Ionic Polymerization

Dr. Saima Shabbir, MS&E

 Ionic Polymerization
Active center is ionic charge instead of free radical.
Therefore, ionic polymerization is more monomer
specific than free radical.
Only monomers that can sufficiently stabilize positive
or negative charge will undergo ionic polymerization.
Cationic Polymerization

Anionic Polymerization
Therefore, most monomers cannot be polymerized
by ionic polymerization.

Dr. Saima Shabbir, MS&E

 Characteristics of Ionic Polymerization
i) Ionic polymerization is faster than free radical
polymerization (generally)
- [M*] = concentration of propagating chain is
higher
- [M+], [M-] = 104 - 106 [M]
ii) Counter ion of opposite charge
- Degree of association (Xn) influences rate of
propagation (kp)
- Polarity of solvent, ability to solvate counter ion
significantly affect

Dr. Saima Shabbir, MS&E

 Characteristics of Ionic Polymerization
iii) Termination cannot occur between two
growing chains
- Active centers are of the same charge and
the same charge repel each other
so that coupling cannot take place

Dr. Saima Shabbir, MS&E

 A. Cationic Polymerization

Dr. Saima Shabbir, MS&E

 Cationic Polymerization
I. Initiation
Creation of +ve active centers:
Monomer + Electrophiles, R+
a) Protonic acids, H2SO4, HClO4
involve addition of H+ to monomer
b) Hydrogen halide acids, HCl ------ not suitable
because Cl- recombines.
c) Lewis acids + co-catalyst such as water, acid,
organic halide

Dr. Saima Shabbir, MS&E

 Cationic Polymerization
Lewis acids: Boron trifluoride BF3, Aluminum
chloride AlCl3, Tin tetrachloride SnCl4
First step
BF3 + H2O (trace) H+ (BF3OH)-
AlCl3 + RCl R+ (AlCl4)-

Dr. Saima Shabbir, MS&E

 Cationic Polymerization
Second Step
H+(BF3OH)- + CH2=CR1R2 CH3-C+R1R2 (BF3OH)-
R+A- + CH2=CR1R2 R-CH2-C+R1R2A-

Initiator Electrophile, R+ Counter ion, A-

Dr. Saima Shabbir, MS&E

 Cationic Polymerization
II. Propagation

Propagation step is similar to free radical

Predominantly head-to-tail
Used for making stereospecific polymers

Dr. Saima Shabbir, MS&E

 Cationic Polymerization
III. Termination
a) Unimolecular rearrangement of ion pair:

b) Chain transfer to monomer is usual

Terminated polymer New chain

Chain transfer to solvent, impurities, H2O,
polymer (branching) are all common.
Dr. Saima Shabbir, MS&E
 Kinetics of Cationic Polymerization
Specific to actual monomer, solvent, initiator
Side reactions are many, and likely.
Sub-zero temperatures are often necessary for high
molecular weight polymers
If water is co-catalyst, it must by stoichiometric
H2O is good charge transfer agent
Rapid; complete conversion in seconds
Problem: heat transfer
non-steady state conditions!

Dr. Saima Shabbir, MS&E

 Kinetics of Cationic Polymerization
Only Commercially Noteworthy Example:
Synthesis of butyl rubber by copolymerization of
isobutylene with small amount of isoprene
At -90oC using Lewis acid initiator (AlCl3) in chlorinated
solvents such as chloromethane.
Solvent/ Counter Ion Effects:

Very polar solvents (dichloromethane) separate ions and

large, bulky counter ions (SbCl6 weakly associated-----
faster
Dr. Saima Shabbir, MS&E
 B. Anionic Polymerization

Dr. Saima Shabbir, MS&E

 Anionic Polymerization
Absence of an inherent termination process
- Ion pair rearrangement involves elimination of a hydride
ion, H-.....highly unfavorable.
- Alkali metal counter ions, +, have no tendency to
recombine with active growing centers to form dead
polymer.
Thus, without chain transfer, there is no tendency to
create unreactive polymer
Polymer chains that permanently retain their active
centers and grow as long as there is monomer ----- Living
Polymerization
Dr. Saima Shabbir, MS&E
 Anionic Polymerization
Example: Polymerization of styrene in liquid
ammonia (one of first examples of anionic
polymerization)
I. Initiation
KNH2 K+ + NH2-
potassium amide amide ion

Dr. Saima Shabbir, MS&E

 Anionic Polymerization
II. Propagation

III. Chain Transfer

2

Dr. Saima Shabbir, MS&E

 Anionic Polymerization
Common Initiator Systems
- Organolithium compounds: Butyl lithium
Very reactive
Used with non-polar hydrocarbon solvents
With low Cs constants ----- living polymerization

Dr. Saima Shabbir, MS&E

 Anionic Polymerization
Solvent/ Counter Ion Effects
M+ counter ions are smaller than A-
- tightly bound
- Propagation 102 - 104 times slower than cationic
- Using polar solvents help solvate and activate ion
pairs

Dr. Saima Shabbir, MS&E

 Anionic Polymerization
Practical Considerations
High reactivity
Low concentration of reacting species
- Purity, dryness, inert gases needed
- H2O, CO2, O2 all kill growing chains
- Despite difficulties: very narrow PDIs
Block copolymers of defined length

Dr. Saima Shabbir, MS&E