Sequence analysis of technora (copolyamide of terephthaloyl chloride, p-phenylenediamine, and 3,4′-diaminodiphenyl ether) using 13C NMR

Article abstract of DOI:10.1021/ma034670b

The dyad sequence analysis of Technora (copolyamide prepared from terephthaloyl chloride, p-phenylenediamine, and 3,4′-diaminodiphenyl ether) was reported using ¹³C NMR in trifluoromethanesulfonic acid at 100 °C. For the detailed peak assignmen

Full text of DOI:10.1021/ma034670b

6160
Macromolecules 2003, 36, 6160-6165
Sequence Analysis of Technora (Copolyamide of Terephthaloyl Chloride,
p-Phenylenediamine, and 3,4′-Diaminodiphenyl Ether) Using 13C NMR
Hir on or i Ma tsu d a a n d Tetsu o Asa k u r a *
Department of Biotechnology, Tokyo University of Agriculture and Technology, Koganei,
Tokyo 184-8588, J apan
Ya su o Na k a ga w a
Material Analysis Research Laboratories, Teijin Ltd., Hino, Tokyo 191-8512, J apan
Received May 21, 2003; Revised Manuscript Received J une 7, 2003
ABSTRACT: The dyad sequence analysis of Technora (copolyamide prepared from terephthaloyl chloride,
p-phenylenediamine, and 3,4′-diaminodiphenyl ether) was reported using 13C NMR in trifluoromethane-
sulfonic acid at 100 °C. For the detailed peak assignment, some model copolymers were synthesized and
the 13C NMR spectra were observed. Well-resolved carbonyl carbon peaks of the terephthalic units of
Technora were observed, which made it possible to analyze the p-phenylenediamine units and the 3,4′-
diaminodiphenyl ether units at dyad level. The information on the head-to-head, tail-to-tail, and head-
to-tail sequences of the 3,4′-diaminodiphenyl ether units was also obtained. It was concluded that the
sequence of Technora was completely random.
In tr od u ction
A few fully aromatic polyamide (aramid) fibers, for
example, under the trade names Kevlar (du Pont) and
Technora (Teijin Technoproducts) have been processed
and provided as high-strength and high-modulus fibers.
Kevlar is a homopolyamide, that is, poly(p-phenylene
terephthalamide) (PPTA), whereas Technora1-3 is a
copolyamide prepared from terephthaloyl dichloride
(TPC), p-phenylenediamine (PPDA), and 3,4′-diamino-
diphenyl ether (3,4′-DAPE), with a TPC/PPDA/3,4′-
DAPE monomer mole ratio of 100/50/50, as shown in
Figure 1. Copolymerization has been performed in order
to improve solubility of aromatic polyamide, and thus,
Technora is processed by dry-jet wet spinning from the
solution of N-methyl-2-pyrrolidone. Ozawa3 has reported
that the physical properties of Technora fiber such as
tenacity, elongation, and modulus change depending on
the molar ratio of two diamine components, and there
is a optimum composition for obtaining excellent physi-
cal properties. However, there are no detailed report
about the sequence of the polymer.
Thus far, a large number of sequence analyses have
been reported using nuclear magnetic resonance
(NMR).4-13 In general, the melt condensation copoly-
mers are formed in thermodynamically equilibrium
state, and therefore most of the sequences should be
random in statistically. However, because Technora is
the condensation copolyamide prepared irreversibly in
nonequilibrium state in N-methyl-2-pyrrolidone solu-
tion, the sequence is not necessarily random. It is
important whether the sequence of the Technora poly-
mer is random or blocky in connection with the physical
properties such as solubility or hydrolytic stability. One
of the reasons why there are no reports on the sequence
analysis is insoluble character of the polymer in common
NMR solvents. Tashiro et al.14 have suggested that the
sequence of Technora is blocky using X-ray diffraction.
