Subject Code:CH301 Course Title: Polymer Materials
Unit-2, Lecture-9,10,11,12,13
Coordination polymerization, ring opening polymerization, Copolymer and their
types, methods of copolymerization, techniques of polymerization: Bulk,
Solution, Suspension & Emulsion, Industrial methods of polymerization
✓ Textbook of Polymer Science/ F.W. Billmeyer/ John Wiley
✓ Polymer Science/ V.R. Gowarikar/ New Age International
✓ Principle of Polymerization/ G Odian/ Wiley
Copolymers and their Types
Two or two monomer pairs are polymerized simultaneously and polymer is composed
of more than one repeat unit.
Example
Styrene-butadiene rubber (SBR): copolymer obtained from free radical polymerization
of styrene and butadiene
In general, copolymerization can be
represented as
xA+yB A-A-B-A-A-A-B-B-A-A-B-B-A
The ratio of A:B and degree of
randomness depends on the quality
of the individual monomers, their
amenability for copolymerization and
the polymerization mechanism
Copolymers and their Types
Types of Copolymer
Alternate Copolymer
Random Copolymer
Block Copolymer
Graft copolymer
Copolymer Composition
Terminal model or First order Markov
The relative copolymerization tendencies of monomers bore little resemblance to their
relative rates of homopolymerization
Some monomers are more reactive in copolymerization than indicated by their rates of
homopolymerization
Example: Maleic anhydride and stilbene
Assumption
The chemical reactivity of the propagating chain (which may be free radical, carbocation
or cabanion) in a copolymerization is dependent only on the identity of the monomer
unit at the growing end and independent of the chain composition preceding the last
monomer
Copolymer Composition: Free radical copolymerization
Let the monomers, M1 and M2, be mixed together and polymerized using a
free radical initiator.
Once the initiator decompose, the free radical can attack M1 or M2
R. +M1 RM1.
Initiation
R. +M2 RM2.
The chain carrying a free radical site on M1 can either add another M1 monomer or M2
Monomer (Propagation reaction)
Similarly, the chain carrying a free radical site M2 can either add another M2 Monomer
or M1 Monomer
RM1. + M1 RM1M1. PR 11 RM2. + M1 RM2M1. PR 21
RM1. + M2 RM1M2. PR 12 RM2. + M2 RM2M2. PR 22
Free radical copolymerization
The rates of these propagation reactions K= propagation rate constant
k11
M1. + M1 M1M1. R11= k11 [M1.] [M1] Homopropagation or
self propagation
k12
M1. + M2 M1M2. R12= k12 [M1.][M2]
Cross propagation
k21
M2. + M1 RM2M1. R21= k21 [M2.][M1]
k22
M2. + M2 RM2M2. R22= k22 [M2][M2.] Homopropagation or
self propagation
Basic assumption: the reactivity of any growing chain depends on the end monomer
unit carrying free radical site and not on the number of type of monomer unit already
added to the chain
All propagation reactions are assumed to be irreversible
Free radical copolymerization
The rate at which the monomers M1 and M2 are consumed during the course of
propagation can be expressed
−𝒅[𝑴𝟏]
= 𝒌𝟏𝟏 𝑴𝟏. 𝑴𝟏 + 𝒌𝟐𝟏 𝑴𝟐. [𝑴𝟏] 1
𝒅𝒕
−𝒅[𝑴𝟐]
= 𝒌𝟏𝟐 𝑴𝟏. 𝑴𝟐 + 𝒌𝟐𝟐 𝑴𝟐. [𝑴𝟐] 2
𝒅𝒕
Steady state condition, where the rate of a particular chain end (consider M1.)
