10.

569 Synthesis of Polymers

Prof. Paula Hammond
Lecture 25: “Living” Cationic Polymerizations, Examples of Cationic
Polymerization, Isobutyl Rubber Synthesis, Polyvinyl Ethers

Cationic Polymerization

Some differences between cationic and anionic polymerization

• Rates are faster for cationic
(1 or more orders of magnitude faster than anionic or free radical)

• C is very reactive, difficult to control and stabilize

→ more transfer occurs

→ more side reactions
→ more difficult to form “living” systems
→ hard to make polymers with low PDI or block copolymers

• Living cationic only possible for a specific subset of monomers

• Most industrial cationic processes are not living

- recent developments are improving this

Kinetic Steps for Cationic Polymerization

Initiation: Use Acids
• Protonic Acids (Bronsted): HA
comes off
strong, but without nucleophilic counterion
HClO4, CF3SO3H, H2SO4, CFCOOH
→ ClO4-
want to avoid
recombination
through counterion

H A + H2C CH H3C CH A
R R

• Lewis Acids
Often as initiator/coordination complexes
helps stabilize counterions and prevent
recombination

BF3 + H2O ↔ [H+BF3-OH]

AlCl3 + RCl ↔ [R+AlCl4-] Equilibrium between
SbF5 + HF ↔ [H+SbF6-] anion-cation pair

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
 Carbenium salts with aromatic stabilization

C Cl + SbCl5 C SbCl6

Propagation
H H H
A H2 A
CH2 C + CH2 C C C
H2C CHR
R vinyl monomer R R
initiation species

Note: rearrangements can occur, especially if a more stable carbocattion can be

formed (e.g. tertiary carbocation)
(most common for 1-alkenes, α olefins)

e.g. 2 methyl butene H2C CH

CH
H3C CH3

H
CH3
C C H2
H2 C C C
H3C C H H2
CH3
CH3
secondary carbocation tertiary carbocation

This occurs via intramolecular hydride (H-) shifts

Usually slow: If Rp ≤ rearrangement rate, will get rearranged product
CH3
H2 H2
C C C
CH3
If Rp > rearrangement rate, will get random copolymer

CH3 H
H2 H2 H2
C C C C C
N m
CH3 H3C CH3
As T↑, m↑ (less rearrangement)
Rate of rearrangement does not increase as fast as rate of propagation.

Hydride shift NOT common for conjugated monomers like: styrene, vinyl ethers and
isobutylene and other tertiary carbocations.
10.569, Synthesis of Polymers, Fall 2006 Lecture 25
Prof. Paula Hammond Page 2 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
Termination and Transfer (Several Possibilities)
A) Termination with counterion: kills propagating cation, kinetic chain (kt)
i) Combination
H H O
kt,comb
CH2 C + CF3COO CH2 C O C CF3

R R

ii) Anion Splitting

H H
kt,s
CH2 C + BF3OH CH2 C OH + BF3
R R

B) Transfer or termination to impurity or solvent

O
To H2O, ROR, NR3, C OR , etc.

Initiator
ktr,s
HMNM(IZ) + XA HMNMA + X(IZ)
Impurity
or Solvent
e.g.
more stable than H
C
H H R
A R
CH2 C + ROR CH2 C O A

R R R
not as reactive,
acts as retardant
- will not propagate further

or
H H
A
CH2 C + R-OH CH2 C OR + H A

R R weak acid
will not initiate

All these processes

kill chain length.

10.569, Synthesis of Polymers, Fall 2006 Lecture 25

Prof. Paula Hammond Page 3 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
Transfer (Kinetic Chain Maintained)
A) Proton transfer to monomer
H H H H H

C C A + H2C CH C C + H3C C A

H R R R R
propagates

B) Hydride ion transfer from monomer

H H
H2C C CH2 CH2 + H2C C A
CH2 C A +
R R R R
propagates

k tr , M
In general, chain transfer to monomer is favorable so CM → can be sizeable.
kp

C) Proton transfer to counterion

(“spontaneous termination”)
CH3 CH3
ktr,ci CH2 C +
CH2 C A H A

CH3 CH2
usually goes on
to initiate again
propagating
continues
protic acid initiators
are possible
+Lewis acids are
less likely

Usually propagates
(does NOT kill chain)

10.569, Synthesis of Polymers, Fall 2006 Lecture 25

Prof. Paula Hammond Page 4 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
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Kinetic Expressions

Inititation: Assume Lewis Acid Pair

⎡Y + ( IZ )− ⎤
I + ZY
1. Y(IZ) ⇒ K = ⎣ ⎦
⎡⎣I ⎤⎡ ZY
⎦⎣ ⎦ ⎤

ki
2. Y(IZ) + M YM(IZ) often rate limiting

If step 2 is rate determining, then

Ri = ki ⎡Y + ( IZ ) ⎤ ⎡⎣M ⎤⎦
−

⎣ ⎦
= ki K ⎣⎡I ⎦⎣ ZY
⎤⎡ ⎦⎣ ⎤⎡M ⎦⎤
*Ri could be determined based on step 1. Then the expressions would be different.

