CY2002D : ORGANIC CHEMISTRY

Dr. Raju Dey

Assistant Professor
Department of Chemistry, NITC
Room No: 210E
Phone no: +91-7558035591
Email: rajudey@nitc.ac.in

Book References:
R. T. Morrison and R. N. Boyd. Organic Chemistry. New Jersey : Prentice Hall, 1992
J. March. Advanced Organic Chemistry : Reactions, Mechanisms and Structure. New York: Wiley, 2006.
Module 3: (17 hours)

Functionalization of alkenes: hydroboration, dihydroxylation, epoxidation

and oxidative cleavage. Oxidation: oxidation of hydrocarbons, alcohols and
ketones. Reduction: catalytic hydrogenation, reduction by dissolving
metals and reduction by hydride transfer reagents.

Methods of polymerization: Radical chain polymerization, step

polymerization: polycondensation, polyaddition, ring opening-lactams,
lactones, electrochemical polymerization, group transfer polymerization,
ion chain polymerization: cationic and anionic and emulsion
polymerization. Molecular weight determination of polymers. Polymer
reactions: hydrolysis, acidolysis, aminolysis, hydrogenation and cyclization.
Cross linking: sulphur and peroxides. Stereochemistry of polymers
 Alkenes: Nomenclature

CH3CH2CH=CH2 CH3CH=CH2CH3 CH3CH=CHCH2CH2CH3

1-butene 2-butene 2-hexene

CH3CH2CH2CH2 C CH2CH2CH3

=
CH2
2-propyl-1-hexene
 Alkenes: Nomenclature

If the same number for the alkene functional group suffix is obtained in
both directions, the correct name is the name that contains the lowest
substituent number.

2,5-dimethyl-4-octane /----------------------------------
4,7-dimethyl-4-octane 2-bromo-4-methyl-3-hexane /-------------------------------------------
5-bromo-3-methyl-3-hexene
vinyl group and allyl group.

H2C=CH- H2C=CHCH2-
Vinyl group Allyl group

H2C=CHCl H2C=CHCH2-Br
Vinyl chloride Allyl bromide

5
The isomers of alkenes

Four isomeric alkenes of molecular formula C4H8:

structural isomers geometrical isomers

6
 Carbon-carbon -bond of alkenes can be reduced easily to the corresponding saturated
C-C bond.
Other -bond bond such as
O
C=O (carbonyl) and CN are not easily reduced by catalytic
O
hydrogenation.H , PtO 2 2
O O
ethanol
The C=C bonds of aryl rings are not easily reduced. H2, PtO2

O O ethanol O
H2, Pd/C H2, PtO2
OH CH3(CH2)16CO2H
O O O
ethanol
H2, Pd/C
nsaturated fatty acid) H2, PtO2 Steric Acid (saturated fatty acid)
C H
5 11 OH CH3(CH2)16CO2H
O
ethanol O O
Linoleic Acid (unsaturated fatty acid) Steric Acid (saturated fatty acid)
OCH3 H2, Pd/C H2, Pd/C
C5H11 OCH3 OOH
O CH3(CH2)16CO
O 2H
ethanol
H2, Pd/C Linoleic Acid (unsaturated fatty acid) OCH3 H2, Pd/C
OH Steric Acid (saturated fatty
OCH acid)
CH3(CH2)16CO2H 3
O ethanol
fatty acid) O
Steric Acid (saturated fatty acid)
H2, Pd/C
C C OCH3 H2, Pd/C
O N N OCH3
ethanol O
ethanol
H2, Pd/C
OCH3 H2, Pd/C C C
OCH3 N N
ethanol ethanol

H2, Pd/C C
C
N N
ethanol
 Hydrogenation of Alkenes:
Addition of H2 to the π-bond of alkenes to afford an alkane.
The reaction must be catalyzed by metals such as Pd, Pt, Rh, and Ni.

