Poly-L-lactic acid (PLA) 1

Poly-L-lactic acid (PLA)

Polymer Solids and Polymer Melts # Data

G. Steiner, C. Zimmerer

Polyester

[26161-42-2]

infrared [cm1] int. Raman [cm1] int. assignm. comments references

515 w (C-CH3), semicryst. 95Kis
(C-CO)
520 m 515 m (C-CH3), semicryst. 95Kis,
(C-CO) 98Kis
578 w 578 w (C-CH3), semicryst. 95Kis,
(C-CO) 98Kis
591 w (C-CH3), amorph. 95Kis
(C-CO)
650 sh (C=O) 98Kis
677 sh 675 m (C=O) semicryst. 95Kis,
98Kis
682 w (C=O) amorph. 95Kis
690 m (C=O) amorph. 95Kis
695 m (C=O) semicryst. 95Kis
700 vw (C=O) amorph. 95Kis
710 m 711 m (C=O) amorph., 95Kis
semicryst.
715 m 715 m (C=O) semicryst. 95Kis,
98Kis
(continued)

Landolt-Bornstein DOI: 10.1007/978-3-642-32072-9_86

New Series VIII/6A1 # Springer-Verlag Berlin Heidelberg 2013
2 Poly-L-lactic acid (PLA)

infrared [cm1] int. Raman [cm1] int. assignm. comments references

736 m 736 m (C=O) semicryst. 95Kis,
98Kis
740 sh 740 m (C=O) amorph., 95Kis
semicryst.
760 s 760 sh (C=O) amorph., 95Kis,
semicryst. 98Kis
790 w (C=O) amorph. 95Kis
845 w (C-COO) 98Kis
860 sh (C-COO) 98Kis
873 vs 873 vs (C-COO) amorph., 95Kis,
semicryst. 98Kis
920 vw (CH3), (C-C) br. 98Kis
923 m (CH3), (C-C) semicryst. 95Kis
925 w 925 w (CH3), (C-C) amorph., 95Kis,
semicryst. 98Kis
953 sh (CH3), (C-C) amorph., 95Kis
semicryst.
960 w (CH3), (C-C) amorph., 95Kis
semicryst.
1042 s as(C-CH3) amorph., 95Kis
semicryst.
1045 s 1045 s (C-CH3) amorph., 95Kis,
semicryst. 98Kis
1088 sh 1090 sh s(C-O-C) 98Kis
1090 vs s(C-O-C) amorph., 95Kis
semicryst.
1092 s s(C-O-C) amorph., 95Kis
semicryst.
1092 s s(C-O-C) 98Kis
1100 vs s(C-O-C) 98Kis
1128 s 1128 s as(CH3) amorph., 95Kis,
semicryst. 98Kis
1179 w 1179 m as(CH3), semicryst. 95Kis,
as(C-O-C) 98Kis
1183 m as(C-O-C) amorph. 95Kis
1185 vs as(CH3), 98Kis
as(C-O-C)
(continued)

DOI: 10.1007/978-3-642-32072-9_86 Landolt-Bornstein

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infrared [cm1] int. Raman [cm1] int. assignm. comments references

1185 vs as(C-O-C) amorph., 95Kis
semicryst.
1211 vs as(C-O-C) amorph. 95Kis
1215 vs as(CH3), 98Kis
as(C-O-C)
1215 vs as(C-O-C) semicryst. 95Kis
1216 m as(C-O-C) amorph., 95Kis
semicryst.
1216 w as(CH3), 98Kis
as(C-O-C)
1264 sh (CH), (C-O-C) amorph. 95Kis
1270 s 1270 s (CH), (C-O-C) amorph., 95Kis,
semicryst. 98Kis
1293 m 1293 s (CH2) semicryst. 95Kis,
98Kis
1296 s (CH2) amorph. 95Kis
1300 m 1300 s (CH2) amorph., 95Kis
semicryst.
1313 m 1313 m CH semicryst. 98Kis
1315 m 1315 s (CH2) amorph., 95Kis
semicryst.
1348 s 1348 s s(CH3) br., semicryst. 98Kis
1353 m (CH), s(CH3) 98Kis
1360 s 1355 m (CH), s(CH3) amorph., 95Kis,
semicryst. 98Kis
1363 m (CH), s(CH3) amorph., 95Kis
semicryst.
1365 m 1365 m (CH), s(CH3) amorph. 95Kis
1368 s (CH), s(CH3) semicryst. 95Kis
1371 m 1371 m (CH), s(CH3) semicryst. 95Kis
1384 m s(CH3) semicryst. 95Kis
1385 s s(CH3) amorph. 95Kis
1386 m s(CH3) amorph. 95Kis
1388 m s(CH3) semicryst. 95Kis
1388 s s(CH3) semicryst. 95Kis
(continued)

