funnel, a thermometer and a gas inlet tube were placed 1.00
g of HCA (6.10 mmol), 0.74 g of triethylamine (7.32 mmol),
and 20 mL of dried tetrahydrofuran. A solution of 1.22 g of
(E)-cinnamoyl chloride (7.32 mmol) and 10 mL of dried
tetrahydrofuran was added dropwise through the dropping
funnel under the slow stream of nitrogen at 5 °C. The reaction
temperature was kept at 5 °C for 2 h and then at 25 °C for 12
h. The reaction mixture was filtrated to remove the triethyl-
amine-HCl salts and acidified by diluted HCl solution. The
white precipitates were collected and washed with water.
Recrystallization from ethyl acetate/n-hexane gave 1.10 g
(76%) of white crystals of (E)-4-[(E)-cinnamoyloxy]cinnamic
acid. The purity was checked by HPLC. Product characteristics
were as follows. Tm: 206 °C. FT-IR (KBr) (cm-1): 3300-2500
(OH), 1735 (ester CdO), 1693 (carboxylic acid CdO), 1627
(vinyl CdC). Anal. Calcd for C18H14O4: C, 73.46; H, 4.79; O,
21.75. Found: C, 73.53; H, 4.75; O, 21.72. 1H NMR (CDCl3/
CF3COOH; δ, ppm): 7.42-7.48 (H-1, H-2, m, 3H), 7.59-7.64
(H-3, H-7, m, 4H), 7.96 (H-4, d, 1H, J ) 16.0 Hz), 6.67 (H-5, d,
1H, J ) 16.0 Hz), 7.24 (H-6, d, 2H, J ) 7.2 Hz), 7.85 (H-8, d,
1H, J ) 16.0 Hz), 6.45 (H-9, d, 1H, J ) 16.0 Hz).
by diluted HCl solution. The white precipitates were collected
and washed with water. Recrystallization from ethyl acetate/
n-hexane gave 0.145 g (82%) of white crystals of PCC. The
purity was checked by HPLC. Product characteristics were as
follows. Tm: 158 °C. FT-IR (KBr) (cm-1): 1735 (ester CdO),
1631 (vinyl CdC). Anal. Calcd for C24H18O4: C, 77.82; H, 4.90;
O, 17.28. Found: C, 77.31; H, 4.81; O, 17.88. 1H NMR (CDCl3/
CF3COOH; δ, ppm): 7.39-7.49 (H-1, H-2, H-11, m, 5H), 7.63
(H-3, d, 2H, J ) 7.8 Hz), 7.98 (H-4, d, 1H, J ) 16.0 Hz), 6.66
(H-5, d, 1H, J ) 16.0 Hz), 7.26 (H-6, d, 2H, J ) 8.0 Hz), 7.68
(H-7, d, 2H, J ) 8.0 Hz), 7.95 (H-8, d, 1H, J ) 16.0 Hz), 6.69
(H-9, d, 1H, J ) 16.0 Hz), 7.15 (H-10, d, 2H, J ) 8.0 Hz), 7.29
(H-12, t, 1H, J ) 8.0 Hz).
13C NMR (CDCl3/CF3COOH; δ, ppm): 131.92 (C-1), 129.52
(C-2), 129.06 (C-3), 133.96 (C-4), 149.59 (C-5), 116.15 (C-6),
168.10 (C-7), 152.84 (C-8), 122.81 (C-9), 130.35 (C-10), 132.37
(C-11), 147.73 (C-12), 117.05 (C-13), 168.85 (C-14), 150.58 (C-
15), 121.82 (C-16), 130.11 (C-17), 126.98 (C-18).
Mea su r em en ts. Morphology of the polymer crystals was
observed by scanning electron microscopy (S-2150, Hitachi Co.