disappearing is equal to the rate of formation of the same chain end
𝒌𝟏𝟐 𝑴𝟏. 𝑴𝟐 = 𝒌𝟐𝟏 𝑴𝟐. [𝑴𝟏]
[𝑴𝟏. ] 𝒌𝟐𝟏[𝑴𝟏]
= 3
[𝑴𝟐. ] 𝒌𝟏𝟐[𝑴𝟐]
Free radical copolymerization
Divide equation 1 by 2 and substitute the values from [M1.]/ [M2.] from equation 3
𝑑[𝑀1] 𝐾11 𝑀1. 𝑀1 + 𝐾21 𝑀2. [𝑀1]
=
𝑑[𝑀2] 𝐾12 𝑀1. 𝑀2 + 𝐾22 [𝑀2. ][𝑀2]
𝑑[𝑀1] 𝑀1 {𝐾11 𝑀1. + 𝐾21 𝑀2. }
=
𝑑[𝑀2] 𝑀2 {𝐾12 𝑀1. + 𝐾22 𝑀2. }
𝐾11 𝑀1.
𝑑[𝑀1] 𝑀1 { 𝐾21 𝑀2. + 1}
=
𝑑[𝑀2] 𝐾12 𝑀1.
𝑀2 {𝐾22 + 1}
𝑀2.
Free radical copolymerization
Copolymer equation 𝒌𝟏𝟏
𝒅[𝑴𝟏] [𝑴𝟏] { 𝒌𝟏𝟐 𝑴𝟏 + 𝑴𝟐 }
=
𝒅[𝑴𝟐] [𝑴𝟐] { 𝒌𝟐𝟐 𝑴𝟐 + 𝑴𝟏 }
𝒌𝟐𝟏
Reactivity ratio 𝒌𝟏𝟏 𝒌𝟐𝟐
= r1 𝒌𝟐𝟏
= r2 For given pair of monomer M1 and M2
𝒌𝟏𝟐
Reactivity ratio “r” defined as it is the ratio of the rate constant for a reactive
propagating species adding to its own monomer to the rate constant for its addition of
the other monomer.
These ratio (r1 and r2) indicate whether a growing chain carrying a free radical on a
particular monomer unit would prefer to add its own monomer species or the
comonomer species
Free radical copolymerization
The tendency of two monomers to copolymerize is noted by “r” values between 0 to 1
If r > 1 , M1. preferentially adds M1 instead of M2
r< 1, M1. preferentially add M2
r=0, M1 is incapable of undergoing homopolymerization
The chemical composition of the copolymer formed depends exclusively on the
monomer concentrations and their reactivity ratio
m1 and m2 are molar concentration
[𝒎𝟏] [𝑴𝟏] { 𝒓𝟏 𝑴𝟏 + 𝑴𝟐 }
Copolymer Composition equation = ∗
[𝒎𝟐] [𝑴𝟐] { 𝒓𝟐 𝑴𝟐 + 𝑴𝟏 }
Free radical copolymerization
We can write molar concentration in terms of mole fraction of monomers
The mole fraction of monomer M1 in the copolymer
n1 and n2 are mole
[𝒎𝟏] 𝒅[𝑴𝟏] fraction of monomer
= = 𝒏𝟏 = 𝟏 − 𝒏𝟐 M1 and M2 in the
𝒎𝟏 + [𝒎𝟐] 𝒅 𝑴𝟏 + 𝒅[𝑴𝟐]
copolymer formed
The mole fraction of Monomer M1 in the monomer feed can be given by
N1 and N2 are the
[𝑴𝟏]
= 𝑵𝟏 = 𝟏 − 𝑵𝟐 mole fraction of
𝑴𝟏 + [𝑴𝟐] monomer M1 and M2
Copolymer Equation
respectively in the
𝒓𝟏 𝑵𝟏 𝟐 + 𝑵𝟏𝑵𝟐 monomer feed
𝒏𝟏 =
𝒓𝟏 𝑵𝟏 𝟐 + 𝟐𝑵𝟏𝑵𝟐 + 𝒓𝟐 𝑵𝟐 𝟐
Reactivity ratio
Reactivity ratio
Depending on the values of r1 and r2 various copolymerization behaviors are possible
Case-1: r1=r2=0 𝒌𝟏𝟏 𝒌𝟐𝟐
𝒌𝟏𝟐
= r1= 0 𝒌𝟐𝟏
= r2=0
The propagation reaction 11 and 22 are not at all possible, hence , a chain ending
with M1 will add only M2 and this M2 will add only an M1
k12 k21
M1. + M2 M1M2. M2. + M1 RM2M1.