They have also tried the sequence analysis of the
F igu r e 1. Production scheme of the Technora polymer.
polymer in sulfuric acid using13C NMR, but they could
not obtain the information on the sequence because of
the low-resolution spectrum. Contrary to this, Blackwell
et al.15,16 have reported that the sequence of Technora
is random using X-ray diffraction. Aoki17 has also
reported that the sequence of the polymer should be
random using computer simulation of the polymeriza-
tion. Thus, to obtain the conclusive information on the
sequence, it is better to find out the suitable condition
including solvent for obtaining a well-resolved NMR
spectrum. Thus far, solvents such as N,N-dimethyl-
formamide or N,N-dimethylacetamide have been used
for 1H NMR studies of fully aromatic copolyamide
consisting of isophthalic acid and two aromatic di-
amines, i.e., 4,4′-oxybisaniline and bis(4-aminophenyl)-
sulfone.18-20 However, the solubility is quite different
between isophthalic and terephthalic unit. Actually, 13
C
NMR spectra of PPTA homopolymer in sulfuric acid
have been reported by English21 because PPTA is
insoluble in N,N-dimethylformamide or N,N-dimethyl-
acetamide. The solvents such as formic acid, trifluoro-
acetic acid, and sulfuric acid have been used for fully
aliphatic and mixed aliphatic/aromatic polyamides.22-30
However, fully aromatic polyamides are insoluble in
formic acid. As will be mentioned in the text, Technora
is decomposed in sulfuric acid (97%).
* To whom correspondence should be addressed.
10.1021/ma034670b CCC: $25.00 © 2003 American Chemical Society
Published on Web 07/08/2003

Macromolecules, Vol. 36, No. 16, 2003
Sequence Analysis of Technora 6161
In this paper, we tried to find out suitable condition
for getting a well-resolved 13C NMR spectrum of the
polymer (solvent; trifluoromethanesulfonic acid and
observed temperature; 100 °C). In addition, for the peak
assignment at dyad level, some rational model copoly-
mers were synthesized. On the basis of the conclusive
peak assignments of the well-resolved 13C NMR spectra,
the detailed sequential analysis was performed.
Exp er im en ta l Section
P olym er P r ep a r a tion . Technora, a copolyamide prepared
from terephthaloyl chloride, p-phenylenediamine, and 3,4′-
diaminodiphenyl ether, was obtained from Teijin Technoprod-
ucts as the precipitate from the N-methyl-2-pyrrolidone (NMP)
solution after the polymerization. Kevlar-29 fibers (du Pont)
were obtained in a parallel bundle. Three model copolyamides
were synthesized for the assignment of the 13C NMR spectrum
of Technora. Two of the model copolyamides were synthesized
from the aromatic diamine monomers that have unsym-
metrical and symmetrical structures containing amide link-
ages. The aromatic unsymmetrical diamine monomer contain-
ing amide linkages was prepared from 3-amino-4′-nitrodiphenyl
ether, p-nitroaniline, and terephthaloyl dichloride; the mole
ratio was 100/100/100, respectively, with subsequent reduction
of the dinitro intermediate. A solution of 116 g of 3-amino-4′-
nitrodiphenyl ether in 300 mL of NMP was added dropwise
to a solution of 101 g of terephthaloyl dichloride in 1000 mL
of NMP at -20 °C, taking 30 min. After stirring for more 20
min, a solution of 69 g of p-nitroaniline in 200 mL of NMP
was added at -20 °C. After the neutralization by a solution of
40 g of sodium hydroxide in 5000 mL of water, the dinitro
intermediate obtained was repeatedly purified by recrystalli-
zation from a dimethylformamide/water solvent mixture. The
dinitro intermediate obtained was subjected to catalytic hy-
drogenation to the corresponding diamine. The catalytic
hydrogenation was performed with Pd/C as catalyst and NMP
as solvent with vigorous agitation under 75 kg/cm2 hydrogen
pressure at 660 °C in an autoclave. The diamine obtained was
repeatedly purified by recrystallization from a dimethylforma-
mide/water solvent mixture. The aromatic symmetrical di-
amine monomer containing amide linkages was prepared from
3-amino-4′-nitrodiphenyl ether and terephthaloyl dichloride;
the mole ratio was 200/100, respectively, with subsequent
reduction of the dinitro intermediate. The model copolyamides
were prepared by solution polymerization. Terephthaloyl
dichloride was added to an NMP solution of an equimolar
amount of the unsymmetrical or symmetrical diamine mono-
mer at room temperature. The reaction mixture was allowed
to stand with stirring at room temperature for 2 h and then
neutralized by addition of an aqueous solution of sodium
hydroxide. The precipitate was washed with a large amount
of water and then dried. Another model copolyamide was
prepared similarly from an equimolar amount of terephthaloyl
dichloride and 3,4′-diaminodiphenyl ether.
