POLYMER SYNTHESIS

FREE-RADICAL POLYMERISATION (the FRP mechanism)

PREVIOUS LESSON
Polymerisation
need I & M

Effect of
substituent on Many many vinyl monomers
monomers

X X X X X
Different
Time
monomers different
pathway of
polymerisation

Different initiators

REMEMBER
Stages of (1) Initiation Stage
the reaction
polymerisation (2) Propagation Stage
(ideal state) (3) Termination Stage STEPS for
each stage
 FREE-RADICAL POLYMERISATION
REVISION

INITIATION STAGE (2 STEPS!!!) Initiator must be a

chemical that can
STEP 1 II 2 I form RADICAL

STEP 2 I + M I M
Radical now on
1st monomer MONOMER

Propagation Stage I M + M I MM

STEP 3 I MM + M I MMM
In general: I MxM + M I(M)x+1M

Termination Stage
STEP 4
I MxM + MMx I I MxM−MMx I Combination

Saturated compd.+
I MxM + M unsaturated compd. Disproportionation
 ALL POLYMERISATION REACTION MUST HAVE :
Initiator Monomers

THE MONOMERS
CH2 CH
All vinyl compounds R
Can have e- withdrawing & e- donating substituents
CH2 C R'
R : substituent which is able to stabilize the radical R
Monomer Name Structure
CH2 CH
[1] Styrene

CH2 C Me
[2] α-methylstyrene

CH2 CH
[3] 1,3-butadiene
CH CH2

CH2 CH
[4] Vinyl ester O C O
R
CH2 C CH3
[5] Methyl C O
methacrylate OCH3
CH2 CH
[6] Vinyl chloride Cl

CH2 C Cl
Vinylidene chloride
[7] Cl

CH2 CH
[8] Acrylonitrile CN

CH2 CH
[9] Acrylamide C O
NH2
 THE INITIATORS

TYPE EXAMPLE
[1] Organic Peroxide BENZOYL PEROXIDE
Or Hydroperoxide O O
C O O C

[2] Azo Compounds AZOBISISOBUTYRONITRILE (AIBN)

Me Me
Me C N N C Me
CN CN

[3] Redox Agents PERSULFATES + REDUCING agents

(water soluble)

[4] Organometallic SILVER ALKYLS

Reagents
[5] Heat, Light, UV,
High-energy
Radiation
[6] Electrolytic e- ELECTROLYSIS
Transfer

[7] Atom Transfer

Radical
 MECHASNIMS
THE INITIATORS Thermally decompose initiators

Example : Dialkyl peroxide Possibility of further

decompose

May further decompose to alkyl radical & aldehyde/ketone

Attack monomer
Refer to initiator-01 (initiate polymerisation) = I

Example : Benzoyl peroxide Refer to initiator-02

Possibility
O O O
 of further
C O O C 2 C O
decompose
60~80°C
Benzoyl oxy
radical
(further decompose) Attack
O monomer

C O  + CO2

Phenyl radical

Example : Azo compounds (AIBN)

Me Me Me
Me C N N C Me 2 Me C + N2
40~60°C
CN CN CN
Refer to initiator-03
 THE MECHANISM
unpaired e-

growing chain end bears an 

unpaired e-

unpaired e- is transferred to the new chain end at each addition of the monomer

Initiation stage
3 process stages

Propagation stage

Termination stage

Example : Polymerisation of vinyl chloride by t-butyl peroxide

Initiation stage

[1] Formation of radical by heating the initiator

Me Me Me

Me C O O C Me 2 Me C O
(60°C) t-butyl oxy radical
Me Me Me

t-butyl peroxide
Attack
(initiator)
monomer
(Me)2C O + CH3

[2] Radical formed attack 1 molecule of monomer

H
CH3 + CH2 CH CH3 CH2 C
Cl Cl
Attacking
monomer Vinyl chloride
(monomer) Initiator 1 monomer
 Propoagation stage Radical formed attack n
molecule of monomer

H H H
CH3 CH2 C + CH2 CH CH3 CH2 C CH2 C
Cl Cl Cl Cl
.
. Initiator 2
. monomers
H H
CH3 CH2 C CH2 C + n CH2 CH H H
Cl Cl Cl CH3 CH2 C CH2 C
Cl Cl
n+1

Termination stage

Combinatio Reaction of 2 active chains

n
H H H H
CH3 CH2 C CH2 C + C CH2 C CH2 CH3
Cl Cl Cl Cl
n n

Initiator (n+1) (n+1) Initiator

monomers monomers

H H H H
CH3 CH2 C CH2 C C CH2 C CH2 CH3
Cl Cl Cl Cl
n n
 H H
I CH2 C + C CH2 I
Combination (simplified)
Cl Cl

Preferred LOW T (40-60°C)

H H
Can increase M.W. of final polymer I CH2 C C CH2 I
Cl Cl

Termination stage More significance at HIGH T

(to break C-H bond)
Disproportionation
H
H H H H
(Me)3C O CH2 C CH2 C + C CH C CH2 O C(Me)3
Cl Cl Cl
n Cl n

H H H H
(Me)3C O CH2 C CH2 C H + C CH C CH2 O C(Me)3
Cl Cl Cl Cl
n n
Saturated compound Unsaturated compound

Hence, the polymer structures formed by FRP

[1] I CH2 CH CH CH2 I

X X
m n
I : Initiator

[2] I CH2 CH CH2 CH2 X : radical stabilising group

X X
m

[3] I CH2 CH CH CH
X X
n