Radical Chain Polymerization:

Chain-Growth Polymerization (Addition

polymerization) Processes

1. Free radical Initiation Processes

2. Cationically Initiated Processes

3. Anionically Initiated Processes

4. Coordination Polymerization

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 Characteristics of Chain-Growth Polymerization
1. Only growth reaction adds repeating units one at a
time to the chain
2. Monomer concentration decreases steadily throughout
the reaction
3. High Molecular weight polymer is formed at once;
polymer molecular weight changes little throughout
the reaction.
4. Long reaction times give high yields but affect
molecular weight little.
5. Reaction mixture contains only monomer, high
polymer, and about 10-8 part of growing chains.
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 The Chemistry of Free Radical Polymerization

Radical Generation R R 2R
-
Initiator Radicals

Initiation R + C C R C C
Monomers

Propagation R C C + nC C R (C C)n C C

Termination R C C + C C C R`

R C C C C C R`
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 Free Radical Polymerization Mechanisms

1. Overview – Free radical polymerization processes

involve at least three mechanistic steps.

A. Initiation
1. Radical Formation (Generation)
D
In In In + In
h v , etc.

2. Initiation

In + M In M

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 B. Propagation

In-M1 . + M2 In-M1M2.

In-M1M2. + M3 In-M1M2M3.

In-M1M2M3…MX. + MY In-M1M2M3…MXMY.

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 C. Termination
1) Radical Coupling (Combination)

In-MX. + .MY-In In-MX-MY-In

In + In In In

2) Disproportionation (-hydrogen transfer)

HH HH
In MxC C + C C My In
HH HH
In Mx CH CH2 + H3C CH2 My In
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D. Chain Transfer (sometimes) – An atom is transferred
to the growing chain, terminating the chain growth
and starting a new chain.

Chain Transfer to Chain Transfer Agent:

Px + H R Px + R
Chain Transfer to Monomer:
Px. + H2C=CH-(C=O)OR

Chain Transfer to Polymer: Causes Branching

H
Px + Py Px + Py
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E. Inhibition and Retardation – a retarder is a substance
that can react with a radical to form products incapable
of reacting with monomer. An inhibitor is a retarder
which completely stops or “inhibits” polymerization.

2. Monomers that are susceptible to free radical addition

A. Vinyl Monomers
H2C CHX H2C CH Cl
Vinyl chloride

H X H F

H Y H F
Vinylidene fluoride
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 B. Allyl Monomers

X Cl

Allyl Chloride

C. Ester Monomers
1) Acrylates

OH OR

O O
Acrylic Acid Acrylate Esters

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 2) Methacrylates

OH OR

O O
Methacrylic Acid Methacrylate Esters
3) Vinyl Esters
O
Vinyl Acetate
O

D. Amide Monomers

NH2

O
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Acrylamide Methacrylamide
3. Monomers that are not susceptible to Free Radical
Addition
A. 1,2-a-olefins (Polymerize to oils only)

x
B. Vinyl ethers
R
O O
methyl vinyl ether
C. 1,2-disubstituted Ethylenes
Cl Cl
1,2-dichloroethylene
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H H 11
4. Initiation – “Getting the thing started!”
A. Radical Generators (Initiators)
1. Benzoyl Peroxide

O O
0
80-90 C
C O O C

O
C O 2 + 2 CO2

(continued)
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 +

New Active Site

Initiator End-Group Ph
Ph
2) t-Butyl Peroxide

CH3 CH3 CH3

1200-140 0C
H3C C O O C CH3 2 H3C C
CH3 CH3 CH3

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(continued) 13
 CH 3
O
H 3C C +

CH 3 O

O
3) Azobisisobutyronitrile (AIBN)
CH3 CH3
~60oC
H3C – C – N=N – C – CH3
CN CN or hn
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(continued) 14
 CH3 CH3
Ph
H3C C + N2 H3C C C CH
H2
CN CN

4) Cumyl Hydroperoxide
CH3
C O OH + OH
Ph O
CH3

(continued)
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 (continued)

O
+
Ph O O

O
Ph O
O

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 Hydroperoxides can generate radicals by “induced
decomposition” from growing polymer chains:

P + H O O R

PH + O O R 2R OO

R-OO-OO-R 2 RO + O2

What effect does this have on the polymerization process?