Propagation
kp
YMj(IZ) + M YMj+1(IZ) Assumption: chain length has
little effect on reactivity
some number Let [M+] = total concentration of
of monomer
all-size propagating carbocations
Rp = kp ⎡YM +j ( IZ ) ⎤ ⎣⎡M ⎦⎤ = kp ⎣⎡M + ⎦⎤ ⎣⎡M ⎤⎦
−
(ion pairs + free ions)
⎣ ⎦

Termination
Must determine primary means of termination (solvent, impurities, counterion
combinations, or all?)

Example case: termination by counterion combination

kt,comb
YM(IZ) YMIZ ⇒ Rt = kt ,comb ⎡YM + ( IZ ) ⎤ = kt ,comb ⎡⎣M + ⎤⎦
−

⎣ ⎦

If we assume steady state [M+]

Rt = kt ⎡⎣ M + ⎤⎦ = ki K ⎣⎡M ⎤⎡
⎦⎣I ⎦⎣
⎤⎡ZY ⎦⎤ = Ri Steady state assumption is that Rt = Ri
Ri ki K ⎡⎣M ⎤⎡
⎦⎣I ⎤⎡
⎦⎣ZY ⎤⎦
⎣⎡M ⎦⎤ = k =
+

t kt
R
Going back to Rp with ⎡⎣ M + ⎤⎦ = i
kt
2
Ri k p ⎣⎡M ⎦⎤ Kki k p
⎡⎣I ⎤⎡
⎦⎣ZY ⎤⎡
⎦⎣M ⎤⎦
Rp = = second order in [M]
kt kt

First order in Ri
10.569, Synthesis of Polymers, Fall 2006 Lecture 25
Prof. Paula Hammond Page 5 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
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 (unlike free radical)

PN : No transfer (to monomer, solvent, counterion)

Rp kp ⎣⎡M ⎦⎤
PN = =
Rt kt

PN : If transfer occurs
Rtr,M: to monomer → create new propagating chain
Rtr,S: to solvent → create new cationic species
Rtr,Ci: to counterion → recreate initiation

Rtr ,Ci = ktr ,Ci ⎡⎣M + ⎤⎦

Rp
PN = with Rtr ,M = ktr ,M ⎡⎣M + ⎤⎦ ⎣⎡M ⎦⎤
Rt + Rtr ,Ci + Rtr ,M + Rtr ,S
Rtr ,S = ktr ,S ⎣⎡M + ⎦⎤ ⎣⎡S ⎦⎤

k p ⎡⎣M ⎤⎦
PN =
kt + ktr ,Ci + ktr ,M ⎡⎣M ⎤⎦ + ktr ,S ⎡⎣S ⎤⎦

1 kt k ⎡S ⎤
= + tr ,Ci + CM + CS ⎣ ⎦
PN k p ⎣⎡M ⎦⎤ k p ⎣⎡M ⎤⎦ ⎣⎡M ⎤⎦

ktr ,M ktr ,S
kp kp

Suppose transfer to solvent or impurity does not result in further propagation.

e.g. NR3 ⇒
R (IZ)
HMNM(IZ) + NR3 HMNM N R
Is stable
R No further propagation
This must be included in
steady state [M+] expression
Kk i k p [I ][ZY ][M ]2
Rp = term from transfer like
k t + k tr ,S [S ]
*does not effect PN expression (do not include in PN calc)

*Note: all of the above assumes the 2nd initiation step is rate determining.

Validity of Steady State Assumption

Not really valid
- rxn rates very rapid (seconds – minutes)
- often Ri > Rt

10.569, Synthesis of Polymers, Fall 2006 Lecture 25

Prof. Paula Hammond Page 6 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.
 - [M+] slowly increases with time
- [M+] reaches maximum late in polymerization
then decreases with further conversion

Application of equations is merely an approximation of what really happens.

10.569, Synthesis of Polymers, Fall 2006 Lecture 25

Prof. Paula Hammond Page 7 of 7

Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date.