H H H H
Pd/C
C C + H H
H
C C
H H°hydrogenation = -136 KJ/mol
EtOH
H H H H

C-C π-bond H-H C-H

= 243 KJ/mol = 435 KJ/mol = 2 x -410 KJ/mol = -142 KJ/mol

The catalysts is not soluble in the reaction media, thus this process is referred
to as a heterogeneous catalysis.
The catalyst assists in breaking the -bond of the alkene and the H-H -bond.
The reaction takes places on the surface of the catalyst. Thus, the rate of the
reaction is proportional to the surface area of the catalyst.
The isomers of alkenes
Heats of Hydrogenation
relative stability of isomeric alkenes

H H H CH3
H2, Pd H2, Pd
CH3CH2CH2CH3
H3C CH3 H3C H

cis-2-butene trans-2-butene

H°hydrogenation: -119 KJ/mol -115 KJ/mol

# The greater release of heat, the less stable the reactant.

# trans isomer is 4 KJ/mol more stable than the cis isomer
Heats of Hydrogenation of Some Alkenes
Alkene H° (KJ/mol)
H2C=CH2 136

H H
monosubstituted
125 - 126
H3C H

H H
117 - 119
H3C CH3

H CH3
disubstituted 114 - 115
H3C H

H3C H
116 - 117
H3C H

H3C H
trisubstituted 112
H3C CH3

H3C CH3
tetrasubstituted 110
H3C CH3
Heats of combustion
Relative stability of isomeric alkenes

H H H CH3

H3C CH3 H3C H

cis-2-butene trans-2-butene

H°combustion: - 2710 KJ/mol - 2707 KJ/mol

# The greater release of heat, the less stable the reactant.

# trans isomer is 3 KJ/mol more stable than the cis isomer

Hydrogenation on metal surface

at the beginning of adsorption physisorbed condition chemisorbed condition

Physisorption of hydrogen Chemisorption of hydrogen

on nickel surface on nickel surface

L-1
Stereochemistry of Alkene Hydrogenation
Mechanism:

H H
H2C CH2 H H H2C CH2

H2C CH2
H2

HH
H H
H H C C
C H H H
H H
C H
Stereochemistry of Alkene Hydrogenation
Mechanism:

The addition of H2 across the -bond is syn,

i.e., from the same face of the double bond

H CH3
CH3 H2, Pd/C CH3 H

EtOH CH3
CH3 CH3
H H

syn addition
of H2 Not observed
Electrophilic Addition

C-C -bond: H°= 368 KJ/mol

C-C -bond: H°= 243 KJ/mol
-bond of an alkene can act as a nucleophile!!

Electrophile can be: X2, HX etc.

 Stereochemistry of Alkene Bromination
Mechanism:
The addition of Br2 across the -bond is anti,
i.e., from the opposite face of the double bond

In this reaction alkene interacts with LUMO of bromine (i.e. empty σ* orbital)to form a
three membered cyclic bromonium ion intermediate.
The bromide anion attacks the cyclic bromonium ion resulting in generation of product 1,2-
dibromide
Bromination of cis 2-butene
Br Me
+
Me Br
Me
Br + Br
Br-Br Me
Me H
Me
H H
H

H H

Me
Me H
Br H Br
Br H
Br
Br H
Me
H
Me
Br Me
H Br Me Me
Br Me
H
Br
H Br H
Me
H H Br
Me
H Br Me Me
Bromination of trans 2-butene
Br H
+
H Br
H
Br + Br
Br-Br Me
Me Me
Me
Me Me
H

H H

Me
Br
H Br H
H H
Br Br
Br H
Me Me
Me Me
Br Me
H Me
H Br H Br
Br
H H Br

Me H Br
Me Me
Me Me
H Br
Explain the observation

HO
CH3 CH3
Br2, H2O
+ HBr
Br
H
Conversion of Alkenes to Vicinal Halohydrins

X2, H2O X
+ HX
OH

anti
stereochemistry

Mechanism involves a halonium ion intermediate

21
Unsymmterical alkenes: Halohydrin formation is governed by
carbocation stability

 CH3

Br 
+


more + charge on the more substituted carbon

H2O adds in the second step

H2O adds to the carbon that has the most + charge

22
Electrophilic Addition of Hydrogen Halides to Alkenes

H H Br H
C C + H-Br C C
H H
H H H H
nucleophile electrophile

Bonds broken Bonds formed

C=C -bond 243 KJ/mol H3C-H2C–H -410 KJ/mol
H–Br 366 KJ/mol H3C-H2C–Br -283 KJ/mol

calc. H° = -84 KJ/mol

expt. H°= -84 KJ/mol
Regioselectivity of Hydrogen Halide Addition:
Markovnikov's Rule