Acting as a chain-transfer agent, it reduces the

degree of polymerization and molecular mass.
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 5) Redox Initiator Systems

2+ 3+
H O O H + Fe HO + OH + Fe

O
R
O 3S O O SO 3 + SO 32- SO 4- +

S-SO 3 - +
SO 42-

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 6) Photoinitiators (Photocleavage – Norrish I)
O O
hv
C

HO +

OH
benzoin
C
H
H
C +
Ph
OH OH

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H
 (continued)
OR
O O
hv
C C

benzil O
2 C

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 7) Photoinitiators (Photo-Abstraction)
O
Photosensitizer
O*
hv

Ph Ph
benzophenone excited state
R R
H C N OH R R
+ C N
Coinitiator R R
Ph Ph R R
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5. Propagation - “Keeping the thing going!”
A. The addition of monomer to an active center (free radical)
to generate a new active center.

H
R C CH2 X R C C C CH
H2 H2 H2
X X X

X X H
R C C C CH
etc. etc. H2 nH2
X X

(continued)
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Examples: Polystyrene
Ph H
R C CH2 R C C C CH
H2 H2 nH2
Ph Ph Ph

O
R C C CH CH 3
H2 H2
C O O

Polymethyl O
Acrylate CH 3
H
R C C C C CH
H2 H2 H2
C O C O
O O
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 B. Configuration in Chain-Growth Polymerization
1) Configuration Possibilities

favored

- H2C CH P C CH
H2 X
attack X
P

H .
HC CH2 X P C CH2
a-
attack X X

sterically
and electronically unfavored
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2) Radical Stability Considerations
Which possible new active center will have the greatest
stability?
.
P C CH2 P C CH
H2 H2

P C CH
-attack produces resonance H2
stabilized free radical

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 H
P C CH2 X No resonance stabilization

______________________________________________
CH2
CH2O
a P CH
HC C O CH3 X
O C O CH3
P

H2C C C O CH3 P C CH
H H H2
O C O
P C CH
Secondary radical H H2 O CH3
is resonance stabilized C O
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O CH3
(more examples)
Cl H Cl
a
X P C CH2
Cl H Cl
P
H Cl Cl

P C C
H2
H Cl Cl

Cl Cl
P C C P C C
H2 H2
Cl Cl
Tertiary radical is
resonance stabilized
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 3) Steric Hinderance Considerations

HC CH2 X

X
P

H2C CH For large X, -substitution

is sterically favored
X

4) Radical Stability
3o > 2o > 1o

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5 ) “Bottom Line”
Resonance and steric hinderance considerations lead to the
conclusion that -substitution (head-to-tail) is strongly
preferred in chain-growth polymerization.

H H H H
C C C C C C C C
H2 H2 H2 H2
X X X X
Alternating configuration

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 6. Termination - “Stopping the thing!”
A. Coupling (most common)

H H
Px C C + C C Py
H2 H2
X X
H H
Px C C C C Py
H2 H2
X X
- occurs head-to-head
- produces two initiator fragments (end-groups)
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per chain. 30
 B. Disproportionation

HH HH
In MxC C + C C My In
HH HH
In Mx CH CH2 + H3C CH2 My In

- Production of saturated chain and 1 unsaturated chain

per termination

- Produce one initiator fragment (end-group) per chain

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C. Factors affecting the type of termination that will take
place.

