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Polymer Science and Technology-CHT411 Polymerization Reactions

The document discusses various types of polymerization reactions including addition, condensation, coordination, and copolymerization. It describes the key steps and characteristics of addition polymerization which includes initiation, propagation, and termination. Within addition polymerization, it distinguishes between free radical and ionic polymerization, providing examples of initiation methods for free radical polymerization such as thermal decomposition, photolysis, and redox reactions. The document also matches common monomers to the polymerization type they are most suitable for.

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Ekansh Choudhary
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29 views20 pages

Polymer Science and Technology-CHT411 Polymerization Reactions

The document discusses various types of polymerization reactions including addition, condensation, coordination, and copolymerization. It describes the key steps and characteristics of addition polymerization which includes initiation, propagation, and termination. Within addition polymerization, it distinguishes between free radical and ionic polymerization, providing examples of initiation methods for free radical polymerization such as thermal decomposition, photolysis, and redox reactions. The document also matches common monomers to the polymerization type they are most suitable for.

Uploaded by

Ekansh Choudhary
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Polymer Science and Technology-

CHT411
Polymerization Reactions

Date: 03-10-2020
Polymerization
• The monomer is taken in a liquid state (or
gaseous state) or dissolved into a solvent and the
initiator is dissolved in the monomer/ solution .
• The reaction medium is in a homogenous phase.
• The system is heated (or exposed to a radiation
source) so that polymerization is initiated.
• Agitation is provided for proper mass and heat
transfer.
• With progress in polymerization, the viscosity of
the medium increases and mixing becomes
gradually difficult, leading to products with variety
of molecular weight and composition.
Types of
Polymerization
• Broad category

– Addition or Chain Growth Polymerization


– Condensation or Step Grow Polymerization

• Other categories
– Coordination polymerization
– Copolymerization
Addition or Chain
Growth Polymerization
• In this type of polymerization, the molecules of the same or
different monomers add to the monomers or the chains.
• Growth happens due to sequential addition of monomers
into the chains.
• Usually monomers containing carbon-carbon double bonds
or cyclic HCs take part in this type of reactions.
• A chain growth consists of three steps:
– Chain initiation
– Chain propagation
– Chain termination
Addition polymerization
Condensation or Step
growth polymerization
• This type of reactions takes place when repetitive
condensation reactions take place.
• Two molecules joined together and reject a small molecule.
• Rejected molecules are like water, alcohol etc.
• Reactions are usually taken place between two functional
groups.
• Two functional groups can be present in
– two ends of a same monomer
– two different monomers
Condensation polymerization

• Chain growth takes place by


– addition of monomers to a chain
– addition of a chain to another chain
Coordination
polymerization
• It is a sub-class of Addition Polymerization
• Involves transition-metal catalysis
• Here the active species is a coordination complex
which initiates the polymerization by adding
carbon-carbon double bonds.
• Ziegler-Natta Catalyst-
Copolymerization
• It is a polymerization reaction where more than one
monomeric units are involved to form a polymer.
• Both addition and copolymerization can be involved in such
reactions.
• It contains multiple units of each monomer used in the
same polymer chain
Addition Polymerization
• Initiation
• Propagation
• Termination
Chain initiation
• In the initiation step, an initiator molecule is thermally
decomposed or allowed to undergo a chemical reaction to
generate an “active species”

• This active species -a free radical/ an ion (cation or anion)


• Active species initiates the polymerization by adding to the
carbon-carbon double bond.
• The reaction occurs in such a way that a new free radical
or an ion is created.
• The initial monomer becomes the first repeat unit in the
emerging polymer
Chain propagation
• In the propagation step, the newly generated active species
adds to another monomer similarly as the initiation step.

• This procedure is repeatedly take place until the chain


termination takes place
Chain termination
• Combination
• Disproportionation
▪ The living chain terminates through reaction with another
living or by reaction with another species (impurity) or by
spontaneous decomposition of the active site.
Characteristics of
Addition polymerization
• Once initiation occurs, the polymer chains form
very quickly
• Each initiator leads to each polymer chain until
termination happens.
• The concentration of active species is very low.
Hence the polymerization mixture consists of
primarily of newly-formed polymer and unreacted
monomer.
• Since the carbon-carbon double bond breaks in
the monomers, these are exothermic reactions.
Classification of Addition
Polymerization
• Mainly two categories
– Free-radical Polymerization
– Ionic Polymerization
• Cationic
• Anionic
▪ Free radical polymerization: Atoms or ions or molecules
having unpaired electrons
▪ Free radicals are highly chemically reactive
▪ Example: Hydroxyl radical ( HO )
Free radical
polymerization
• Free radicals initiation can be categorized in number of
ways
– Thermal decomposition
– Photolysis
– Redox reactions
– Persulfates
– Ionizing radiation
– Electrochemical
– Plasma
– Sonication
Thermal decomposition
• The stability of radicals varies
widely.
• Primary radicals are less
stable and more reactive than
secondary radicals,
• Less stable than tertiary radicals (Some tertiary radicals,
such as the triphenylmethyl, can be isolated in the solid
• state without decomposition )
• The phenyl radical is more reactive than the benzyl radical,
allyl radical is quite unreactive, and so on.
• To be useful in initiating polymerization, a compound
undergoing thermal-decomposition to free radicals should
have a first-order decomposition rate constant 10-5 to 10-
6
sec-1 at the desired polymerization temperature, usually
50- 150 0C.
• Rate of generation of free radicals cannot be controlled
rapidly because of heat capacity of the system
Photolysis
• Photo-initiated polymerization can be controlled with high
precision, since the generation of radicals can be made to
very instantaneously by controlling the intensity of initiating
light.
• Light of short enough wavelength (i.e., high enough
energy per quantum) can initiate polymerization directly.
• a photochemical initiator such as benzoin or azo-bis-
isobutyronitrile is decomposed into free radicals by
ultraviolet light in the 3600 Å region
– where direct initiation through decomposition of
monomer does not occur
• Such polymerization doesn’t require high temperature (no
thermal degradation of monomers or initiator).
• Source light are available in the form of mercury-arc lamps
or fluorescent lamps, special phosphors, and lasers.
Ionic polymerization
• Chain carriers : carbenium ions (for cationic) or carbanions
(for anionic)

Carbenium

• Type of monomer polymerizing best by each mechanism is


related to the polarity of the monomer and the acid-base
strength of the ion formed.
• Monomers with electron-donatlng groups attached to the
double bonded carbons form stable carbenium ions and
polymerize best with cationic catalysts.
• monomers with electron-withdrawing substituents form
stable anions and require anionic catalysts.
Types of Chain Polymerization
Suitable for Common Monomers

Source: Textbook of polymer Science, Billmeyer (3 rd edition), page-83

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