F igu r e 2. Expanded 100 MHz 13C NMR spectra (the carbonyl
carbon region) of the Technora polymer. The solvents are (a)
sulfuric acid at room temperature, (b) methanesulfonic acid
at 100 °C, (c) trifluoromethanesulfonic acid at room temper-
ature, and (d) trifluoromethanesulfonic acid at 100 °C.
Resu lts a n d Discu ssion
Selection of Solven t. It is important to find out the
suitable solvent for obtaining a well-resolved NMR
spectrum without decomposition during NMR measure-
ment. For the copolyamide containing the isophthalic
unit as the acidic component, Curnuck et al.19 used N,N-
dimethylacetamide (DMAc) for the NMR solvent. Kang
et al.31 used N,N-dimethylformamide (DMF)/CCl4 sol-
vent system for the analysis of the NH proton peaks of
1
the H NMR spectrum of similar copolyamides. How-
ever, Technora having the terephthalic unit as the acidic
component is insoluble in such solvents. We tried to use
sulfuric acid, methanesulfonic acid, and trifluoromethane-
sulfonic acid as the solvent. Although these solvents
have been used for the sequence analyses of the fully
aliphatic and mixed aliphatic/aromatic copolyamides,22-30
the applications for the fully aromatic copolyamides
have not been reported. Technora could be dissolved in
these solvents after standing the mixtures overnight.
The carbonyl carbon regions of the 13C NMR spectra in
sulfuric acid, methanesulfonic acid, and trifluoromethane-
sulfonic acid are shown in Figure 2. In the case of
sulfuric acid (97%), four peaks were observed (Figure
2a), but the peak observed at 173.8 ppm seems to be
assigned to the decomposition product of polymer or
reaction product with sulfuric acid. Thus, sulfuric acid
(97%) is not suitable for the sequence analysis of the
polymer. As shown in Figure 2b, three peaks were
observed in the case of methanesulfonic acid at 100 °C.
However, there are no further well-resolved peaks, and
therefore methanesulfonic acid is also not suitable for
the sequence analysis of the polymer. The roughly three
peaks were also observed in the case of trifluoromethane-
sulfonic acid even at room temperature as shown in
Figure 2c. However, at 100 °C (Figure 2d), the spectrum
was dramatically changed and the well-resolved peaks
could be observed. Thus, we used the experimental
condition, trifluoromethanesulfonic acid at 100 °C, for
NMR measurement of Technora in this paper.
NMR Mea su r em en ts. 100 mg of the polymer in a 10 mm
diameter NMR tube was dissolved in 3.5 mL of sulfuric acid
(97%), methanesulfonic acid, and trifluoromethanesulfonic acid
by standing overnight at room temperature. Deuterated di-
methyl sulfoxide was inserted as the NMR lock solvent. The
13C NMR spectra were recorded by using a J EOL R-400
spectrometer operating at 100 MHz. The observed temperature
was room temperature or 100 °C. Tetramethylsilane in deu-
terated dimethyl sulfoxide was used as a standard chemical
shift reference. The spectra were obtained with a digital
resolution of 0.83 Hz/point, corresponding to a spectral width
of ca. 27 kHz and a data point of 32K. The flip angle and the
pulse delay were 45° and 2.5 s, respectively. The spectra were
obtained with a digital resolution of 0.21 Hz/point after zero-
filling. Two-dimensional NOESY spectra of the model mono-
mers synthesized were obtained with a mixing time τ ) 800
ms in deuterated dimethyl sulfoxide at room temperature.