The copolymer formed will have an equal number of M1 and M2 monomeric
units arranged alternatively in the copolymer chain
Copolymer formation does not depend on feed ratio
of monomer
Individual monomer under this category cannot form
homopolymer Alternate Copolymer
Reactivity ratio
Case-1: r1=r2=0
Example:1 N1= N2= 1
𝒓𝟏 𝑵𝟏 𝟐 + 𝑵𝟏𝑵𝟐
𝒏𝟏 =
𝒓𝟏 𝑵𝟏 𝟐 + 𝟐𝑵𝟏𝑵𝟐 + 𝒓𝟐 𝑵𝟐 𝟐
(𝑵𝟏𝑵𝟐) 𝟏
𝒏𝟏 = = = 𝟎. 𝟓
𝟐(𝑵𝟏𝑵𝟐) 𝟐
Example:2
N1=0.8, N2=0.2
Reactivity ratio Ideal copolymerization
𝒌𝟏𝟏 𝒌𝟐𝟐 The copolymer composition can be
Case-2: r1=r2=1 = r1= 1 = r2=1
𝒌𝟏𝟐 𝒌𝟐𝟏 ideally controlled by adjusting the
initial monomer feed ratio
All four type of Propagation reactions are equally possible
k11 k21
M1. + M1 M1M1. M2. + M1 RM2M1.
k12 k22
M1. + M2 M1M2. M2. + M2 RM2M2.
The probability of M1 or M2 adding to the M1 or M2 depends purely on the monomer
concentrations.
The copolymer formed will have the same ratio of the monomeric components as
that of the monomer feed ratio
The two component arranged in the copolymer
chain in a purely random sequence
Random Copolymer
Reactivity ratio
Case-2: r1=r2=1
Example:1 N1= N2= 0.5
𝒓𝟏 𝑵𝟏 𝟐 + 𝑵𝟏𝑵𝟐
𝒏𝟏 =
𝒓𝟏 𝑵𝟏 𝟐 + 𝟐𝑵𝟏𝑵𝟐 + 𝒓𝟐 𝑵𝟐 𝟐
𝒏𝟏 =0.5
Example:2
N1=0.8, N2=0.2
𝒏𝟏 =0.8
Reactivity ratio
When the feed compositions and copolymer composition remain constant throughout
the course of the polymerization, this type of copolymerization is called as azeotropic
copolymerization.
𝒌𝟏𝟏 𝒌𝟐𝟐
Case-3: r1>1, r2<1 = r1> 1 = r2<1
𝒌𝟏𝟐 𝒌𝟐𝟏
k11 k21
M1. + M1 M1M1. M2. + M1 RM2M1. Preferred propagation reaction
The probability of M1 entering into the copolymer chain is higher as compared to M2.
The copolymer formed will be richer in M1
If r1 and r2 differ very widely, the copolymer formed will comprise almost entirely M1
It is very difficult to incorporate any appreciable quantity of M2 in the copolymer
chain.
Control on the copolymer composition can be achieved by adjusting the monomer feed
ratios.
Reactivity ratio
Case-4: r1<1, r2>1 𝒌𝟏𝟏 𝒌𝟐𝟐
= r1< 1 = r2>1
𝒌𝟏𝟐 𝒌𝟐𝟏
k12 k22
M1. + M2 M1M2. M2. + M2 RM2M2. Preferred propagation reaction
The probability of M2 entering into the copolymer chain is higher as compared to M1.
The copolymer formed will be richer in M2
If r1 and r2 differ very widely, the copolymer formed will comprise almost entirely M2
It is very difficult to incorporate any appreciable quantity of M1 in the copolymer
chain.
Control on the copolymer composition can be achieved by adjusting the monomer feed
ratios.
