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Table 1 Summary of thermal properties of PLAs.
Run
c
d
Sample IDa
Mnb
(×103)
8.1
PDIb
Tm
T10
(ºC)
168
168
160
169
169
158
230
224
(ºC)
254
237
230
343
355
353
313
359
1e
2
PLLA
PLLAb
PDLAb
1.4
50
55
8.5
8.3
8.3
11.4
9.6
1.19
1.20
1.4
1.16
1.12
N.D.
N.D.
3
4e
5
DACA-PLLA
DACA-PLLAb
DACA-PDLAb
SCb
6
7
8
N.D.
N.D.
DACA-SCb
a ‘b’ indicates benzyl group in the initiator. SC means stereocomplex.
b Determined by SEC in THF with polystyrene standards.
c Determined by DSC upon a second heating (10 ºC min-1).
d Determined by TGA under nitrogen (20 ºC min-1).
e Reference 16.
Tm and T10 values when their Mn were same (Table 1, run 2 and 3).
DACA conjugation contributed to improve T10 values, but it did
not change Tm values (Table 1, run 5 and 6). Stereocomplexation
of PLLAb and PDLAb improved Tm values, accompanied with
T10 values to some extent (Table 1, run 7). Finally, DACA
conjugated stereocomplex, DACA-SCb, reflected the both
improvements of Tm and T10 (Table 1, run 8). The significant
factors of Tm and T10 individually depended on the
10 stereocomplexation formation and aromatic groups conjugation,
respectively. DACA-polymers had minimum structural changes
from the original polymers, thus they were allowed to form
specific polymer-polymer interaction, i.e. stereocomplexation.
The obtained bio-based polymer DACA-SCb is highly
15 anticipated as a novel thermal-resistant biomaterial. Further
investigations of molecular weight effect with the present dual
approaches are currently underway.
In conclusion, we selected two approaches to improve
thermal properties of PLAs using aromatic groups conjugation
20 and stereocomplexation. Both Tm and T10 values of the bio-based
polymer increased at the same time. This improvement is
expected to contribute tremendously in industrial biotechnology.
This work was partly supported by a Grant-in-Aid for
Scientific Research (S) from the Ministry of Education, Culture,
25 Sports, Science and Technology (23225004). We acknowledge
Mr. Y. Takahashi for the syntheses of PLLA and PDLA. We are
also grateful to Drs. T. Kida, M. Matsusaki, and T. Akagi for the
fruitful discussion.
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