6162 Matsuda et al.
Macromolecules, Vol. 36, No. 16, 2003
F igu r e 3. Possible dyad sequences on the diamine units of
the Technora polymer along with the notations of carbonyl
carbons. T, A, and B indicate terephthalic unit, p-phenylene-
diamine unit, and 3,4′-diaminodiphenyl ether unit, respec-
tively. (3) and (4′) indicate the binding site of the B unit for
the T unit, 3-position and 4′-position, respectively.
F igu r e 4. Synthetic scheme of the (ATB + T) model polymer
for the assignment of the NMR spectrum of the Technora
polymer.
If there are small amounts of water in sulfuric acid,
the decomposition of PPTA occurs at modest tempera-
ture as pointed out by English previously.21 Thus,
sulfuric acid (97%) used here is expected to decompose
Technora. However, in the case of trifluoromethane-
sulfonic acid, the crystalline of the monohydrate with
melting point: 34 °C will be formed in the solid state if
there is trace of water in this acid. Therefore, if the
liquid part was used for the solvent, it is possible to used
the acid without trace of water which is one reason why
trifluoromethanesulfonic acid is favorable than sulfuric
acid as the solvent for Technora.
Mod el P olym er s for th e Assign m en t. As shown
in Figure 3, there are six possible dyad sequences on
the diamine units in Technora because of unsym-
metrical structure of diamine unit B. Therefore, nine
different carbonyl carbons should be considered.
F igu r e 5. Synthetic scheme of the (BTB + T) model polymer
for the assignment of the NMR spectrum of the Technora
polymer.
For the assignment of the peaks in Figure 2d to the
dyad sequences (Figure 3), the 13C NMR spectra of the
model polymers, (ATB + T) and (BTB + T), prepared
according to the schemes of Figures 4 and 5,32 respec-
tively, were used. Here, ATB and BTB indicate the
unsymmetrical and symmetrical diamine monomers,
respectively, that have a selective binding site of the B
unit to the T unit. The structures of ATB and BTB
monomers were checked by two-dimensional NOESY
spectra as shown in Figures 6 and 7, respectively. It
was confirmed that synthesized ATB monomer has the
unsymmetrical diamide structure centered on tereph-
thalic unit because two amide proton peaks, (7) and (10),
were observed, as shown in Figure 6. For the amide
proton peak (7), the NOE’s were observed between the
proton peaks (3) and (6). Peaks (3) and (6) could be
assigned to the protons of meta-disubstituted benzene
of the 3,4′-diaminodiphenyl ether unit, as shown in
Figure 6. There is NOE between the proton peak (11)
and the other amide proton peak (10). Peak (11) could
be assigned to the proton of the p-phenylenediamine
unit. Therefore, it made clear that the ATB monomer
has the unsymmetrical diamide structure centered on
terephthalic unit, as shown in Figure 6. Arrows in the
structural formula in Figure 6 indicate that the NOE
was observed between the corresponding protons. Simi-
larly, it was checked that synthesized BTB monomer
has the symmetrical diamide structure centered on
terephthalic unit because one amide proton peak (7) was
observed. There are NOE’s between proton peaks (3)
and (7) and the peaks (6) and (7). Peaks (3) and (6) could
be assigned to the protons of the meta-disubstituted
benzene of the 3,4′-diaminodiphenyl ether unit. The
NOE between peak (1) and peaks (3) or (6) of the para-
disubstituted benzene of the 3,4′-diaminodiphenyl ether
unit was not observed. Therefore, it is clear that the
BTB monomer has the symmetrical diamide structure
centered on terephthalic unit, as shown in Figure 7.
