Journal of Thermal Analysis and Calorimetry, Vol.

70 (2002) 703–711

SELF-ORDERING PROCESS OF PHENANTHRENE

POLYESTERS OBSERVED BY THE SIMULTANEOUS
DSC-XRD METHOD

H. Yoshida1*, M. Yang1, K. Masaka2, Y. Houshito2, K. Mashiko2 and

S. Nakamura2
1
Graduate School of Engineering, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397,
Japan
2
Department of Applied Chemistry, Kanagawa University, Kanagawa-ku, Yokohama 221-8686,
Japan

Abstract
Phase transition behavior of polyesters derived from 2,7-phenanthrene dicarbonic acid diethylester
and alkanediols with even methylene carbon number was investigated by the simultaneous
DSC-XRD method. The smectic A phase was observed on cooling from the molten state. The transi-
tion entropy from the isotropic state to the smectic A phase was about 9.0 J mol–1 K–1, which de-
pended on the methylene carbon number. The linear expansion coefficients, based on the (001) spac-
ing of the crystalline phase at room temperature, were 1.3·10–4 K–1 (crystalline phase), 5.7·10–4 K–1
(crystallization region), 1.7·10–3 K–1 (smectic A phase) during cooling, and 1.5·10–4 K–1 (crystalline
phase), and 1.0·10–3 K–1 (melting region) on heating.

Keywords: DSC-XRD, liquid crystal, phenanthrene, polyester, thermal expansion

Introduction
The thermotropic polyesters based on 2,7-phenanthrene dicarbonic acid diethylester and
alkanediols assume the smectic liquid crystalline phase above their melting temperatures
due to the intermolecular interaction between phenanthrene moieties [1, 2]. Phenanthrene
moieties as a mesogenic unit are connected by alkyl chain in the main chain of
phenanthrene polyester; PPE. These polyesters having phenanthrene moieties in the main
chain exhibit the odd-even effect of methylene carbon number (n) on the phase transition
temperature and the transition enthalpy of PPE. The transition temperature of PPEs with
even n number is higher than that of PPEs with odd n number [1, 2].
Poly(oxyheptamethyleneoxy-2,7-phenanthrenedicarbonyl) (PPEn7) demonstrates
the smectic A and C phases on cooling by the simultaneous DSC-XRD [3]. At the transi-
tion from the smectic A to the smectic C phases on cooling, the (001) spacing of PPEn7
changed discontinuously from 1.9 to 1.8 nm, however, the linear expansion coefficients

* Author for correspondence: E-mail: [email protected]

1418–2874/2002/ $ 5.00 Akadémiai Kiadó, Budapest

© 2002 Akadémiai Kiadó, Budapest Kluwer Academic Publishers, Dordrecht
704 YOSHIDA et al.: LIQUID CRYSTAL

in both smectic A and C phases were the same [3]. The same linear expansion coefficient
indicates that the smectic phase exists on heating for PPEn7 [3]. Liquid crystalline phase
of polymer is often observed on cooling, while it is hard to observe on heating due to the
narrow temperature range [4–6]. The linear expansion measurement is powerful tool to
determine the phase which exists in the narrow temperature region between the melting
and the isotropic transitions. The temperature range of the smectic phase observed on
cooling is considerably narrow for PPEs with even n number comparing with that for
PPEs with odd n number. In this study, the phase transition and linear expansion of PPEs
with even n number were determined by the simultaneous DSC-XRD method.

Experimental
Phenanthrene polyesters (PPE) (Scheme 1) were prepared by polycondensation of
2,7-phenanthrene dicarbonic acid diethylester and corresponding alkanediols. The
PPE samples were purified by the precipitation method from m-cresol/o-chloro-
phenol solution to a large amount of methanol. The intrinsic viscosity [h] evaluated at
30°C using the mixed solvent of phenol and 1,1,2,2,-tetrachloroethane (6:4) were
0.34, 0.34 and 0.51 dL g–1 for PPEn6, PPEn7 and PPEn8, respectively. The PPE pow-
der was pressed into a disk with 0.5 mm thickness. The disk of PPEs with about 3 mg
was sealed by aluminum foil and was clamped in the aluminum pan for the
DSC-XRD measurement.

