Polymerizability of Lactones Calculated by Molecular Mechanics,

Semiempirical and Density Functional Theory Methods

Anchalee Junkaew, Jitrayut Jitonnom, Piyarat Nimmanpipug, and Vannajan

Sanghiran Lee *

Department of Chemistry, Faculty of Science,

Chiang Mai University, Chiang Mai, 50200 Thailand

nuch96@thaimail.com
jmanu@chaiyo.com
npiyarat@chiangmai.ac.th
vannajan@chiangmai.ac.th

Abstract

Molecular mechanics, semiempirical and density functional theory were

used to calculate the heat of polymerization for a series of lactones of different
ring sizes. The change in the internal energy upon polymerization was
calculated from the difference in the minimized energy between the 5- and 4-
mers and the monomer. Comparison of the calculated bond angles and
lengths of cyclic ester monomers with the experimental results were also
discussed.

Keywords: cyclic esters; ring strain; polymerizability.

1. Introduction

Recent advances in the development of new biodegradable polyesters

for use in medical applications, such as polymer carriers for targeted drug
delivery and controlled drug release, are in an area of interest at the present
time. Of fundamental importance are the development of a clear
understanding of the factors affecting the chemistry of the ring-opening
polymerization of cyclic esters and the influence of polymer microstructure on
properties, for both academic and technical reasons.
A detailed understanding of the factors affecting the ring-opening
polymerization of cyclic esters is the starting point for developing polymer
properties relevant to the intended application. The main factors to consider
are ring size, ring strain and the polymerization conditions used. Of these
factors ring strain is particularly important. The major contributions to ring
strain are bond angle distortion (angular strain), bond stretching or
compression, repulsion between eclipsed hydrogen atoms (conformational
strain, bond torsion) and non-bonding interactions between substituents
attached to different parts of the ring (transannular strain).
The polymerizability of a cyclic monomer is generally expressed by the
extent to which the free energy of the polymerizing system changes as it
converts into polymer. Molecular mechanics, semiempirical and density
functional theory were used to calculate the difference in internal energy
between the polymer and the monomer in each case and thus obtain an
estimate of polymerizability.

2. Method

Geometry optimizations were carried out using a molecular mechanics

method (MM+) for the monomer (M), the 4-, and 5-mers of the polymer (P4
and P5). The internal energy of a single polymer unit was estimated as the
difference in energy between the 5- and 4-mers. Therefore, the change in
internal energy upon polymerization ( Hp) could be calculated from:

Hp = (P5 - P4) - M

Further single point energy calculations were performed at AM1 and

B3LYP/6-31G* levels on MM+ optimized geometries. The structures of the
cyclic lactones studied in this work are illustrated in Figure 1. The
polymerisation of -butyrolactone was shown in Figure 2.

O O
O O
O O O
O

-propiolactone -butyrolactone -valerolactone -caprolactone

O O
O
O O
O

Heptanolactone Octanolactone Nonanolactone

Figure 1: Structures and nomenclature of the cyclic lactones (ring 4-10)

O O
O O-H
O H n

Figure 2: Polymerisation of -butyrolactone

3. Results and Discussion

The important factor affecting the ring opening polymerization of cyclic

esters is the ring strain. From our calculated bond angles and lengths of the
molecular mechanics optimized cyclic ester geometries in Table 1, the major
contribution to the ring strain is bond angle distortion. The high deviations
from the equilibrium values for bond angles were found in ring 4 and ring 7-10
whereas the bond lengths are mostly equivalent in all cases.

Reported values of the change in free energy ( Gp) and entropy ( Sp) during
the ring opening of cyclic esters are included in Table 2. It can be seen that
Sp remains essentially constant over the series of lactones studied.
Therefore, the variations in Hp can be used to indicate the relative
thermodynamic polymerizabilities in place of Gp. The lower Hp means that
the more readily polymerizability can be found. Comparison of the calculated
with molecular mechanics (MM+), semiempirical (AM1) and density functional
theory (B3LYP/6-31G*) and the reported heats of polymerization are shown
in Table 2 and Figure 3. As the ring size changes from 4-10, the magnitude of
Hp from AM1 methods shows the most similar trends with the experiment.
Uncorrelated results were found in the ring 9-10 for AM1 method and in the
ring 6-7, 9 and 10 for B3LYP/6-31G*. However, Hp from AM1 are consistent
with the calculation from B3LYP/6-31G* for all cases except ring 6. For the
ring size of 6-10, Hp becomes likely constant.
Figure 3: Hp from our molecular modeling calculations compared with the
experimental results.

4. Conclusions

Our calculations with molecular mechanics, semiempirical and density

functional theory for the lactone series as the ring size increase from 4-10
have demonstrated the correlation of bond angles, the ring strain and the
thermodynamic polymerizability. The best observed trends for Hp were found
from the semiempirical (AM1) method.
For more experiment, we will search for exactly conformers of single
polymer chains before calculation to make the results more accuracy. The
molecular optimized geometries calculated by single point energy on both
AM1 and B3LYP/6-31G* method will be changed into full optimized
geometries. Besides, we will try to compare the results which used by
difference formular such as
Hp = (P4 – P3) – M
or Hp = (P5 – P4) – M
or Hp = (P6 – P5) – M
.
.
.
and which one has the best experiment.

Acknowledgements

Authors would like to thank the Department of Chemistry, Faculty of

Science, Chiang Mai University for their support.

References

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