H H
C H H-Br Br H
H-Br Br H
H Br H Br
R C R
C
C
H
R C C H + R C
R C C C H+ R C C H
H x
H H H H H HH H H H
none of this none of this
R R
Br H
H-Br Br H
H Br H Br
C H-Br
H of HX R C H + RtoCthe
For the electrophilic
R addition
C across
C a C=C bond,
R C C H the H
+ (of
R CHX)
C will
H
R C C H add C carbon
H
of the double bond withHthe most H’s (the
H least substitutent carbon)
R H
R H and the X Rwill
R H H add to
the carbon of the double bond that has the most alkyl groups.none of this none of this
R
R Br H H Br
C H H-Br
Br H H Br +
C H R
H-Br C R C C R R C C R
R C + RR C
R R C C R H C R R H
R R H R H none of this
Reactivity of HX correlates with acidity

Slowest HF << HCl < HBr < HI fastest

Mechanism: Electrophilic addition of HX to alkenes
Explain the observation

H
Cl H
H H
H3C C H H-Cl H3C C H
+ H3C C H
C C C C
C C
H3C H3C H
H H H H H3C H
Cl H

~ 50% ~ 50%
expected product
Regioselectivity of Hydrogen Halide Addition in presence of peroxide:
Anti Markovnikov's Rule

H H H
H-Br C Br H
H-Br H H
Br Br H Br
H-Br Br H
R
C
C
H
R C
H
R C C H + RR RC
C
C CCCH
H
H + R C C H R C C H x+ R
H H HH2HO2 H H
H HH H H H H
none of this none of this no
R R R
H-Br Br H
H-Br H
Br HBr H Br
H-Br Br H
C electrophilic
ForR the H C C
H of HX across+a C=C bond, H
C R addition
C R C C H RRC
R C C CCH Hthe+H (of
R HX)
C Cwill
H addRtoCthe
C carbon
H + R
of the double
H bond withH the most
R H’s
H (the least substitutent
R H
R HH carbon)
R H and the X R
willHadd to
the carbon of the double bond that has the most alkyl
none of thisgroups.
none of this no
R R R
Br H H H
Br Br H Br Br H
C H H-Br C H H-Br C H H-Br
R C R C R C C R + RRR C C
C C CRR + R C C R R C C R + R
R R R H R H
R HR R H R H
Addition of Radicals

Markovnikov addition

Anti Markovnikov addition

Heterolysis & Homolysis
Heterolytic bond cleavage or heterolysis

H Br H+ + Br

H Br H+ + Br
Homolytic bond cleavage or homolysis
H Br H + Br

H Br H + Br

Homolysis produces radicals, which are very reactive species

Radical chain reactions
Radical chain reactions
Radical chain reactions
The regiochemistry of free radical addition of H-Br to alkenes
reflects the stability of the radical intermediate.

H H R
R C• R C• R C•
H R R
Primary (1°) < Secondary (2°) < Tertiary (3°)

34
Acid-Catalyzed Hydration of Alkenes

C C + H—OH H C C OH

acid catalyzed hydration reaction in 50% H2SO4-50% H2O

Follows Markovnikov's Rule

H3C H CH3
50% H2SO4
C C CH3 C CH2CH3
50% H2O
H3C CH3 OH
(90%)
Step (1) Protonation of double bond

H3C H
+
C CH2 + H O:

H3C H
slow
H3C H
+
C CH3 + :O:

H3C H
Step (2) Capture of carbocation by water

H3C H
+
C CH3 + :O :

H3C H
fast

CH3 H
+
CH3 C O:

CH3 H
Step (3) Deprotonation of oxonium ion

CH3 H H
CH3 C O: + :O :
+
CH3 H H
fast
CH3 H
.. +
CH3 C O: + H O:

CH3 H H
Principle of microscopic reversibility

H3C CH3
H+
C CH2 + H2O CH3 C CH3
H3C OH

In an equilibrium process, the same intermediates and transition states

are encountered in the forward direction and the reverse, but in the
opposite order
Hydroboration reaction

C C + H—BH2 H C C BH2

Hydroboration can be viewed as the addition of borane (BH3) to the

double bond
Hydroboration Step

C C + H—BH2 H C C BH2

Hydroboration reagents:
1. Borane-tetrahydrofuran complex (H3B-THF)
H

H2B BH2 Diborane (B2H6) normally used in an

2. ether-like solvent called "diglyme"
H
Oxidation Step

H2O2, HO–
H C C BH2 H C C OH

Organoborane formed in the hydroboration step can be oxidized into

alcohol by hydrogen peroxide
Hydroboration-Oxidation of Alkenes:
Anti-Markovnikov addition of H-OH/ syn addition of H-OH