Scheme 1

DSC measurements were carried out by Seiko DSC 200 at various scanning
rates from 10 to 1 K min–1 under dry nitrogen gas flow. The transition temperature
and enthalpy were evaluated by extrapolating to zero heating rates. Indium and tin
were used as reference standards for temperature and enthalpy.
The simultaneous DSC-XRD instrument [7] was set on a Mac Science MXP18
SRA X-ray diffractometer (DSC-WAXRD) [8] operated at 40 kV and 300 mA. The
wavelength of monochromatic X-ray was 0.1540 nm. The scintillation counter was
scanned at 10° min–1 in the 2q range from 4° to 8°, which corresponded to 1.1 nm<s–1=
(2sinq/l)–1<2.2 nm with the space resolution of 10–4 nm. The XRD profile for the fiber
and crystalline specimens were observed by an imaging plate detector DIP-2000.
For the small angle X-ray measurement, the DSC-XRD instrument was set on the
small angle X-ray scattering optics (DSC-SRXRD) at BL-10C of Photon Factory, High
Energy Accelerator Research Organization, Tsukuba, Japan. The wavelength of mono-
chromatic X-ray for DSC-SRXRD was 0.1488 nm. The scattering X-ray was detected by
a one-dimensional position sensitive proportional counter (PSPC). The distance between
specimen and PSPC was 680 nm, which covered 1.25 nm<s–1=(2sinq/l)–1<200 nm. The
simultaneous DSC-XRD measurement was carried out at 5 K min–1, and XRD profiles

J. Therm. Anal. Cal., 70, 2002

 YOSHIDA et al.: LIQUID CRYSTAL 705

were stored for each 2.0 K (DSC-SRXRD) and 2.5 K (DSC-WAXRD), respectively. The
temperature and enthalpy were calibrated by pure indium and tin.

Results and discussion

DSC curves of poly(oxyhexamethyleneoxy-2,7-phenanthrenedicarbonyl) (PPEn6) with
various thermal history are shown in Fig. 1. The heating curve a for the precipitated pow-
der on heating of PPEn6 shows two endothermic peaks at around 220 and 240°C. The
cooling curve b from the molten state shows one exothermic peak at 228°C. The curve c,
obtained by heating immediately after cooling from the molten state to 205°C, shows two
endothermic peaks at 230 and 245°C. The cooling curve d from the molten state to 100°C
shows two exothermic peaks at 228 and 195°C. From the optical microscopic observa-
tion, the clear domain boundary and the focal conic texture indicated.

Fig. 1 DSC curves of PPEn6 with various thermal histories measured at 2 K min–1

The existence of smectic phase between two exothermic peaks on cooling. How-
ever, the temperature range between two endothermic peaks on heating was too nar-
row to determine the structure. DSC curves of PPEn8 showed almost the same ten-
dency with PPEn6.
The transition temperature and enthalpy of PPEn6 on cooling were obtained by
extrapolating the initial temperature of transitions to zero scanning rate as shown in
Fig. 2. The obtained transition temperature and enthalpy for PPEn6, n7 [3] and n8
were listed in Table 1. The equilibrium thermodynamic quantities are: TL–S=230.5°C,
DHL–S=4.5 kJ mol–1 (molar enthalpy was evaluated for repeating unit) for the transi-
tion from the isotropic liquid to the smectic phase, and TS–C=200.2°C, DHS–C=
9.0 kJ mol–1 for the smectic phase to the crystalline phase for PPEn6. The transition
entropy from the isotropic liquid to the smectic phase of PPEn6 (DSL–S) and PPEn8
were 9.0 and 9.6 J mol–1 K–1, respectively. These DSL–S were almost double of the tran-
sition entropy (4.5 J mol–1 K–1) [5] reported for the polyesters containing biphenyl
moieties as a mesogen unit in the main chain, which formed the smectic phase for odd

J. Therm. Anal. Cal., 70, 2002

706 YOSHIDA et al.: LIQUID CRYSTAL

Fig. 2 Relationship between the cooling rate and transition temperatures; ¡ – the initial
transition temperature; l – the transition peak temperature

methylene carbon number family and the nematic phase for even carbon number on
cooling. The larger DSL–S value of PPEn6 is due to the strong interaction between
phenanthrene moieties comparing with biphenyl moieties.