Arrows in the structural formula in Figure 7 indicate
that the NOE was observed between the corresponding
protons. The structure of these ATB and BTB monomers
was also confirmed by 1D NOE difference spectra (data
not shown). DQF-COSY spectra were also used for the
assignment of the aromatic proton peaks of diamine
units. The (B + T) model polymer that has no selective
binding site of the B unit to the T unit was also
synthesized. The relationship between these model
polymers and dyad sequences is shown in Figure 8. By
using this relationship, the assignment of the carbonyl

Macromolecules, Vol. 36, No. 16, 2003
Sequence Analysis of Technora 6163
F igu r e 8. (a) Relationship between the model polymers and
the dyad sequences. The solid lines show the dyad sequences
to be present in the model polymers. (b) The observable peak
patterns of the carbonyl carbons of each model polymer. The
numbers indicate the notations of carbonyl carbons in Figure
3. The order of the numbers in a block is indefinite.
F igu r e 6. NOESY spectrum of the synthesized ATB diamine
monomer. A mixing time τ ) 800 ms. The solvent is deuterated
dimethyl sulfoxide at room temperature. Arrows in the struc-
tural formula indicate that the NOE was observed between
corresponding protons.
F igu r e 9. Expanded 100 MHz 13C NMR spectra (the carbonyl
carbon region) of the Technora polymer and the model
polymers in trifluoromethanesulfonic acid at 100 °C: (a)
Technora, (b) the Kevlar-29, (c) the (ATB + T) model polymer,
(d) the (BTB + T) model polymer, and (e) the (B + T) model
polymer. The assignments of the carbonyl carbons in Figure
3 are shown.
F igu r e 7. NOESY spectrum of the synthesized BTB diamine
monomer. A mixing time τ ) 800 ms. The solvent is deuterated
dimethyl sulfoxide at room temperature. Arrows in the struc-
tural formula indicate that the NOE was observed between
corresponding protons.
indefinite. For example, in the case of the (ATB + T)
polymer, maximally six carbonyl carbon peaks, 1, 2, and
4 of the T-A bond, 3 of the T-(3)B bond, and 5 and 9 of
the T-(4′)B bond, are expected to observe.
Assign m en t of th e P ea k s Usin g Mod el P olym er s.
For the assignment of the peaks in Figure 2d to the dyad
sequences in Figure 3, the Kevlar-29 corresponding to
the (A + T) polymer and three model polymers were
dissolved in trifluoromethanesulfonic acid, and the 13C
NMR spectra were measured at 100 °C. Expanded 100
MHz 13C NMR spectra (the carbonyl carbon region) are
shown in Figure 9. To assign the peaks observed in the
region from 171.0 to 171.5 ppm that is the region of the
carbonyl carbon of the T-A bond, the peak position was
carbon peaks of all dyad sequences of Technora is
possible. For example, the (BTB + T) polymer have two
dyad sequences of B(3)-T-(3)B and B(4′)-T-(4′)B, as
shown in Figure 8. On the other hand, the (ATB + T)
polymer has also B(4′)-T-(4′)B sequences. Therefore, the
peaks of (3)-T-(3)B and B(4′)-T-(4′)B sequences will be
assigned respectively by a comparison of the spectra of
the (BTB + T) and (ATB + T) polymers. The observable
peak patterns of the carbonyl carbons of each model
polymer were also summarized in Figure 8. The num-
bers indicate the notations of the carbonyl carbons in
Figures 3. The order of the numbers in a block is