Reactivity ratio
𝒌𝟏𝟏 𝒌𝟐𝟐
Case-5: r1<1, r2<1 = r1< 1 = r2<1
𝒌𝟏𝟐 𝒌𝟐𝟏
k21
k12
M1. + M2 M1M2. M2. + M1 RM2M1. Preferred propagation reaction
The preference for one of these will depend on the actual values of r1 and r2 and on the
monomer feed ratio
When, r1=r2
[𝒎𝟏] [𝑴𝟏] { 𝒓𝟏 𝑴𝟏 + 𝑴𝟐 }
[M1]= [M2] = ∗
[𝒎𝟐] [𝑴𝟐] { 𝒓𝟐 𝑴𝟐 + 𝑴𝟏 }
Reactivity ratio
Case-6: r1>1, r2>1
Such system does not undergo random copolymerization
It forms either a mixture of two homopolymer or under certain favorable condition, block
copolymer having long sequence of M1 followed by a long sequence of M2
Reactivity ratio
A: r1>1, r2<1
Azeotropic
composition B: r1=r2=1
for plot C
C: r1=r1<1
D: r1<1, r2>1
Azeotropic
composition
E: r1<1, r2<1 and r1<r2
for plot E
𝒓𝟏 𝑵𝟏 𝟐 + 𝑵𝟏𝑵𝟐
𝒏𝟏 =
𝒓𝟏 𝑵𝟏 𝟐 + 𝟐𝑵𝟏𝑵𝟐 + 𝒓𝟐 𝑵𝟐 𝟐
Q.1 Consider the following monomer reactivity ratios for the copolymerization of
various pairs of monomers
Case r1 r2
1 0.1 0.2
2 0.1 10
3 0.1 3
4 0 0.3
5 0 0
6 0.8 0.2
7 1 15
What is the composition of the copolymer that would be formed from
equimolar mixture of the two monomers in each case.
Coordination Polymerization
Constitutional (Structural) isomerism
Encountered when polymers have the same overall chemical composition (molecular
formula) but differ in connectivity- the order in which the atoms are connected to each
other
Example -[C2H4O-]n
Coordination Polymerization
Example -[C3H5ON]n-
Isomeric polymers can also be obtained from single monomers if there is more than one
polymerization route (termination reaction).
Coordination Polymerization
Stereoisomerism
Stereoisomers have the same connectivity, but differ in their configurations
Configuration is the relative orientation in space of the atom of a stereoisomers,
independent of spatial change that occurs by rotations about single bonds
Geometric isomers (Cis-trans) arise from different configuration of substituents on a
double bond or on a cyclic structure
Example
Tacticity
Coordination Polymerization
In a linear asymmetric polymer chain, the pendant groups can either be arranged into
orderly configurations or they can be completely random. The steric order is
called tacticity. The difference in configuration affects its physical properties.
Isotactic
Semicrystalline
Semicrystalline Syndiotactic
Amorphous Atactic
Coordination Polymerization
Reaction of olefines and dienes, catalyzed by organo-metallic compounds
Steps of polymerization
1. Formation of monomer catalyst complex between the organometallic compound
and the monomer
Coordination bond is involved
between carbon atom of the
monomer and the metal of the
catalyst
Where: Mt represents transition metals such as Ti, Mo, Cr, V, Ni, Rh
Coordination Polymerization
2. The coordination metal-carbon bond formed in the monomer catalyst complex acts as
the active center from where propagation starts
The incoming monomer is
incorporated at the active
center of the metal-carbon
bond and chain growth start
Coordination Polymerization
The catalyst-monomer complex is a heterogeneous system, with the metal ion in the solid
phase and carbanion of the alkyl group in the solvent phase.
The monomer is inserted in
between the metal ion and the
carbanion with the result that the
polymer chain formed pushed out
from the solid catalyst surface.
Also known as Insertion Polymerization
Depending on the polarity of the
metal-carbon bond and solvent
medium, the metal counter ion
placed in a particular spatial
arrangement with respect to anion.
Coordination Polymerization
In certain catalyst system,
The spatial arrangement has tremendous effect on the spatial orientation of
the incoming monomer and also on the on the manner in which the monomer
is inserted into the growing chain imparts stereo regularity to the polymer
formed.