CH3 1) B2H6, THF H

2) H2O2, NaOH, H2O CH3

H
HO

44
Mechanism of Hydroboration
syn addition of the H2B–H bond to the same face of the -bond in an anti-
Markovnikov sense
H3C CH3 H OH
1. H3B-THF C C
C C CH3 CH3
2. H2O2, HO–
H3C H CH3 H

(98%)
Epoxidation of alkenes
Stereochemistry
H
of the epoxidation: syn addition
O
of oxygen
H H3CCO3H H H
R R R R
Groups that are trans on the alkene will end up
cis-alkene trans cis-epoxide
on the epoxide product.

H R H3CCO3H O
H R
R H R H
trans-alkene trans-epoxide

Groups that are cis on the alkene will end up cis on the epoxide product.

H H H3CCO3H O
H H
R R R R
cis-alkene cis-epoxide
 Epoxidation of Alkenes
Reaction between alkene and peroxy acid

O H
OH
O
H3C O + O
H3C O

Epoxide (oxirane): three

O H O membered cyclic ethers
O HO OH
H3C O H3C OH

peroxyacetic acetic peroxide

acid acid
Barry Sharpless
Epoxidation: reactivity
Epoxidation: diastereoselectivity
Relative Rates of Epoxidation

ethylene H2C=CH2 1
propene CH3CH=CH2 22
2-methylpropene (CH3)2C=CH2 484
2-methyl-2-butene (CH3)2C=CHCH3 6526
Other methods

?
Dihydroxylation of alkenes
 ++
O _
Ozonolysis of Alkenes O O-

Oxidative cleavage of an alkene to carbonyl compounds (aldehydes and ketones).

The - and -bonds of the alkene are broken and replaced with C=O double bonds.

1) O3
2) Zn
O + O

1) O3
2) Zn H
H + O C
H
O

1) O3
2) Zn O

H
O
 Mechanism

O3, CH2Cl2 O
R1 R3 -78 °C O O O O R1 R3
R1 R3 Zn
-or- O + O
R2 R4 R1 R3 R2 R4
O (H3C)2S R2 R4
R2 R4
molozonide ozonide + ZnO or (H3C)SO

Electrical discharge
Ozone (O3): 3 O2 2 O3
Example
CH3 CH2CH3

C C
H CH2CH3

1. O3
2. H2O, Zn

CH3 CH2CH3

C O + O C
H CH2CH3
(38%) (57%)
Dihydroxylation of alkenes
Dihydroxylation : mechanism

VIII
Dihydroxylation : diastereoselectivity
Dihydroxylation : via epoxide ring opening
Predict the products

Me

mCPBA
CF 3COOH
Me ?
+
H H3O

H
H

mCPBA
CF 3COOH
Me ?
Me +
H3O

H
Oxidative cleavage of alkenes
Oxidative cleavage of alkenes
 Oxidative cleavage: Ozonolysis

O O O R1 R3
R1 R3 Zn
-or- O + O
R3 R2 R4
O (H3C)2S R2 R4
R4
onide ozonide + ZnO or (H3C)SO
Allylic oxidation
Oxidation

Oxidation states in organic species are not always easy to assign, due to the
covalent nature of bonding for organic molecules.
 Oxidation

Instead of oxidation state, we define an oxidation number :

The contribution to each carbon is:

– 1 for H
0 for C
+ 1 for electronegative elements
Oxidation of Alcohols to Aldehydes, Ketones or Carboxylic Acids

The most widely employed transition metal oxidants for alcohols are based on Cr(VI).
Chromium trioxide = CrO3 Dichromate = Cr2O72-

Chromium trioxide will oxidize 2o alcohols to ketones. A specific cocktail of CrO3 and H2SO4
in acetone is called the Jones reagent, and is particularly effective for this transformation.
Oxidation of primary alcohols to carboxylic acids

1o alcohols are oxidized to aldehydes, but in the presence of water form the hydrate
which can be further oxidized to the carboxylic acid.
Oxidation of alcohols to aldehydes, ketones or carboxylic acids

Pyridinium chlorochromate (PCC) and pyridinium dichromate (PDC) are also useful
reagents for stopping at the aldehyde oxidation state. PCC is less acidic than the
Jones reagent and PDC is even further reduced in acidity.
Mechanism of Alcohol Oxidation by Chromic Acid
A. Allylic Oxidation B. Epoxidation

D. Ozonolysis C. Dihydroxylation
Catalytic hydrogenation reactions

Notes:
- usually gives syn addition if a heterogeneous catalyst is used
Can be applied to alkenes, alkynes and imines (but not yet very useful for ketones).

