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Addition Polymerization (Chain Growth) Step Growth Polymerization (Condensation)

There are two main types of polymerization: step-growth (condensation) polymerization and chain-growth (addition) polymerization. Step-growth polymerization involves monomers reacting together in steps to form the polymer backbone, leading to a slow increase in molecular weight even at high conversions. Chain-growth polymerization involves monomers adding onto the active end of a growing polymer chain, allowing for rapid increase in molecular weight at early stages. Key differences between the two types include the presence of an initiator and different reaction mechanisms for chain-growth versus the same mechanism throughout for step-growth.

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410 views15 pages

Addition Polymerization (Chain Growth) Step Growth Polymerization (Condensation)

There are two main types of polymerization: step-growth (condensation) polymerization and chain-growth (addition) polymerization. Step-growth polymerization involves monomers reacting together in steps to form the polymer backbone, leading to a slow increase in molecular weight even at high conversions. Chain-growth polymerization involves monomers adding onto the active end of a growing polymer chain, allowing for rapid increase in molecular weight at early stages. Key differences between the two types include the presence of an initiator and different reaction mechanisms for chain-growth versus the same mechanism throughout for step-growth.

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Addition Polymerization (Chain Growth)

Step Growth Polymerization (Condensation)

Differences between step-growth


polymerization and chain-growth
polymerization
Step-growth polymerization

Chain-growth polymerization

Growth throughout matrix

Growth by addition of monomer


only at one end of chain

Rapid loss of monomer early in


the reaction

Some monomer remains even at


long reaction times

Same mechanism throughout

Different mechanisms operate at


different stages of reaction (i.e.
Initiation, propagation and
termination)

Average molecular weight


increases slowly at low
conversion and high extents of
reaction are required to obtain
high chain length

Molar mass of backbone chain


increases rapidly at early stage
and remains approximately the
same throughout the
polymerization

Ends remain active (no


termination)

Chains not active after


termination

No initiator necessary

Initiator required

Steps of Radical Chain


Polymerization
Initiation
Propagation
Termination

INITIATION

PROPAGATION

TERMINATION
Dead Polymer
i.) Coupling or Combination;

ii.) Disproportionation

CHAIN TRANSFER
REACTIONS
Transfer to monomer
reaction

Transfer to initiator reaction

Transfer to solvent reaction

IONIC CHAIN POLYMERIZATION


Using catalyst, not initiator
Highest reaction rate
Termination step is just disproportionation
Environment must be pure
Reaction occurs in the cold

Anionic Polymerization=Living Polymerization


If the starting reagents are pure and
the polimerization reactor is purged of all
oxygen and traces of water, polimerization
can

proceed

consumed.

until

all

monomer

is

CONDENSATION
POLYMERIZATION
Using catalyst
Minumum two functional groups required
Usually linear
Molecular weight increases slowly at low

conversion
High extents of reaction are required to obtain

high chain length

KINETICS OF
POLYMERIZATION
Reaction rate of ionic polimerization more

than radicalic polimerization


So kinetics of ionic polimerization are not

calculated
But kinetics of radicalic polimerization can be

analysed

Kinetic of Radicalic
Polymerization
Initiation;

Propagation;

Termination;

Kinetic of Radicalic
Polymerization
Ro = overall rate of

polimerization
Rp = rate of chain

propagation
Ri = rate of

initiation step
Rt = rate of

termination step

Kinetic of Condensation
Polymerization
Equivalent

reactivity of
functional groups.
It may be first,

second or third
order by
depending upon.

Kinetic of Condensation
Polymerization

Assumption = a stoichiometry balance of monomer concentration

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