POLYMERIZATION OF

LACTONES AND
CHARACTERIZATIONS OF
YIELDED POLYMERS BY FTIR

Author:
Carlos David Cumba Burgos

Organic Chemistry II P1

Ph. D. Haci Baykara

15/11/2018

GUAYAQUIL - ECUADOR

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 Table of contents

1. Introduction ............................................................................................................... 2
1.1. Purpose................................................................................................................... 2
1.2.Scope ....................................................................................................................... 3
2. Method ...................................................................................................................... 3
2.1 Literature Review ................................................................................................... 3
3. Conclusions ............................................................................................................... 5
4. Recomendations and implementation ....................................................................... 5
5. Declaration/Disclaimer.............................................................................................. 5

List of figures
Illustration IPolymerization of E-Caprolactone to Poli-E-Caprolactone ...................................... 3
Illustration IIMechanism of the polymerization of lactones ......................................................... 4
Illustration IIIMechanism of the polymerization of lactones by cationic catalysis ....................... 4

List of tables
Table IExamples of polymerization of lactones ............................................................................ 4

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 Summary
This document contains the polymerization of lactones catalyzed by enzymes and the
corresponding spectroscopic characterization by FTIR, where the polymerization reaction
of certain cyclic esters is explained, together with the mechanism. Also comparing
physical states and molecular weight between the monomers and the polymers obtained
from these.

1. Introduction

For years, polymers or macromolecules have become increasingly important in our

society to a point where it is difficult to imagine situations in our daily life where
polymers are not present. Materials composed of polymers that today are everyday such
as insulating windows, non-stick pans, car bumpers, contact lenses or children's diapers
were nonexistent just a few years ago. The polymeric materials can be classified into two
groups; polymers of natural origin and synthetic polymers or those obtained industrially
by chemical reactions.1

In recent years, obtaining biodegradable plastics from natural materials has been one of
the great challenges in different sectors: industrial, agricultural and materials for various
services. Aliphatic polyesters such as polyhydroxyalkanoates, PHA's, and polylactones
are natural thermoplastic polyesters that can be obtained from renewable natural sources
as they are produced by a wide range of microorganisms and in some cases by plants.
They have the advantage of being biodegradable, a fact that has received a wide attention,
besides that it can be a very good option to produce polymers that allow to replace to a
large extent the synthetic polymers coming from petroleum.2

The polymerization of the lactones provides a simple way to synthesize polyesters and
that does not involve long reaction processes and also avoiding the high temperatures in
the condensation reaction. To select the initiator or catalyst to perform the polymerization,
depends on the structure of the monomer (in this case lactone).3

Most of the polymers that are absorbable and used as implants are obtained by ROP (ring
opening polymerization) of lactones. These polyesters have been successfully modified
in some ways, and their applications are from the textile area to the development of drugs.
The polymers that are made today are synthesized continuously, and there is a great
demand to implement new materials developing better synthesizing processes. Obtaining
an understanding of the mechanisms that control synthesis is very important.4

1.1. Purpose

Know the type of reaction involved in the polymerization of lactones, using the lipase
enzyme as a catalyst and analyzing the type of polymer that will be obtained by enzymatic
polymerization along with other factors such as temperature.

Finally, analyze the characterization of yielded polymers using FTIR.

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 1.2. Scope

To inform the students cursing the current organic chemistry II subject in ESPOL, on the
types of polymerization that exist, which is the indicated one to form a macromolecule
that in this case is a polyester, from an organic compound of the cyclic ester type
"lactone".

2. Method

This document will be focused on the mechanism and main facts that influence the
polymerization of lactones through an enzymatic polymerization for the obtaining of
polymers.
The knowledge that was gathered to make this document was found in several external
references, such as documents, scientific documents and articles that talk about the
method and the facts that influence the polymerization of lactones, such as the specialty
and selectivity of enzymes to be able to perform an enzymatic polymerization towards
lactones.5
The characterization by FT-IR of specific polyester is mentioned and analyzed, using the
spectroscopic IR of a compound with polycaprolactone that will be used to explain the
behavior of this functional group in this characterization.
The information acquired in this document will serve to clarify doubts about future
research or experiments related to the enzymatic polymerization of lactones and
corresponding infrared spectroscopes. 6

2.1 Literature Review

For the polymerization of lactones using enzymes as a catalyst, we need to determine

the important factors that determine the selectivity of the enzymes, such as spatial
restrictions, electrostatic interactions, the hydrophobicity of the area around the active
site and the means by which the transition state is stabilized. Thus, enzymes
discriminate between different chemical groups, chemoselectivity.7
Now for the synthesis of polyester catalyzed by enzymes can be developed by two types
of polymerization: by polycondensation or polymerization by ring opening. Lipases
catalyze the polycondensation of hydroxy acids and the polycondensation of diacids or
anhydrides with diols.
Lipase is any enzyme; these enzymes come from animals, plants or microorganisms, and
are used to catalyze the hydrolysis of lipids (fats).8

Illustration IPolymerization of E-Caprolactone to Poli-E-Caprolactone

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Although studies of the polymerization mechanism of lactones are scarce, in certain
documents they recommend that the anionic polymerization of lactones must develop the
fission of acyl-oxygen with diffusion through an alkoxide anion.