Landolt-Bornstein DOI: 10.1007/978-3-642-32072-9_86

New Series VIII/6A1 # Springer-Verlag Berlin Heidelberg 2013
4 Poly-L-lactic acid (PLA)

infrared [cm1] int. Raman [cm1] int. assignm. comments references

1452 s 1452 s as(CH3) semicryst. 95Kis,
98Kis
1749 s 1749 s (C=O) semicryst. 95Kis,
98Kis
1755 sh (C=O) amorph. 95Kis
1760 vs 1760 vs (C=O) amorph., 95Kis,
semicryst. 98Kis
1763 s 1763 s (C=O) semicryst. 95Kis,
98Kis
1769 sh 1769 s (C=O) amorph. 95Kis,
98Kis
1773 s 1773 s (C=O) semicryst. 95Kis,
98Kis
2295 s as(CH3) semicryst. 95Kis
2877 m 2877 m (CH) amorph., 95Kis,
semicryst. 98Kis
2882 w 2882 w (CH) amorph., 95Kis,
semicryst. 98Kis
2901 w 2901 w (CH) semicryst. 95Kis
2882 w (CH) 98Kis
2943 vs 2942 vs s(CH3) amorph., 95Kis,
semicryst. 98Kis
2947 m 2947 m s(CH3) amorph., 95Kis,
semicryst. 98Kis
2960 sh as(CH3) semicryst. 95Kis
2970 sh as(CH3) semicryst. 95Kis
2995 s as(CH3) 98Kis
2997 m 2997 s as(CH3) amorph. 95Kis
3014 m as(CH3) 98Kis
2997 m as(CH3) amorph., 95Kis
semicryst.
3000 sh as(CH3) 98Kis

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Comments and Explanations to the Data

Structure of the Tables

If available, molecular structure and CAS number are represented. The molecular structure of the polymer
is related to the vibrational modes. Carbon and hydrogen atoms of an aromatic unit are mostly not indi-
cated. Polymers or structural units of polymers that can have a para-, meta-, or ortho-arrangement are
drawn in the para-arrangement. The headline and structure of tables is shown in Fig. 12.

Fig. 12 Headline
of the tables.

Column Description
Spectral position of IR absorption bands, given in the wavenumber unit [cm1].
Intensity of IR absorption bands (see acronyms paragraph 2.1.6).
Spectral position of Raman bands, given as Raman shift in the unit [cm1].
Intensity of Raman bands (see acronyms paragraph 2.1.6).
Assignment to molecular bonds or structural units.
Comments to assignments and type of the vibrational modes (if available and necessary), listed
in an alphabetical order.
References to the bands, assignments and comments, listed by year of publishing.

Spectral positions of IR and Raman bands

The spectral positions were taken from the references as listed. If there were more than one reference to the
same vibration where the band positions varied within 4 cm1, the median was calculated and listed. In
case of an even number the wavenumber of band position were round down. It should be noted, that the
spectral resolution of the reported results was usually poorer than 2 cm1. In very few cases obviously
wrong numbers were corrected without remarks within the tables. IR and Raman bands below 500 cm1
were not considered.

Band Intensities
Band intensities, if available, were taken from the references. Usually the intensities are summarized as
weak, medium and strong bands. Shoulders arise from overlapping bands. Several references used the term
shoulder together with the term weak. Overlapping bands may be separated by sophisticated methods of
deconvolution or curve fitting. Fig. 13 shows the IR spectrum of LDPE in the range of the C-H deforma-
tion vibrations. The registrated absorption band (black curve) consists of three individual bands (dotted
curves). A weaker mode at 1440 cm1 appears as shoulder. The other two bands are merged together in
a broad band. The listed band intensities are relative to other bands in the spectrum.

Landolt-Bornstein DOI: 10.1007/978-3-642-32072-9_86

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6 Poly-L-lactic acid (PLA)

Fig. 13 IR spectrum of LDPE in the region

between 1440 and 1500 cm1. The black curve is
the measured spectrum. Three subbands (dotted
lines) were separated by a curve fitting algorithm.
The dashed line is the sum of the subbands.