Ltd.) at 20 kV. FT-IR spectra were measured on a FT-IR
spectrometer (FT/IR-410, J ASCO Co. Ltd.). The chemical
structures of ACA and the oligomer model compounds were
characterized by 1H and 13C NMR (Bruker AVANCE500)
operating at 500 MHz (1H) and 125 MHz (13C). The NMR
spectra were measured in CDCl3/CF3COOH. Signal assign-
ments were carried out with the help of C-H COSY spectra
and the spectral data of cinnamic acid described in the
Integrated Spectral Data Base System for Organic Compounds
(SDBS) presented by the National Institute of Advanced
Industrial Science and Technology (AIST), J apan. The chemi-
cal structure of POC was characterized by solid-state 13C NMR
(Bruker AVANCE500) operating at 75 MHz. The purity of
oligomer model compounds was checked by HPLC (Waters
600E-490E system) with a Nova Pack HR C18 column. The
eluent was a mixture of water containing 2 wt % acetic acid
and acetonitrile, and the mixing volume ratio of these two
solvents was changed linearly from 90/10 to 0/100 for 40 min.
The WAXS pattern was measured by a diffractometer (Gaiger
flex, Rigaku Co. Ltd.) with nickel-filtered Cu KR radiation (35
kV, 20 mA). Thermal stability was measured on a Perkin-
Elmer TGA 7 at a heating rate of 20 °C min-1 in a nitrogen
atmosphere. Tg and Tm were measured on a Perkin-Elmer DSC
7 at a scanning rate of 10 °C min-1 in a nitrogen atmosphere.
The densities of the microspheres were measured by the
flotation method using tetrachloromethane and p-xylene at 25
°C. The diameter of the microspheres was determined by the
average of over 100 observation values.
13C NMR (CDCl3/CF3COOH; δ, ppm): 131.86 (C-1), 129.42
(C-2), 128.61 (C-3), 133.98 (C-4), 149.44 (C-5), 116.22 (C-6),
167.83 (C-7), 152.99 (C-8), 122.77 (C-9), 130.36 (C-10), 132.08
(C-11), 148.40 (C-12), 116.55 (C-13), 173.79 (C-14).
Into a 50 mL flask equipped with HCl gas trap were placed
0.50 g of (E)-4-[(E)-cinnamoyloxy]cinnamic acid and 15 mL of
thionyl chrolide. Three drops of N,N-dimethylformamide were
added into the reaction mixture, and the mixture was stirred
at 25 °C for 12 h. The excess of thionyl chloride was stripped
off, and recrystallization from dried n-hexane gave 0.53 g (67%)
of (E)-4-[(E)-cinnamoyloxy]cinnamoyl chloride (67%). FT-IR
(KBr) (cm-1): 1741 (acid chloride CdO), 1721 (ester CdO),
1629 (vinyl CdC).
Into a 100 mL flask equipped with a dropping funnel, a
thermometer and a gas inlet tube were placed 0.09 g of phenol
(0.96 mmol) and 20 mL of dried tetrahydrofuran. A solution
of 0.15 g of (E)-4-[(E)-cinnamoyloxy]cinnamoyl chloride (0.48
mmol) was added at 5 °C under a slow stream of nitrogen. A
solution of 0.06 g of triethylamine (0.96 mmol) and 5 mL of
dried tetrahydrofuran was added dropwise through the drop-
ping funnel at 5 °C. The reaction temperature was kept at 5
°C for 2 h and then 25 °C for 12 h. The reaction mixture was
filtrated to separate the triethylamine-HCl salts and acidified
Deter m in a tion of Nu m ber -Aver a ge Degr ee of P olym -
er iza tion of P olym er s. 10 mg of sample and 1 mL of 7.0 wt
% potassium hydroxide methanol solution were placed in a
test tube and kept at 25 °C until the sample was completely
hydrolyzed to HCA. The solution was neutralized with dilute
hydrochloric acid and then analyzed by using gas chromatog-
raphy (GC-14B Shimadzu Co. Ltd.) with a Thermon-3000 (60-
80 mesh) packed column. Number-average degree of polym-