Ring Opening Metathesis Polymerization (ROMP) of Cyclooctene

Prepared By: Muhammad Farooq Matriculation # 764316

INTRODUCTION In ring opening metathesis polymerization, a mutual exchange of unsaturated carboncarbon bonds takes place in the presence of transition metal-catalyst.

ROMP is thermodynamically favored for strained ring systems, in other words ring strain is the driving force in this typical polymerization process. The olefin metathesis reaction was reported in 1955 in a Ti (II)-catalyzed polymerization of norbornene.

Ring opening polymerization reaction is generally reversible and the reacting alkenes need not be identical. After the development of highly active Grubbs catalyst, the ROMP has been successfully applied in many field of research. A metathesis reaction is defined as a chemical transformation in which atoms from different functional groups interchange with one another resulting in the redistribution of functionality yielding similar bonding pattern for both molecules. In olefins two carbon double bonds reacts and forms two new olefins. Efficiency of process is dependent on catalyst whereas polymer is also dependent on monomer structure.

Major difference in ROMP and condensation/ free radical polymerization is that, in condensation polymerization there is a loss of small molecule whereas in ROMP there is no loss of a molecule, and driving force is not attained from unsaturation. ROMP does not involve a loss of multiple bonding enthalpies also.

Following is the example of monomers, which can be, polymerizes by ROMP.

Cyclooctane

Cyclobutane

Fig 1. Monomers Examples

Initiators for ROMP are primarily ionic initiators and other can be molecular species like water. This later class of initiators is generally only effective for the more reactive cyclic monomers. Ionic initiators are usually more reactive against monomers containing carbon-carbon and carbon-oxygen double bonds.

Fig 2. ROMP Examples

Reaction Mechanism

Mechanisms of ring-opening polymerization differ according to monomer type and initiator, but most of the times they fit in following general form:

Monomer is attacked by some ionic or coordination species at the functional group that causes ring opening. This is followed by the attack of the ring-opened monomer on another cyclic unit, and so on.

Reaction Mechanism scheme

Initiation

Propagation

Termination

Fig 3. ROMP Reaction Scheme

Backbiting in this particular reaction also takes place; consider the polymerization of polyacetylene from cyclotetraene. After the ring opening and the growing polymer can divide itself on molecular level and can form benzene.

Fig 4. Backbiting in ROMP

Features Some very important features of romp are as follows It is stable against H2Oand ROH We have good control on end group Block copolymers can also be made Telechelic polymer formation is also possible

EXPERIMENT Following values of monomer, initiator, solvent and quenching agent were consumed Table 1 Sr. No 1 2 3 4 5 Regent & material DCM Cyclooctene Grubbs Catalyst HCl Phenol Mol. wt. (g/ mol) 84.93 110.2 822.96 36.46 94.11 Amount 2 mL 0.81ml .0055 g One Drop One Drop

Ruthenium based Grubbs Catalyst was used in our experiment.

Fig 5. Benzylidene-bis(tricyclohexylphosphine)dichlororuthenium Procedure 0.81 mL of Cycloocten was dissolved in 2 ml DCM in a schlenk flask. Flask was kept under inert atmosphere. 0.0055 grams of Grubbs catalyst was added in the flask. Flask was closed as the imitator was introduced to the monomer. Polymerization reaction starts immediately after the introduction of initiator. Reaction scheme is given below.

Fig 6. Polymerization Reaction scheme of Cyclooctene

After continuous stirring of one 1 hr., 2ml of DCM, one drop of HCl and one drop of Phenol was added to quench the reaction. Solution changes its color upon the addition of quenching agents. After 20 minutes, the resultant product was precipitated in 40 mL acidic methanol.

Answer.1 There are significant no of monomers, which can be polymerized by using ROMP. The ability of any cyclic monomer to be polymerized using this specific method depends upon couple of very important factors.

Primarily, cyclic olefin should have sufficient ring strain favorable for the ROMP reaction and secondarily there should be a corresponding polymerization mechanism present, that can convert the monomer into the polymer. Thermodynamics also plays very vital role in ROMP. Reaction equilibrium should be shifted toward the conversion of monomer into polymer side. If we analyze closely the ring strain which is certainly the driving force in ROMP reactions. It is a force, which is caused by the angular distortion of the atoms in the ring. It is also known that free energy of the cycloalkanes is also responsible for the monomer to polymer conversion. Benzene has positive free energy due to which its structure is not exposed to any ring strain thus it is not process able by ROMP. Functional groups also decrease the ability of a cycloalkane to be processed by ROMP. ANSWER 2

ROMP is capable of producing telechelic polymers and block co polymers. For example, Cyclooctene can be polymerized with PEG to produce a block copolymer. Apart from that, ROMP can be combined with ATRP and RAFT to produce block copolymers. References

Edited by Philippe Dubois, Handbook of Ring-Opening Polymerization, PP 1 Nicolas Spassk, Ring Opening Polymerization. PP 3-10 Robert Ebewele O Ebewele, Polymer Science and Technology, PP 52 Lecture Notes