Assignments
Assignments were taken as given in the references. In differences to some references the assignments of
vibrational modes of amide groups are general labeled as amide A, amide 1, etc. In several references
the different types of C-H deformation vibrations such as twisting rocking and wagging modes are sum-
marized under the general term deformation (). When the precise type of the vibration mode was not
mentioned or not known, the denotation as deformation mode was taken. Ring vibrations of aromatic com-
ponents are denoted with the symbol when a deformation mode is predominant. It should be also noted
that not all data of vibrational modes and their assignments were available in the literature. In some cases
bands are assigned to bonds or molecular units which do not exist in the structural formula. These bands
may arise from monomers, intermediates, impurities or from residual traces of solvents.

Symmetries
Since the molecular symmetry is important in vibrational spectroscopy few explanations will be given
shortly with regards to comments within the tables. For more details the reader is referred to basic litera-
tures on the theory of molecular symmetry. Vibrations of functional groups of a polymer chain can be
described by the so-called point groups. The point group theory means that during the vibration at least
one point in the molecule remains unaffected. Furthermore, for molecular units with some symmetry, point
group theory can be used to predict how many vibrational modes should appear in the IR and Raman
spectra. As different molecular symmetries lead to different numbers of IR and Raman active bands this
is a useful approach for determining the symmetry of a polymer chain. A vibration is IR active when
the dipole moment on going from the ground to the excited state is changed. Raman excitation occurs only
when there is a change in polarizability on going from the ground to the excited state. Among the numbers
of different types of symmetry few important examples are represented in Fig. 14.
In according to the common denotations [see 55IUP], the symbols indicate

A symmetrical to the main axis,

B antisymmetrical to the main axis,
g symmetric to the center of inversion,
u antisymmetric to the center of inversion,
1 the vibration is also symmetric to other axis,
2 the vibration is only symmetric to main axis.

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Fig. 14 Illustration of selected complex vibrations and

their relation to the type of symmetry [05Hes].

Abbreviations

Vibrational modes and assignments

ar aromat
Fermi res. Fermi resonance
stretching vibration
as antisymmetric stretching vibration
s symmetric stretching vibration
deformation vibration
as antisymmetric deformation vibration, bending
s symmetric deformation vibration, bending
wagging vibration
as antisymmetric wagging vibration
s symmetric wagging vibration

Landolt-Bornstein DOI: 10.1007/978-3-642-32072-9_86

New Series VIII/6A1 # Springer-Verlag Berlin Heidelberg 2013
8 Poly-L-lactic acid (PLA)

twisting, torsion vibration

rocking vibration
ring vibration
vibration of skeleton atoms

Intensity of bands

sh shoulder
vw very weak
w weak
m medium
s strong
vs very strong

Comments

ads. adsorbed
aliphat. aliphatic
amorph. amorphous
aniso. anisotropic
aque. aqueous solution
ata. atactic
arom. aromatic
br. broad
chlor. trichlormethane solution
conf. configuration
copol. co-polymer
cryst. crystalline
Des Desmosine
deut. deuterium solution
G gauche form
hydb. hydrogen bonded
iso. isotactic
heterocyc. heterocyclic

DOI: 10.1007/978-3-642-32072-9_86 Landolt-Bornstein

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hex. hexagonal
hum. human
Hypro Hydroxyproline
intramol. intramolecular
i.p. in plane vibration
i.ph. in phase vibration
Isodes Isodesmosine
mod. modification
molt. molten
o.p. out of plane vibration
o.ph. out of phase vibration
o-substituted ortho substituted
orth. orthorhombic
p parallel
Phe Phenylalanine
Pro Proline
pp perpedicular
p-substituted para substituted
res. resonance
sol. solution
semicryst. semicrystalline
syn. syndiotactic
streg. stereoregular
T trans form
tert. tertiary
tetra. tetrachlormethane solution
Tyr Tyrosine

References
95Kis Kister, G., Cassanas, G., Vert, M., Pauvert, B., Terol, A.: J. Raman Spectr. 26 (1995) 307.
98Kis Kister, G., Cassanas, G., Vert, M.: Polymer, 39 (1998) 267.

Landolt-Bornstein DOI: 10.1007/978-3-642-32072-9_86

New Series VIII/6A1 # Springer-Verlag Berlin Heidelberg 2013