6164 Matsuda et al.
Macromolecules, Vol. 36, No. 16, 2003
Ta ble 1. Resu lts of th e Sequ en ce Distr ibu tion An a lysis of
th e Tech n or a P olym er by 13C NMRa
(X ) A or B) were calculated with the following equa-
tion:33
average
dyad
sequences
sequence
lengths
RAB ) (fAB/2)/FA + (fAB/2)/FB
LA ) (fAA + fAB/2)/(fAB/2)
LB ) (fBB + fAB/2)/(fAB/2)
(1)
(2)
(3)
fractionsb
randomness
A-T-A
A-T-B
B-T-B
fAA
fAB
fBB
0.248 (0.250) RAB 1.03 (1.00) LA 1.96 (2.00)
0.514 (0.500)
0.238 (0.250)
LB 1.93 (2.00)
A-T-(3)B
A-T-(4′)B
fA3B 0.499 (0.500)
fA4′B 0.501 (0.500)
where subscripts A and B indicate the A (p-phenylene-
diamine unit) and B (3,4′-diaminodiphenyl ether unit)
units, respectively. fAA, fAB, and fBB indicate the molar
fractions of the dyad sequences, A-T-A, A-T-B, and
B-T-B, respectively (fAA + fAB + fBB ) 1). Here, the
binding site of the B unit, 3-position or 4′-position, is
ignored. FA ) 0.50 and FB ) 0.50 are the molar fractions
of the A and B units in the polymer, respectively. RAB
indicates the degrees of randomness, and LA and LB
indicate the number-average sequence lengths of the
T-A and T-B units, respectively. As is listed in Table 1,
RAB ) 1.0 and LA ) LB ) ca. 2.0 were obtained.
Therefore, it is clear that the sequential unit distribu-
tion on the A and B units in the polymer is random.
The molar fractions of A-T-(3)B and A-T-(4′)B in
A-T-B units, fA3B and fA4′B (fA3B + fA4′B ) 1), respectively,
are also shown in Table 1. Because of fA3B ) fA4′B ) 0.5,
it is also clear that the sequential unit distribution on
the binding site (3-position or 4′-position) of the B unit
for the A-T unit is random in the polymer. Furthermore,
the molar fractions of B(3)-T-(3)B, B(3)-T-(4′)B, and
B(4′)-T-(4′)B in the B-T-B unit, f3B3B, f3B4′B, and f4′B4′B
(f3B3B + f3B4′B + f4′B4′B ) 1), respectively, and its degrees
of randomness (RBB) are also shown in Table 1. Here,
(3) and (4′) indicate the binding site of the B unit for
the T unit, 3-position and 4′-position, respectively. RBB
) 1.0 was calculated with eq 1; therefore, it is also clear
that the sequential unit distribution on the binding site
(3-position or 4′-position) of the B unit for T-B unit is
random in the polymer. Thus, it can be concluded that
all of the possible dyad sequences in Technora are
random.
On the sequence of Technora, different views have
been reported by different analytical methods. Tashiro
et al.14 have used the Technora fiber annealed at 400
°C, and the structure was analyzed with X-ray diffrac-
tion and infrared spectra. They have suggested the
possibility that the sequence of the polymer is blocky
because some crystalline domains consisting only poly-
(p-phenylene terephthalamide) (T-A segment in the
present paper) remained after annealing. Although they
have tried the analysis of the polymer in sulfuric acid
using 13C NMR, it could not obtain the information on
the sequence because of the low-resolution NMR spec-
trum. On the other hand, Blackwell et al.15,16 have also
applied the X-ray diffraction method for the Technora
fiber. They have reported that the sequence of the
Technora polymer is random because the best agree-
ment between the positions of the observed aperiodic
meridional maxima and those calculated for a com-
pletely random sequence was obtained. Aoki17 predicted
that the sequence of Technora is random by means of
computer simulation of the polymerization. From our
NMR analysis reported here, it was concluded that the
sequence of Technora is completely random as reported
by Blackwell et al.15,16 and Aoki.17 Because Tashiro et
al.14 have analyzed the residue after heat treatment,
the parts of the short sequence lengths of p-phenylene
B(3)-T-(3)B f3B3B 0.251 (0.250) RBB 0.99 (1.00)
B(3)-T-(4′)B f3B4′B 0.496 (0.500)
B(4′)-T-(4′)B f4′B4′B 0.253 (0.250)
a
The values in parentheses were theoretical values on the basis
b
of a Bernoullian dyad distribution. The molar fractions were
calculated as fAA + fAB + fBB ) 1, fA3B + fA4′B ) 1, and f3B3B + f3B4′B
+ f4′B4′B ) 1.