Table 1 Transition temperature and enthalpy obtained by extrapolation to zero cooling rate
I to SA SA to SC SX to C
T/°C DH/kJ mol –1
T/°C DH/kJ mol –1
T/°C DH/kJ mol–1
n6 230.5 4.5 200.2 9.0
n7 148.2 1.2 129.8 6.1 105.0 10.5
n8 195.3 4.5 189.1 9.2

Two-dimensional X-ray diffraction pattern of PPEn6 fiber is shown in

Fig. 3 (A). The PPEn6 fiber was drawn at 210°C in the smectic A phase and quenched
to room temperature. A couple of diffraction spot was observed in the parallel direc-
tion to the fiber axis. The spacing calculated from the diffraction was 1.98 nm, which
was close to the calculated length of the extended length of repeating unit of PPEn6
assuming all trans conformation of alkyl chain. Therefore, the diffraction spot is as-
signed to the (001) diffraction of PPEn6 fiber. The fiber X-ray diffraction profile in-
dicates that the extended PPEn6 molecules are oriented perpendicular to the smectic
layer. Namely, this fiber diffraction pattern strongly suggests the smectic A structure
of PPEn6 between 220 and 200°C on cooling. Figure 3 (B) is the X-ray diffraction
pattern of the crystalline PPEn6 film prepared by cooling at 1 K min–1 from the mol-
ten state to room temperature. The (001) diffraction peak was also observed slightly
in Fig. 3 (B). However, other diffraction peaks were found clearly in the crystalline
state of PPEn6.

J. Therm. Anal. Cal., 70, 2002

 YOSHIDA et al.: LIQUID CRYSTAL 707

Fig. 3 A – Fiber X-ray diffraction profile of PPEn6 drawn at 210°C and B – X-ray dif-
fraction profile of crystalline state of PPEn6

The relationship between the (001) spacing (d(001)) evaluated from the X-ray diffrac-
tion of the crystalline state of PPEs and the methylene carbon number (n) is shown in
Fig. 4. The linear relationship between d(001) and n indicates the same relation between the
crystalline structure and molecular conformation for the PPEs with even methylene car-
bon number. The slope of this relationship gives the length of one methylene group, and
also the value obtained by extrapolating this relationship to n=0 gives the length of main
chain except alkyl chain, in other word, the length of mesogenic group. From the rela-
tionship between d(001) and n, the increase of length with methylene group and the length
of mesogenic unit were 0.124 and 1.126 nm, respectively.

Fig. 4 Relationship between methylene carbon number (n) and (001) spacing (d(001))
observed by X-ray diffraction profile of the crystalline phase for PPE at room
temperature

J. Therm. Anal. Cal., 70, 2002

708 YOSHIDA et al.: LIQUID CRYSTAL

From these results, the possible conformational model of PPEs with even meth-
ylene carbon number is shown in Fig. 5. The methylene groups are aligned to the
c-axis of crystal, and the phenanthrene group exists obliquely with angle 30° to the
c-axis. The molecular model shown in Fig. 5 is based on the molecular conformation
in the smectic A phase.

Fig. 5 Conformational model of PPEs with even methylene carbon number. Model
shows PPEn6

The simultaneous DSC-SRXRD result of PPEn6 on cooling was shown in Fig. 6.

PPEn6 was cooled from 275 to 160°C at 2 K min–1. Two exothermic transitions were ob-
served in DSC curve (A), the peak at 240 and 210°C are the isotropic–smectic transition
and the crystallization, respectively. The temperature resolved XRD profiles changed at
both transitions. The diffraction peak at 0.5 nm–1 (s=2sinq/l) appears at the isotro-
pic–smectic transition and grow during the transition peak at around 240°C. Only one
diffraction peak at 0.5 nm–1 was observed in the smectic A phase same as Fig. 3 (A). The
sharp diffraction peak suggests that phenanthrene group stacks each other and forms reg-
ular spacing in the smectic A phase. This sharp diffraction peak changed to the broader
one at the crystallization. During the crystallization, new diffraction peaks appeared at
0.3 and 0.62 nm–1. The broad diffraction peaks at temperature below 200°C indicates the
lower crystallinity of PPEn6. The diffraction peak from the smectic layer close to
0.02 nm–1 is hard to evaluate the maximum value (smax). However, 2nd and 4th order dif-
fraction peaks were observed at 0.15 and 0.3 nm–1, respectively. The layer thickness cal-
culated from these higher-order diffraction peaks is 13 nm, that is, five or six repeating
units consist the layer.

J. Therm. Anal. Cal., 70, 2002

 YOSHIDA et al.: LIQUID CRYSTAL 709

Fig. 6 Temperature resolved XRD profiles at various temperatures (upper) and DSC
curve (lower) for PPEn6 observed by DSC-XRD at 2 K min–1 from the molten
state to the crystal state
The temperature dependency of d(001) of PPEn6 observed by DSC-WAXRD is
shown in Fig. 7. On heating, the d(001) increased linearly at temperature up to 170°C and
increased rapidly at temperature above 180°C, at which the endothermic peak started.
This diffraction peak disappeared at 230°C. On the other hand, the diffraction peak of
s=0.51 nm–1 appeared at 225°C on cooling indicating the isotropic smectic transition. The
d(001) decreases linearly with decreasing temperature from 225 to 205°C, which corre-

