Polymerization Mechanism

Polymerization mechanisms

- Step-growth polymerization
 Step growth polymerization
Polymerization mechanism in which bi-
functional or multifunctional monomers react to
form first dimers, then trimers, longer oligomers
and eventually long chain polymers.
Eg: polyesters, polyamides, polyurethanes. Etc
Polymer+molecule with low molecular weight.
 Stepwise (Condensation) polymerization Reaction

Requirements for Step-Growth Polymerization

High monomer conversion
High monomer purity
High reaction yield
Stoichiometric equivalence of functional groups

The characteristic features of this type of polymerization process as

follow .
1-Growth occurs throughout the matrix
2-There is the rapid loss of the monomer species
3-The molecular weight slowly increases throughout the reaction
4- The same mechanism operate throughout the reaction
5-The polymerization rate decreases as the number of functional group decreases
6-No initiator is required to start the reaction
 Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer
Example
formation of polyester
nHO-R-OH + nHOOC-R-COOH H-(O-R-OOC-R-CO-)nOH+(2n-1)H2O

Kinetics of condensation (step Growth ) polymerization

Consider the synthesis of polyester from a diol and a diacid. The first step is the reaction
of the diol and the diacid monomers to form dimer,
HO-R-OH + HOOC-R"-COOH--> HO-R-OCO-R'-COOH + H2O The dimer
then forms trimer by the reaction with diol monomer,
HO-R-OCO-R'-COOH + HO-R-OH--> HO-R-OCO-R'-COO-R-OH +H2O and also
with diacid monomer,
HO-R-OCO-R'-COOH + HOOC-R'-COOH-->
HOOC-R'-COO-R-OCO-R'-COOH + H2O
 Kinetics of Condensation (Step-Growth) Polymerization
Step-Growth polymerization occurs by consecutive reactions in which the
degree of polymerization and average molecular weight of the polymer
increase as the reaction proceeds. Usually (although not always), the
reactions involve the elimination of a small molecule (e.g., water).
Condensation polymerization may be represented by the following reactions:
Monomer + Monomer Dimer + H2O
Monomer + Dimer Trimer + H2O
Monomer + Trimer Tetramer + H2O
Dimer + Dimer Tetramer + H2O
Dimer + Trimer Pentamer + H2O
Trimer + Trimer Hexamer + H2O
Generally, the reactions are reversible, thus the eliminated water must be
removed if a high molecular weight polymer is to be formed.
Based on the assumption that the polymerization kinetics are independent of
molecular size, the condensation reactions may all be simplified to:
~~~~COOH + HO~~~~ ~~~~COO~~~~ + H2O
 Chain growth polymerization
Addition polymerization
All the atoms in monomer is used to produce a
polymer.
Steps in chain reaction:
initiation
propagation
termination
 I____ R*
R* + M_____R M*_M__R-M-M*___
 Addition polymerization has three steps

C2H4 is stable does not spontaneously change

into polyethylene requires severe conditions
1. Initiation of the chain process
2. Propagation of the chain process
3. Termination of the chain process
 Chain polymerization

Radical polym. Ionic polym.

The C=C is prefer the
Polym. by R.P.
and also can be used in Anionic polym. Cationic polym.
the steric hindrance of Electron with drawing Electron donating
the substituent substituent decreasing substituent increasing
the electron density on the electron density on
the double bond and the double bond and
facilitate the attack of facilitate the attack of
anionic species cationic species
such as cyano and such as alkoxy, alkyl, alkenyl,
carbonyl and phenyl
+ - - +
CH2=CH Y CH2 =CH Y

X X X

radical cationic anionic

 Free radical polymerization
Initiation: active center created.
2 steps
Radicals from initiators
Transfer to monomer
Types of initiation:
Thermal decomposition
Photolysis
Redox reactions
Persulfate
 Propagation:

Termination :
Combination of two active chain ends
Impurities
Combination of an active chain end with an initiator radical
 Cationic polymerization
Cationic initiator binds & transfers charge to monomer.
Reactive monomer reacts with other monomer to form a
polymer.
Active site:
carboniumion , oxonium, sulfonium or phosphonium ion
Monomers: alkoxy. phenyl, vinyl, 1,1-dialkyl-substituted
alkene monomers.
Initiator: provide electrophile
eg: bronsted acids(acetic acid,HCL), Lewis
acids+electron donor.
Application :polyisobutylene.
Cationic polymerization
 Anionic polymerization
Carried out through carbanion active species.
Monomer: vinyl monomers with substituents on
double bond able to stabilise a ve charge.
Eg: styrene, dienes, methacrylate,
vinyl pyridine, aldehydes, epoxide, episulfide cyclic siloxane,
and lactones
Polar monomers:
eg: acrylonitrile, cyanoacrylate, propylene oxide,
vinyl ketone, acrolein, vinyl sulfone,
vinyl sulfoxide, vinylsilane andisocyanate.
.
 Solvents- polar solvents decrease stability.
initiation : electron transfer, strong acids.
Propagation: very fast,low temp, heat is
released.
Termination: quenching, water, alcohol, chain
transfer.
Application :polydiene synthetic rubbers,
solution styrene/butadiene rubbers (SBR), and
styrenic thermoplastic elastomers
 Differences between step-growth polymerization and
chain-growth polymerization
Step growth Chain growth
Growth throughout matrix Growth by addition of monomer
Rapid loss of monomer early in only at one end of chain
the reaction Some monomer remains even at
Similar steps repeated long reaction times
throughout reaction process Different steps operate at different
Average molecular weight stages of mechanism.
increases slowly at low Molar mass of backbone chain
conversion and high extents of increases rapidly at early stage and
reaction are required to obtain remains approximately the same
high chain length. throughout the polymerization
Ends remain active (no Chains not active after termination
termination)
No initiator necessary Initiator required