Coordination Polymerization

1 What is coordination polymerization?

Coordination polymerization is a form of polymerization that is catalyzed by transition metal
salts and complexes through formation of monomer-catalyst co-ordination complex.
Polymerization reactions, especially for olefins & dines, catalyzed by organometallic compounds.

2 General process for coordination polymerization

2.1 Initiation
A coordination bond formed between metal atom of catalyst and carbon atom of monomer

Mt represent transition metal such as Ti, Mo, Cr, Ni, V, Rh

Coordinated metal carbon bond formed in monomer-catalyst complex acts as the active center from
where propagation can start.

2.2 Propagation
In propagation step a incoming monomer is inserted at active centre of metal carbon bond
2.2.1 Heterogeneous system
• In coordination polymerization, the catalyst monomer complex is a heterogeneous system,
with metal ion in solid phase and carbanion of alkyl group in the solvent phase.
• The monomer inserted between metal ion and carbanion with result that polymer chain
formed is pushed out from the solid catalyst surface. Due to this coordination polymerization
also called as ‘Insertion Polymerization’.

• Here M1,M2,M3 and so on are the first, second and third and so on monomer units added in
to growing chain.

3 Stereoregularity in coordination polymerization

• Depending on the polarity of metal-carbon coordination bond and that of solvent medium, the
metal counter ion is placed in a particular spatial arrangement with respect to the anion.
• The spatial arrangement has tremendous effect on spatial orientation of incoming monomer
and also on in which manner monomer is inserted in to the growing chain
• The specific spatial arrangement of monomeric unit inserted in to the growing chains impart
stereoregularity to the polymer formed
• By choosing proper catalyst, solvent system we can formulate highly stereoregular polymer
 4 Classification of coordination polymerisation

Coordination Polymerization

Heterogeneous Coordination Homogeneous Coordination Polymerization

Polymerization Ziegler Nata process
Catalyst is in solid phase and Monomer
& Polymer formed in solvent phase
Reaction ate is lower that Homogeneous
system
ZN initiators are multisite initiators
Eg. TICl4 + Al(Et)3
Metallocene catalysis
Catalyst, Cocatalyst, Monomer & polymer
formed all in solvent phase.
Reaction rate is higher than heterogeneous
system
The metallocene initiators are single-site
initiators
Eg. bis(cyclopentadienyl)zirconium dichloride
& Methylaluminoxane
4.1 Ziegler-Nata Polymerization (Heterogeneous system)
• Ziegler-Nata catalyst system consists of two components Catalyst and Co-catalyst, catalyst
components consist of halides of IV-VIII group elements and co-catalyst consist of organic
metallic compounds alkyl/aryl/hydrides of I-IV group metals.
• Catalyst : TiCl4/ TiCl3 acts as electron donor
• Co-catalyst : Al(Et)3/ Al(Et)2Cl acts as electron acceptor
• There are two mechanisms are proposed Monometallic mechanism by Cossee and
Bimetallic mechanism by Nata

4.1.1 Bimetallic mechanism by Nata

4.1.1.1 Activation of catalyst
• Nata suggested that when catalyst & cocatalyst are mixed, chemisorption of aluminum alkyl
(electropositive in nature) occurs on the titanium chloride solid surface resulting formation of
electron deficient bridge complex.

TiCl4 + Al(Et)3

• Aluminum alkyls acts like a electron acceptor and electron donor is Titanium halide, therefore
readily formed a coordination complex. The coordination complex formed is insoluble in
solvent, hence ‘Heterogeneous in nature’.
• This complex acts now a active center.

4.1.1.2 Initiation
• The monomer is attracted towards Ti-C bond in active center and forms a pi complex with Ti
atom.

• The bond between Ti & R opens up producing electron deficient Ti and a carbanion.
 • The Ti atom attract pi electron pair of monomer and form a sigma bond, while counter ion
attracts the electron deficient center of monomer. The monomer get inserted in to a transition
state ring structure.