Illustration IIMechanism of the polymerization of lactones

In the case of a cationic catalysis, in the absence of active hydrogen initiators, it is

recommended to involve propagation through a carbon ion with acyl oxygen being the
main mode of ring opening.

Illustration IIIMechanism of the polymerization of lactones by cationic catalysis

Below are some examples of results, where the mechanism of polymerization of lactones
catalyzed by enzymes such as lipase is used, factors such as names, molecular weight and
physical state can be compared.

Monomer Physical Molecular weight Polymer Physical Molecular

state (g/mol) state weight (g/mol)
-Caprolactone Liquid 114.4 Poli(-Caprolactone) Solid 25523*
-Butirolactone Liquid 86.09 Poli(-Butirolactone) Wax 716
-Decanolactone Liquid 170.25 Poli(-Decanolactone) Oil 450
Table IExamples of polymerization of lactones

Spectroscopic Characterization by FTIR

- The signals at 2969 cm-1 and 2906 cm-1 indicate the tension of the C-H bond
within a linear carbon chain (alkane). The signal at 1302 cm-1 corresponds to the
flexion of CH2 and the signal at 736 cm-1 represents the rolling of a chain of
type -(CH2)n-.
- The peak pronounced at 1743 cm-1 corresponds to the voltage of the C = O bond
of the carbonyl group, and in turn, belongs to the ester functional group. In
addition, more signals are presented at 1236 cm-1, 1172 cm-1, 1141 cm-1 and
1018 cm-1 corresponding to the symmetric and asymmetric tension of the C-O
bond.
- The signal at 2110 cm-1 indicates an isothiocyanate functional group and is
confirmed present in an aliphatic chain with the small overtone located at 1089
cm-1. 6

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 3. Conclusions

In a lactone polymerization reaction, we will have as a product a polyester, because the

lactones are organic compounds of cyclic esters.
In a condensation polymerization, reaction occurs if the monomer molecule loses atoms
when it becomes part of the polymer. The molecules you lose are usually small molecules,
like water.
Through ROP (ring opening of the polymerization), better results can be obtained without
the need to extract water.
The major peaks to be considered are the highest for example, the peak pronounced at
1743 cm-1, corresponds to the C = O bond, and the peaks of 1236 cm-1, 1172 cm-1, 1141
cm-1 and 1018 cm-1 that correspond to the C-O bond.

4. Recomendations and implementation

- The use of lipases as a catalyst is important because it allows us to obtain a high

reaction yield.
- When performing any type of polymerization reaction, such as: ROP or
condensation polymerization, it is important to control certain factors such as:
amount of reagents, temperature and catalyst used to perform the polymerization.
- For the spectroscopic characterization by FT-IR, it is important to analyze all the
peaks that are present in the spectra that appear the functional groups and certain
interferences that can occur.
The implementations that could be considered for the polymerization reaction of lactones:
- The ring opening reaction of the lactones to polymerize polyesters of degradable
characteristics, which can be easily disintegrated, being important from an
environmental point of view.
- The synthesis with lipases as a catalyst can also catalyze the hydrolysis or
synthesis of a broad group of carboxylic esters.

5. Declaration/Disclaimer

I accept that I have not been able to use the information or the subject of the present
document for some kind of future work and I accept that Ph.D. Haci Baykara could use it
for whatever purpose he wants.

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References
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nueva generación de catalizadores para la síntesis de polímeros. An Quim.
2013;109(3):173-181.
2. En D, Materiales CDE, Wilberth MC, Herrera A, Aguilar M, Cicy V. “ Síntesis
enzimática y propiedades térmicas de Poli ( lactonas ) y sus copolímeros
obtenidos vía polimerización por apertura de anillo .” 2014.
3. Von Schenck H, Ryner M, Albertsson AC, Svensson M. Ring-opening
polymerization of lactones and lactides with Sn(IV) and Al(III) initiators.
Macromolecules. 2002. doi:10.1021/ma011653i
4. Von Schenck H, Ryner M, Albertsson AC, Svensson M. Ring-opening
polymerization of lactones and lactides with Sn(IV) and Al(III) initiators.
Macromolecules. 2002;35(5):1556-1562. doi:10.1021/ma011653i
5. Plou FJ. Catalizadores Para Nuestra Vida Cotidiana ”.
6. Contreras J, Vivas M, Torres C. Disponible en:
http://www.redalyc.org/articulo.oa?id=93320205. 2007.
7. Y PRK, S RCJ. Análisis de espectros FTIR de dos muestras de textil de poliéster
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8. Gonz J, Rodr J, Mart M. Las lipasas : enzimas con potencial para el desarrollo de
biocatalizadores inmovilizados por adsorción interfacial Lipases : enzymes
having the potential for developing immobilised biocatalysts by interfacial
adsorption. XII(1).