By choosing a proper catalyst /solvent system , the coordination mechanism can
be used to formulate highly stereo[regular polymers
Coordination Polymerization
Zieglar-Natta Catalyst system
Karl Zeigler of Germany in 1953 developed a series of catalysts that polymerizes ethylene at
low temperature and low pressure to give high molecular weight and very little branching.
Giulio Natta’s discovery (1954)
Coordination Polymerization
Zieglar-Natta Catalyst system
Special coordination catalyst comprising two compounds : catalyst and co-catalyst
Catalyst: halides of IV-VIII group element having transition valence
Co-catalyst: Organo-metallic compounds such as alkyls, aryls and hydrides of group I-IV
Organometallic Compounds Transition Metal salt
• Triethyl Aluminium Titanium tetrachloride
• Diethyl Aluminium Chloride Vanadium tetrachloride
• Diethyl Aluminium Chloride Triacetyl acetone vanadium
• Diethyl Aluminium Chloride Triacetyl acetone chromium
• Diethyl Aluminium Chloride Cobalt chloride pyridine complex
• Butyl Lithium Titanium tetrachloride
• Butyl Magnesium Iodide Titanium trichloride
• Ethyl Aluminium Dichloride Dichloro dicyclo pentadienyl titanium
Coordination Polymerization
Aluminum alkyl acts as the electron acceptor
Titanium halides act as electron donor
The complex formed is insoluble in solvent
Coordination Polymerization
The active centers, from where the polymer chain growth propagates are formed at the
surface of the solid phase of the catalyst complex.
Monomer is complexed with the metal ion of the active center before its insertion into
the growing chain
Natta’s Bimetallic mechanism
When the catalyst and co catalyst components are mixed, chemisorption of the
aluminum alkyl (electropositive) on the titanium chloride solid surface, formation of
electron deficient bridge complex
This complex acts as the active center.
Coordination Polymerization
The monomer is attached towards the Ti-C bond (Carbon from alkyl group) in the active
center
When it forms a Pi complex with Ti ion, the bond between R and Ti opens up, producing
an electron deficient Ti and Carbanion at R
The Ti ion attracts the pi electron pair of the monomer and
forms a bond, while the counter ion attracts the electron
deficient center of the monomer.
Coordination Polymerization
This transitional stat gives rise to the chain growth at the metal carbon bond, regenerating
the active center.
Repeating the whole sequence, with the addition of a second monomer molecule, get
the structure of the resultant chain growth
The monomer insertion is repeated and the orientation of the substituted group of the
monomer is always taken from the metal ion end resulting stereo regulated polymer
Coordination Polymerization
Monometallic mechanism of Cossee
Assume that the active center is at the Ti-R part of the catalyst, while the aluminum
alkyl performs only the function of alkylating the TiCl3.
When catalyst and co-catalyst are mixed, the aluminum is chemisorbed on the solid TiCl3
The five coordinated titanium ion on the surface of the catalyst is assumed to have d-
orbital
Coordination Polymerization
The active catalyst has an octahedral structure, with four Cl attached to the lattice
and ethyl group attached to the Ti through bond and vacant orbital
The monomer is attracted towards the vacant d orbital which then form
transition complex with the Ti
The transition state gives rise to the growth of the polymer chain by the monomeric
insertion at Ti-Et bond.
Coordination Polymerization
While the monomeric group is inserted and the chain grows, the vacant d orbital
can either be regenerated at the same position or at the position where the ethyl
group was originally attached
When the vacant d orbital is regenerated at the same position all the time , the
incoming monomeric units will inserted with the same spatial arrangement,
resulting in the formation of an isotactic polymer
Coordination Polymerization
With the insertion of each monomeric unit, if the d orbital migrates from one position
to the other alternatively, the monomers get inserted with alternating spatial
arrangement, resulting in the formation of a syndiotactic polymer.