1) Steric factors - large, bulky groups attached directly

to the active center will hinder coupling

2) Availability of labile -hydrogens

3) Examples – PS and PMMA

H H
Px C C + C C Py
H2 H2

Polystyrene Combination (coupling)

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 H H
Px C C C C Py
H2 H2
Ph Ph Ph =

PMMA CH3 H3C

~~~PX – CH2-C. + . C-CH - P ~~~
2 Y
C=O O=C
1. Sterically
hindered O O
2. 5 -Hydrogens CH CH3
3
3. Disproportion-
ation dominates
10/17/2020 (continued) 33
 CH3 H3C

~~~PX – CH2=C + HC-CH2- PY~~~

C=O O=C

O O

CH3 CH3
4) Electrostatic Repulsion Between Polar Groups –
Esters, Amides, etc.

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 Polyacrylonitrile (PAN)
~~~PX – CH2-CH. + . HC-CH2- PY~~~
d+ CN d- d- NC d+

One might assume electrostatic repulsion in this case.

BUT, how about electrostatic attraction from the
nitrogen to the carbon? Also, steric hindrance is
limited.

At 60oC, this terminates almost exclusively by

coupling!

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 D. Primary Radical Termination

~~~PX – CH2-CH. + . In
X

~~~PX – CH2-CH-In

More Likely at X
High [In.]

So molecular mass can be controlled using chain-transfer

agents, hydroperoxide initiators, OR higher levels of
initiator!
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 7. Chain-Transfer - “Rerouting the thing!”
A. Definition – The transfer of reactivity from the
growing polymer chain to another species. An
atom is transferred to the growing chain,
terminating the chain and starting a new one.

~~~PX – CH2-CH. + X-R  ~~~PX – CH2-CHX + R.

Y Y
B. Chain-transfer to solvent:

~~~PX – CH2-CH. + CCl4  ~~~PX – CH2-CHCl + Cl3C.

Y Y
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 C. Chain-transfer to monomer:

~~~PX – CH2-CH. + H2C =CH

~~~PX – CH2-CH2 + H2C =C.

OR

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 H H
~~~PX – CH - C. + H2C =CH

~~~PX – CH2=CH. + H3C - C.

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 Propylene – Why won’t it polymerize with Free Radicals?

~~~PX – CH2-CH. + HCH=CH

CH3 CH3

~~~PX – CH2-CH2-CH3 + CH2=CH-CH2.

H2C-CH-CH2

Chain-transfer occurs so readily that propylene won’t polymerize
with free radicals.
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 D. Chain-transfer to polymer:

~~~PX – CH2-CH2-CH2. + ~~~CH2-CH2-CH2~~~

~~~PX – CH2-CH2-CH3 + ~~~CH2-CH-CH2~~~



Increases branching and broadens MWD!

E. Chain-transfer to Initiator (Primary Radical
Termination):
~~~PX – CH2. + R-O-O-R  ~~~PX – CH2-OR + . OR

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 F. Chain-transfer to Chain-transfer Agent:
Definition – The transfer of reactivity from the
growing polymer chain to another species. An
atom is transferred to the growing chain,
terminating the chain and starting a new one.
Examples: R-OH; R-SH; R-Cl; R-Br

~~~PX – CH2-CH2. + HS-(CH2)7CH3

~~~PX – CH2-CH3 + . S-(CH2)7CH3

H2C CHX . CXH-CH

2- S-(CH2)7CH3
H2C CHX
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etc., etc., etc. 42
 8. Inhibition and Retardation - “Preventing the thing
or slowing it down!”
Definition – Compounds that slow down or stop poly-
merization by forming radicals that are either too
stable or too sterically hindered to initiate poly-
merization OR they prefer coupling (termination)
reactions to initiation reactions. (MWt. Controlling agents
~~~PX – CH2-CH. + O= =O
para-Benzoquinone
Will Not
~~~PX – CH2-CH2-O- -O.
Propagate

~~~PX – CH2-CH. + O=O ~~~PX – CH2-CH-O-O .

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Complete example for free radical polymerization

Example: butyle acrylate

Intiation:

Initiator breaks down smoothly to generate a low, steady-state concentration of44

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radicals.
Propagation:

Monomer adds quickly to the small number of growing chains present at any given time.

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 Termination:

Disproportionation in this example

Termination is a bimolecular process, and occurs when two growing

chain ends find each other.
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