Fig. 7 ¡ – temperature dependence of d(001) of PPEn6 on heating; l – cooling observed

by DSC-XRD at 2 K min–1

J. Therm. Anal. Cal., 70, 2002

710 YOSHIDA et al.: LIQUID CRYSTAL

sponds to the isotropic smectic transition region (DSC curve d in Fig. 1). The slope of
d(001) changes slightly between 205 and 170°C, which closes to the crystallization. The
d(001) decreases again linearly with decreasing temperature from 170 to 120°C.
The linear expansion coefficient of d(001) based on the d(001) value of the crystal-
line state at room temperature, 1.88 nm, was evaluated from Fig. 6. The linear expan-
sion coefficient was obtained as follows;
Heating: 1.5·10–4 K–1 (120–165°C), and 1.0·10–3 K–1 (165–230°C)
Cooling: 1.3·10–4 K–1 (120–160°C), 5.7·10–4 K–1 (165–200°C) and 1.7·10–3 K–1
(205–220°C)
The linear expansion coefficient of d(001) in the crystalline state is almost the
same on heating and cooling. Comparing with the data of PPEs of odd n number, the
linear expansion coefficient of d(001) in the crystalline state of PPEn6 is smaller than
that of PPEn7 due to the conformational difference. The mesogenic group of PPE
with even n number was expected to tilt with angle 30° to the c-axis, as described
above. However, the mesogen group of PPE with odd number family is thought to be
parallel to the c-axis [3, 9]. The linear expansion coefficients of d(001) for PPEn6,
n7 [3] and n8 observed during both heating and cooling are listed in Table 2.

Table 2 Thermal expansion coefficient of the d(001) spacing

Crystalline phase/ Transition region/ SC phase/ SA phase/
K–1 K–1 K–1 K–1
1.5·10–4 1.0·10–3
n6 Heating
(120–165°C) (165–230°C)
1.3·10–4 5.7·10–4 1.7·10–3
Cooling
(120–160°C) (165–200°C) (205–220°C)
2.3·10–4 4.7·10–4 2.1·10–3
n7 Heating
(30–110°C) (115–150°C) (150–165°C)
2.9·10–4 1.7·10–3 1.7·10–3
Cooling
(30–90°C) (100–120°C) (120–100°C)
1.2·10–4 1.0·10–3
n8 Heating
(90–150°C) (190–200°C)
1.2·10–4 1.5·10–3
Cooling
(90–130°C) (190–195°C)

The linear expansion coefficients of d(001) in the smectic A phase of PPEn6 and
PPEn7 are almost the same (1.5·10–3 K–1 for PPEn7) [3]. However, linear expansion coef-
ficients of d(001) observed during melting on heating (1.0·10–3 K–1) was about a half of that
obtained in the smectic phase on cooling (1.7·10–3 K–1), and was about double of that ob-
served during the crystallization on cooling (5.7·10–4 K–1). As expected from the (001)
diffraction peak in the smectic phase and the crystalline phase shown in Fig. 6, the crys-
talline structure of PPEn6 was based on the molecular conformation and alignment of the

J. Therm. Anal. Cal., 70, 2002

 YOSHIDA et al.: LIQUID CRYSTAL 711

smectic A phase. These facts suggest that the smectic phase coexist with the crystal phase
on heating in the temperature region between two endothermic peaks.

References
1 H. Yoshida, K. Masaka and S. Nakamura, Reports on Progress in Polymer Physics in Japan,
41 (1998) 211.
2 H. Yoshida, M. Honma, K. Masaka and S. Nakamura, Photon Factory Activity Report,
16 (1998) 117.
3 H. Yoshida, Y. Houshito, K. Mashiko, K. Masaka and S. Nakamura, J. Therm. Anal. Cal.,
60 (2001) 453.
4 J. Watanabe and M. Hayashi, Macromolecules, 22 (1989) 4083.
5 W. R. Krigbaum, J. Watanabe and T. Ishikawa, Macromolecules, 16 (1983) 1271.
6 H. Sackmann and D. Demus, Mol. Cryst. Liq. Crys., 21 (1973) 239.
7 H. Yoshida, R. Kinoshita and Y. Teramoto, Thermochim. Acta, 264 (1995) 173.
8 H. Yoshida, Thermochim. Acta, 267 (1995) 239.
9 H. Yoshida, K. Mashiko, K. Masaka and S. Nakamura, unpublished data.

J. Therm. Anal. Cal., 70, 2002