Title: Ring Opening Metathesis Polymerization

Author: Alexander Paul Espinoza Vsquez

Faculty of Natural Sciences and Mathematics

Chemical Engineering

Guayaquil, Ecuador

Organy Chemistry II

Dr. Haci Baykara

Ring Opening Methatesis Polimerization

In 1950, Anderson and Merckling were the first researchers that made of develop
polymer, and in 1964, Bailey and Banks reported the first olefin metathesis reaction
making use of catalyst such as (6 ), ()6 3 . The reaction was carried
out at elevated temperatures and it was not selective. Some years later, new catalysts (
6 , 2 5 2 5 2 ) were developed which under certain conditions increased
the selectivity in the reaction. Some studies revealed that the product was governed by
thermodynamic stability1.

The importance of the study of this reaction is the manufacture of polymers, which are
useful in different labor fields:

In medicine, the copolymers have been developed. They have an anti-

inflammatory agents (indomethacin), which help fight certain types of cancer,
such as leukemia and melanoma.
In the oil industries, Polynorbornene is used to reduce the impact of oil spills on
the environment, because these polymers have a high capacity for the absorption
of oils and certain hydrocarbons.

ROMP n
n

Scheme 1: The ROMP of the norbornene

Mecanismo de la reaccin
Initiation R
LnM Coordinetion [2+2] LnM
R LnM
Metal LnM
R
alkylidene R
Metallacyclobutane

Propagation
R
R
LnM LnM
LnM m+2
R

Terminamination
R

R LnM X Y m+2
X Y
LnM
m+2

The ring opening metathesis polimerization is catalyzed by an alkylidene metal. The

initiator reacts with the more stable part of the monomer, the double bond. Then, a cyclic
olefin intermediate is formed which it will be broken to give rise to a new olefin2.

The ring opening methatesis polimerization has three steps:

Initiation: The reaction begins with the coordination of the transition metal of the
alkylidene (initiator) with the cyclic olefin. Then, the formation of a metal cyclO
butane occurs. Finally, the intermediate compound is broken and formed a new
metal alkylidene.
Propagation: The new metal alkylidene has the properties similar to those of the
initiator to interact with the olefins, due to the metal that it has. The metal
alkylidene interacts with the monomer allowing the growth of the polymer.
Termination: The growth of the molecule is defined until to consume all the
monomer in the reaction. There is an equilibrium where even the reaction is
reversible. To complete the reaction, a specialized chemical compound is added
to remove the transition metal and replace it with a known functional group.

This reaction occurs only in cyclic olefins made up of three, four, eight or more carbons,
because their energy of strain degree is greather that 1,5 kcal/mol 3 (Table 1). If the energy
of strain degree is greather that 1,5 kcal/mol, the reaction is energetically favored.
 Ring size Strain energy (/)

3 27.5
4 26.3
5 6.2
6 0.1
7 6.2
8 9.7
9 12.6
10 12.4
11 11.3
12 4.1
13 5.2
14 1.9
15 1.9
16 2.0
Table 1: Energy strain of cyclic olefins. Recovered from:
https://www.revolvy.com/topic/Ring%20strain&item_type=topic.

If cyclic olefins do not have a energy, there is not enough energy to promove the reaction.
In case, that the reaction does not have enough energy happens a ring closing metathesis.
Also, the ring closing metathesis is favored, if there is low concentration of monomer and
high temperatures in the reaction.

In conclusion, the ring opening methatesis polymerization reaction requires a metal

alkylidene catalyst, low temperatures and high concentrations of monomer so that the
reaction is successfully carried out. Also, the strain energic of ciclic olefins influences in
the reaction. The advantage of this mechanism is that it allows a variety of polymers to
be obtained, for example: copolymers have been synthesized to combat certain types of
cancer. Another example would be polynorbornene which is used such as vibration
damper and noises.
Bibliography

1. Piotti ME. Ring opening metathesis polymerization. Curr Opin Colloid Interface
Sci. 1999;4(1999):539-547.

2. Park H, Kang EH, Mller L, Choi TL. Versatile Tandem Ring-Opening/Ring-

Closing Metathesis Polymerization: Strategies for Successful Polymerization of
Challenging Monomers and Their Mechanistic Studies. J Am Chem Soc.
2016;138(7):2244-2251. doi:10.1021/jacs.5b12223.

3. Bielawski CW, Grubbs RH. Living Ring-Opening Metathesis Polymerization.;

2009. doi:10.1002/9783527629091.ch6.