Coordination Polymerization
Whether the vacant site is regenerated at same position or migrates to the other
site alternatively depends on interactive forces existing between
Techniques of Polymerization
Addition Polymers
Bulk Solution Emulsion Suspension
Polymerization Polymerization Polymerization Polymerization
Homogeneous System Heterogeneous system
Condensation Polymers
✓ Melt Polycondensation
Homogeneous system
✓ Solution Polycondensation
✓ Interfacial condensation Heterogeneous system
Bulk Polymerization
This method involves only the monomer molecule, an initiator and a chain transfer
agent ( if necessary).
dissolve
Monomer Homogeneous
in liquid Initiator +Chain mixture
state transfer agent
Heating
Continuous
stirring
Polymer
formed
Kept under agitation for proper mass and heat transfer.
As the polymerization proceeds, the viscosity of the medium increases
Mixing become progressively difficult, leading to a broad molecular weight distribution.
Bulk Polymerization
The product of polymerization obtained: the purest form of polymer, and the
greatest yield of polymer per unit volume.
The main disadvantage of this method is that as the medium gets viscous, the diffusion
of the growing polymer chain become restricted, collisions becomes less and thereby
termination becomes difficult
Due to active radical sites accumulation, the rate of
polymerization increases enormously and sometimes, the
uncontrolled exothermic reactions can leads to an
explosion. The whole phenomenon is called “auto
acceleration”
Examples: The free radical polymerization of styrene or
methyl methacrylates to get transparent moulding powder
and cast sheets and also of vinyl chloride to get PVC resins.
Solution Polymerization
In this process, the monomer is dissolved in a suitable inert solvent along with the
chain transfer agents wherever used.
The free radical initiator is also dissolved in the
solvent medium.
The solvent enhances the heat capacity, thereby
reducing the viscosity and promotes proper heat
transfer.
Solution polymerization techniques can advantageously be used where the polymer is
used in solution form ( as adhesive and coating compositions).
Solution Polymerization
Chain transfer to the solvent used can not be ruled out, hence it is difficult to obtain
very high molecular weight products.
The polymer formed will also have to be isolated from
the solution either by evaporation or precipitation in a
non-solvent and removal of their final traces is always
extremely difficult.
Examples: production of polyacrylonitrile by free radical
polymerization, polyisobutylene by cationic polymerization,
poly(vinyl acetate) to be converted to poly(vinyl alcohol)
Suspension polymerization
In order to control the enormous amount of heat release in bulk polymerization,
suspension polymerization method was developed.
Only water insoluble monomer can be polymerized by this technique.
The monomer is suspended in water in the form of fine droplets, which are stabilized
and prevented from coalescing by using suitable water soluble protective colloids,
surface active agents and by stirring.
Agitators are used along with suspending agents in the aqueous phase in order to
maintain a specific droplet size and dispersion.
Suspension polymerization
The size of the droplets formed depends on the monomer-water ratio, the type and
concentration of stabilizing agents and also on the type and speed of the agitation
employed
Since each monomer droplets are isolated and independent of other droplets, each of
these droplets act as tiny bulk reactors.
Heat transfer occurs from the droplets to the water having large heat capacity and low
viscosity
As the entire bulk of the monomer is divided into innumerable tiny droplets, control of the
kinetic chain length of the polymer is also quite good, so the product has a narrow
molecular weight distribution.
The polymerization proceeds to 100% conversion and the product is obtained as a
spherical beads or pearls. So, the technique is also know as Bead or Pearl polymerization.
Suspension polymerization
Isolation of the polymer becomes easy as this involves only the filtration of the
bead and removal of the surface active agents and protective colloids by just
washing with water.
The water washed and dried product can be used as such for molding purposes or
can be dissolved in a suitable solvent medium for use as an adhesive and coating
agents.
Examples: Expandable polystyrene beads ( from which polystyrene foams are
made), styrene-divinyl benzene copolymer beads( ion exchange) by free radical
initiators. Typical stabilizer used: Gelatin, methyl cellulose, poly(vinyl alcohol),
sodium polyacrylate
Emulsion Polymerization
In emulsion polymerization, the monomer is dispersed in an aqueous phase as fine
droplets which are then stabilized (emulsified) by surface active agents (surfactants- soaps
or detergents), protective colloids and also by certain buffers.
The surfactants can be cationic ( alkali salts of fatty acids and of aryl and alkyl sulfonic
acids), or non-ionic (alkyl glycosides).