• This transition state now give rise to the chain growth at metal carbon bod & regenerating the

4.1.1.3 Propagation
• Repeating the whole sequence, with addition of second monomer molecule, we get structure
of resultant chain growth

• The orientation of substituent group of monomer is always taken from metal ion end,
resulting stereoregular polymer.
4.1.2 Monometallic mechanism by Cossee
• It assume that active center is Ti-R part of the catalyst, while aluminum alkyl perform only the
function of alkylating the TiCl3

4.1.2.1 Activation of catalyst

• On the crystal surface, a Ti atom is surrounded by 5 chlorine atoms with one empty orbital to
be filled. When Et3Al comes in, it donates an ethyl group to Ti atom and the Al atom is
coordinated to one of the chlorine atoms. Meanwhile, one chlorine atom from titanium is kicked
out during this process. Thus, the catalyst system still has an empty orbital

4.1.2.2 Initiation
• Once active catalyst is formed, the monomer is attracted towards vacant d orbital which then
form a transition π-complex with Titanium

pi complex Transition state

• The transition state quickly give rise to the growth of the polymer chain by monomeric
insertion of Ti – Et bond. While monomeric group is inserted and chain grows, the vacant d-
orbital can be regenerated at the same position or at position where the ethyl group was
originally attached
 • When vacant d-orbital is regenerated at same position all the time, the incoming monomer
unit inserted with same spatial arrangement, resulting in formation of ‘Isotactic Polymer’
• If d-orbital migrate from one position to other alternately, the monomers get inserted with
alternate spatial arrangement, resulting in formation of ‘Syndiotactic Polymer’.
• This depends on interactive force exist between
1) A substituent group on incoming monomer and already inserted monomeric unit
2) The substituent group of incoming monomer and chlorine atoms of active catalyst
3) Catalyst system
4) Catalyst crystal structure
5) Molar ratios of catalyst components
6) Temperature of catalyst complex

4.1.2.3 Prpagation
• When other alkene molecules come in, this process starts over and over, giving linear
polyalkene.

4.1.2.4 Termination
• β -hydride Hydride transfer directly to the transition metal

• Chain transfer to Monomer

• Chain transfer to Aluminium

• Chain transfer to active hydrogen compound

Total Ziegler-Nata process in simple form

4.2 Homogeneous coordination polymerization
• In homogeneous system the catalyst, reactant & product are in same phase. Here
Metallocene catalysis is followed.
• Metallocene catalyst: These are the organometallic compound which a metal cation is
sandwiched between two cyclopentadiene anions derivatives

Me : Zr, Ti, Hf

Me Me

• Cocatalyst : Methylaluminoxane [Al(CH3)O]n

• Acts as Initiator/Activator & has two functions: alkylation of a transition metal–chloride bond
followed by abstraction of the second chloride

4.2.1.1 Activation of catalyst

• Alkylation : Catalyst is alkylated by MAO by replacing one chlorine atom

bis(cyclopentadienyl)zirconium dichloride
 • Abstraction of second chlorine : MAO will abstract second chlorine to give a active catalyst
with vacant d-orbital where monomer get attracted

4.2.1.2 Initiation
• Once active catalyst is formed, the monomer is attracted towards vacant d orbital which then
form a transition π-complex with Zirconium
• This lead to form a transition state and transition state lead to migration of alkyl group to Zr
by regenerating vacant d orbital

4.2.1.3 Propagation
• The monomer insertion process get repeated to form a polymer

4.2.1.4 Termination : same as 6.1.2.4

5 Tacticity
• Tacticity is defined as the relative stereochemistry of adjacent chiral centers within a
macromolecule / polymer.
• Tactcity is the orderliness of the succession of configurational repeating units in the main chain
of a polymer molecule.

5.1 Isotactic Polymer

• In isotactic polymer all the substituents are located on the same side of the polymer backbone

5.2 Syndiotactic Polymer

• In syndiotactic macromolecules all the substituents are located on the alternate position on
both side of the macromolecular backbone.

5.3 Atactic/Heterotactic Polymer

• The substituents are located randomly to one side or other of the polymer chain and so the
polymer is a mixture of many diastereoisomers.

6 Properties of stereoregular polymer

• The ordered polymers are dramatically different from the corresponding structure in
morphological and physical properties
• The stereoregular polymers usually obtained as high crystalline material.
• Crystallinity leads to high physical strength and increased solvent and chemical resistance
• Properties of some stereoregular polymers mentioned below

Tg (° Tm (°
Polymer Isomer Properties Use
C) C)
Strong,
Polypropene Isotactic - 165 Plastic & fiber
Crystalline
Crystalline, more
Polypropene Syndiotactic - 20 soluble in organic --
solvents
Polypropene Atactic - - In asphalt blends,
 Amorphous with
Formulation for
oily to wax soft
lubricants
appearance
Strong, harder,
Trans-1,4
Trans -58 74 less elastic, Golf ball covers
polyisoprene
Abrasion resistant
Cis-1,4 Low crystallinity,
Cis -73 28 Rubber for tires
polyisoprene excellent elastomer