compared among Technora, Kevlar-29, and the (ATB +
T) polymers. As summarized in Figure 8, three carbonyl
carbon peaks, 1, 2, and 4, are expected to observe in
the region of the carbonyl carbon of the T-A bond of
(ATB + T) polymer. From the relative peak area in
Figure 9c and the corresponding peak position of Kevlar-
29 (Figure 9b), peaks 2 and 4 are considered to be
overlapping. Consequently, peaks 1, 2, and 4 of the
Technora polymer as shown in Figure 9a were assigned
to the carbonyl carbons 1, 2, and 4 in Figure 3,
respectively. Then, the peaks observed in the region
from 169.2 to 170.2 ppm in Figure 9 can be assigned to
the carbonyl carbon peaks of the T-(3)B and T-(4′)B
bond. In the spectrum of the (ATB + T) polymer as
shown in Figure 9c, one peak was observed in the region
from 169.7 to 170.1 ppm was assigned to the carbonyl
carbon of the T-(3)B bond, and two peaks in the region
from 169.2 to 169.6 ppm were assigned to the carbonyl
carbon of the T-(4′)B bond because one peak, 3, and two
peaks, 5 and 9, are expected to observe in the each
region of the (ATB + T) polymer, as shown in Figure 8.
On the other hand, because only two peaks, 6 and 9,
are expected to be observed in the (BTB + T) polymer
(Figure 8), peaks 6 and 9 of the (BTB + T) polymer could
be easily assigned as shown in Figure 9d. Therefore, two
peaks, 5 and 9, of the (ATB + T) polymer observed in
the region from 169.2 to 169.6 ppm could be assigned
by comparison of the peak position between parts c and
d of Figure 9. Similarly, by comparison of the peak
position between (BTB + T) and (B + T) polymers, peaks
6, 7, 8, and 9 of the (B + T) polymer could be assigned
(Figure 9e). By comparison of the peak position among
Technora, the (ATB + T) polymer, the (BTB + T)
polymer, and the (B + T) polymer, peaks 3, 5, 6, 7, 8,
and 9 of the Technora in Figure 9a were clearly assigned
to the carbonyl carbons 3, 5, 6, 7, 8, and 9 in Figure 3,
respectively. Consequently, all of the carbonyl carbon
peaks of dyad sequences of Technora were assigned.
Thus, the 13C NMR spectrum of Technora observed in
trifluoromethanesulfonic acid at 100 °C gives not only
the dyad sequence information on the A and B units
but also the head-to-head, tail-to-tail, and head-to-tail
sequence information on the B units.
Sequ en ce Distr ibu tion An a lysis of th e Tech n or a
P olym er . To estimate the degree of randomness of
Technora, the dyad molar fractions centered on tereph-
thalic unit were determined on the basis of the observed
relative peak area. The degree of randomness and the
number-average sequence length are summarized in
Table 1. These parameters on the sequence of X-T-X

Macromolecules, Vol. 36, No. 16, 2003
Sequence Analysis of Technora 6165
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(15) Blackwell, J .; Cageao, R. A.; Biswas, A. Macromolecules 1987,
20, 667.
terephthalamide units or the parts of the 3,4′-diamino-
diphenyl ether units were expected to be degraded.
(16) Cageao, R. A.; Schneider, A.-I.; Blackwell, J . Macromolecules
1990, 23, 2843.
(17) Aoki, H. Kobunshi Ronbunshu 1994, 51, 428.
(18) Curnuck, P. A.; J ones, M. E. B. Br. Polym. J . 1973, 5, 21.
(19) Gan, L. H.; Blais, P.; Carlsson, D. J .; Suprunchuk, T.; Wiles,
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Ack n ow led gm en t. The authors thank Mr. Yasuhiro
Marumoto at Teijin Technoproducts Ltd. for his support
of the polymer offer.
Refer en ces a n d Notes
(1) Ozawa, S.; Nakagawa, Y.; Matsuda, K.; Nishihara, T.;
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