Water soluble initiators are used (persulfates).
Surfactants serves the purpose of lowering the surface tension at the monomer water
interface and facilitate emulsification of the monomer in water.
The surfactant will form micelles when their concentration exceeds critical micelle
concentration (CMC), that are dispersed throughout the solution
Emulsion Polymerization
Emulsion Polymerization
In micelle formation, the emulsifier molecule aggregates in such a way that the polar
end of the molecule align themselves outward and the hydrocarbon end come close
to each other at the interior.
Due to the close proximity of the hydrocarbon ends of all emulsifier molecule, the
interior of the micelle acts a hydrocarbon phase where the monomer can be
stabilized.
When the monomer is added and agitated, emulsification take place.
The resultant emulsion is a complex system: A molecular solution of the emulsifier in
water is the continuous phase wherein the monomer droplets and micelle (having
solubilized monomer at their interior) are uniformly dispersed.
Emulsion systems generally utilize a water soluble initiators as persulfate or hydrogen
peroxide.
Emulsion Polymerization
Emulsion Polymerization
With the more and more polymer formation, the polymer aggregate into fine particles
and get surrounded and then stabilized by the emulsifier layer of the micelle.
At the end of the polymerization, the fine particles of the
polymer stabilized by the emulsifier and dispersed uniformly
in the aqueous layer. This milky white dispersion is called
Latex.
The latex either can be used for making adhesives, water
soluble emulsion paints etc. or the polymer can be isolated
from the latex by destabilizing the emulsion (using
electrolyte) by spray drying or freezing.
Most widely used industrial technique for polymerization of monomer such as vinyl
chloride, butadiene, chloroprene, vinyl acetate, acrylates, methacrylate.
Ring Opening Polymerization
Polymerization of cyclic monomer is carried out by Ring opening Polymerization
(ROP)method.
Examples of cyclic monomers
Cyclic ether Amides (lactams) Ester (lactones) Siloxane
Ethylene oxide -Caprolactam -Caprolactones Octa methyl cyclo-
tetra siloxane
Ring Opening Polymerization
Examples
Cyclic anhydrides Cyclic sulfide Cyclic olefines
N-carboxy amino acid Ethylene sulfide Cyclopentene
anhydride
Ring Opening Polymerization
The ease of polymerization of cyclic monomer depends on both thermodynamics and
kinetic factors
Thermodynamic factor means relative stabilities of the cyclic monomer and liner monomer
structure
Thermodynamics of polymerization of cycloalkanes at 25°C
Cyclic (CH2)n H (kJ/Mol) S (J/mol.K) G (kJ/Mol)
Number (n)
3 -113 -69 -92.5
4 -105 -55 -90
5 -21 -42 -9.2
6 +2.9 -10 +5.9
7 -21.8 -15.9 -16.3
8 -34.8 -3.3 -34.3
Ring Opening Polymerization
Polymerization is favored thermodynamically for all except the 6-member ring
The order of thermodynamic feasibility is 3,4 > 8 > 7,5
Above ceiling temperature, G becomes positive, and polymerization is no longer
favorable
Polymerization requires a kinetic path way for the ring to open and undergo reaction
Ring Opening Polymerization
The cycloalkanes do not have bond in the ring structure that is easily prone to attack by
an initiator species
The lactams, lactones, cyclic ether, cyclic acetals monomers stand marked contrast to the
cycloalkanes
The presence of hetro atom in the ring provides a site for nucleophilic or electrophilic
attack by an initiator species, resulting in initiation and subsequent propagation by
ring opening.
Such monomer are polymerized since both thermodynamics and kinetics factors are
favorable
Polymeriability is higher for rings 3,4 and 7-11 members
Practical point of view: ROP limited to monomer of less than 9 members ring due to
unavailability of larger cyclic monomers
Ring Opening Polymerization
Example : Ring Opening Polymerization of cyclic ether (hetrocyclic oxirane)
The polymerization of ethylene and propylene oxide can be catalyzed by metal
hydroxide, alkoxides, oxides, metal alkyls and
Ring Opening Polymerization
Polyaddition
Polycondensation
