Anionic and coordination

polymerization
BY-VIVEK SHARMA
INDEX

• ANIONIC POLYMERIZATION
• Monomer characteristics
• Anionic initiation ,propagation and termination
• Mechanism and Reactivity
• Coordination polymerization
• Ziegler-natta catalyst
Anionic polymerization
• Ionic polymerization  in which the active centres
are anions or carboanion
• Anionic is a type of chain growth (addition)
polymerization.
• Like all chain-growth polymerizations, it takes
place in three steps: chain initiation, chain
propagation, and chain termination
Monomer characteristic
• Monomer must have a functionality greater than or equal
to 2.
• Electron-withdrawing substituents decrease the electron
density of the double bond and thus facilitate attack of an
anionic species on the double bond .
• Vinyl monomers with substituents that stabilize
the negative charge through charge
delocalization, undergo polymerization without
termination or chain transfer.
Initiation

• Anionic initiators are all electron donors of

varying base strengths.
• The initiator type required for a particular
polymerization depends on pKa values for the
conjugate acids of carboanion and
electronegativity of the substituent .
• Two main initiation pathways involve
(a) Nucleophilic initiators.
(b) electron transfer (through alkali metals)
By Nucleophilic initiators.
• Initiation takes place by a nucleophilic attack
that includes covalent or ionic metal amides such
as NaNH2 and LiN(C2H5)2, alkoxides, hydroxides,
cyanides, phosphine, amines, and organometallic
compounds such as n-C4H9Li and MgBr .
• Alkyl-lithium compounds are
probably the most useful of
these initiators, commercially
in the polymerizations of 1,3-
butadiene and isoprene.

• In the relatively few anionic

polymerizations initiated by
neutral nucleophiles such as
tertiary amines or
phosphine's the proposed
propagating species is a
zwitterion.
By Electron Transfer

• Polymerizations initiated by the aromatic

radical-anions such as sodium naphthalene
• Initiation proceeds by the prior formation of
the active initiator, the naphthalene radical–
anion by transfer of an electron from the alkali
metal to naphthalene
Propagation

• Propagation in anionic addition polymerization

results in the complete consumption of
monomer.
• It is very fast and occurs at low temperatures.
• This is due to the anion not being very stable,
the speed of the reaction as well as that heat is
released during the reaction.
• The stability can be greatly enhanced by
reducing the temperatures to near 0˚C
Termination

1) Polymerization without termination

2) Termination by impurities and deliberately

added transfer agents

3) Spontaneous termination
1)Polymerization without termination

• In I.P there is no compulsory chain termination

through recombination, because the growing
chains carrying same ionic charges .
• Thus active chain ends have indefinite lifetimes,
so they called as living polymerization.
• living anionic polymerization is evident from the
fact that if a reaction system is highly purified.
• Polymerization can be effected by adding more
monomer, either the same monomer or a
different monomer.
2)Termination by impurities and deliberately added
transfer agents

• Most anionic (as well as cationic) polymerizations

are carried out in an inert atmosphere with
rigorously cleaned reagents and glassware since
trace impurities lead to termination.

• Living polymers are terminated by the deliberate

addition of chain-transfer agent such as water or
alcohol to the reaction system after all of the
monomer has reacted.
• Oxygen and carbon dioxide from the
atmosphere add to propagating carbanions to
form peroxy and carboxyl anions. These are
normally not reactive enough to continue
propagation.
• Polymers with specific end groups can be
prepared by deliberately introducing particular
reagents that terminate living polymers.
• Telechelic polymers -that is, polymers with
reactive end groups.

• Hydroxyl-terminated polybutadiene (HTPB) can be

caused to grow in molecular size and to cross-link,
Spontaneous termination
• Living polymers do not live forever. In the
absence of terminating agents the concentration
of carbanion centers decays with time.
Coordination polymerization
• The polymerization of olefins and dienes catalysed
by organometallic compound is known as
coordination polymerization.
• The coordination polymerization is invented by two
Italian scientists: Karl Ziegler and Giulio Natta.
• They shared the Nobel prize in chemistry in 1963
using Ziegler–Natta catalysts to polymerize
nonpolar monomers: 1-alkene, cycloalkanes, dienes,
and alkynes through coordination mechanism
instead of common chain or step polymerization.
Ziegler-natta catalyst

• Ziegler-Natta catalyst may be simply defined as

a combination of two components:
• (1) a transition metal compound of an element
from groups IVB to VIIIB
• (2) an organometallic compound of a metal
from groups I to III
• The transition metal compound is referred to as
the catalyst and the organometallic compound
as the co-catalyst.
Types of Ziegler-natta catalyst

• 1) Heterogeneous catalysts -consist of transition

metal compound (e.g., titanium chloride) and
organometallic compounds (e.g., aluminium alkyl
halide) as co-catalyst.
• 2) The homogeneous catalysts are made from
transition metal metallocene and aluminum alkyl
halide.
Mechanism
• The organometallic component is believed to activate
the site by alkylation of a transition metal atom at the
surface.
• Of the various mechanisms that have been proposed,
the two that are most generally accepted are the so-
called monometallic and bimetallic mechanisms.
• Coordination catalysts perform two functions. First,
they supply the species that initiates the polymer and
secondly orient the monomer as stereospecific
addition.
Bimetallic Mechanism

• According to the bimetallic theory the truly

active catalysts are complexes that have an
electron-deficient bond, e.g., Ti-.-C.--AI in (II).
• The bimetallic mechanism involves propagation
in which growth occurs at two metal centers of
the bridge complex.
• The monomer is then incorporated into the
growing chain between the Al and the C, thereby
regenerating the complex
Monometallic mechanism
• Majority opinion now favors the concept that the
d-orbitals in the transition element are the main
source of catalytic activity and that chain growth
occurs at the Ti-alkyl bond, which acts as the
polymerization center, the function of the
aluminium alkyl being only to alkylate TiCI3.
• The first stage is the formation of the active
centre and the active centre formation was due
to the interaction of aluminium alkyl with an
octahedral vacancy around Ti.
Chain Termination
• 1)chain transfer to monomer

• 2)Chain transfer to the Group I-III metal alkyl

3)Spontaneous intermolecular ß-hydride transfer:

4) Chain transfer to an active hydrogen compound

such as molecular hydrogen
Main Advantages

• Reduction in branching in the final product

• Better stereo control
• Producing polymer with great crystallinity and
hence better physical properties.
• Formation of higher molecular weight polymer
• Ability to produce copolymer with polar co-
monomer.
 Thank you

• Design and editing by - Trippy