Use of a heterogeneous catalyst (e.g. Pd on carbon) generally affords a syn addition

of hydrogen. In other words the reaction is stereospecific.
Stereochemistry of Alkene Hydrogenation
Mechanism:

The addition of H2 across the -bond is syn,

i.e., from the same face of the double bond

H CH3
CH3 H2, Pd/C CH3 H

EtOH CH3
CH3 CH3
H H

syn addition
of H2 Not observed
Identify the products
Me

Ni/D2
Me ?
H

H
Et

Ni/D2
Me ?
H

H
Hydrogenation on metal surface

Me
H
Me D H D
H D
H H
Me Me H D

Me Me
Me D Me
H D D Me
Ni/D2 D
D H
H D H
H D
D H
Me Me H
H Me Me
H Me
Me
Me

H
Use of a heterogeneous catalyst (e.g. Pd on carbon) generally affords a syn addition
of hydrogen. In other words the reaction is stereospecific.

Relative to the size of a molecule, the heterogeneous catalyst is also huge. This
means that the hydrogen will be delivered from the most accessible face of the
molecule. In other words, the reaction is stereoselective.
Catalytic hydrogenation of Alkyne
Hydrogenation of alkynes will afford alkanes…

… unless a special poison is introduced into the catalyst!

Catalytic hydrogenation of Alkyne

In the Lindlar catalyst, the lead (and sometimes quinoline) poisons the
palladium, allowing the skilled experimentalist to stop at the alkene.
This is a particularly good way to generate cis double bonds.
Reduction by dissolving metals

M + NH3 M+ [H3N------ e- ------NH3]

Solvated electron

The solution of alkali metal in ammonia (at -33°C) can generate solvated
electrons and metal cations.

These solvated electrons can reduce alkynes into trans alkene.

Reduction by dissolving metals
Mechanism
Reduction by hydride transfer reagents
Reduction by hydride transfer reagent
LiAlH4 is a stronger reducing agent than NaBH4

LiAlH4 is used to reduce compounds that are nonreactive toward NaBH4

 more reactive

more selective

•LiAlH4 and Red-Al will reduce almost anything: aldehydes, ketones, alcohols and esters
(to provide the corresponding alcohols), nitriles (to 1o amines), and even – under
forcing conditions – carboxylic acids! These reagents can even reduce alkyl tosylates!!

•DIBAL will reduce aldehydes and ketones as well, but in reactions with esters and
nitriles, it is possible to stop at the corresponding aldehyde or imine (which hydrolyzes
to aldehyde).
DIBAL allows the addition of one equivalent of hydride to an ester

Replacing some of hydrogens of LiAlH4 with OR groups decreases the

reactivity of the metal hydride
Formation of Amines by Reduction
NaBH4 can be used to selectively reduce an aldehyde or a
keto group in a compound
Lots of functional groups can be reduced: alkenes, alkynes,
C=O, C=N, and even alkyl halides.
Functional Group Interconversions: an Incomplete Summary
Functional Group Interconversions: an Incomplete Summary
Polymers
What are Polymers?
Long chains of repeating monomers

Poly mer
many repeating unit
 HO O
[O ]n OH

HO HO
OH OH HO
OH
Natural Polymers

Silk/Wool
Cellulose/Lignin
Starches/Polysaccharides
Rubber
DNA/RNA
Proteins
Synthetic Polymers

Plastics
Synthetic Fibers (nylon, polyester, etc.)
Films
Elastomers
Adhesives
Synthetic rubbers
 Polymer Composition

Most polymers are hydrocarbons

– i.e. made up of H and C
• Saturated hydrocarbons
 Polymer Composition

Many polymers are contains heteroatom

– i.e. made up of H, C and hetero atom
Chemistry of Polymers

Free radical polymerization

H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer

Initiator: example - benzoyl peroxide

H H H
C O O C 2 C O =2R
H H H
Chemistry of Polymers
Bulk or Commodity Polymers
Molecular Structures

Covalent chain configurations and strength:

 Range of Polymers

Traditionally, the industry has produced two main types of synthetic polymer –
plastics and rubbers.

# Plastics are (generally) rigid materials at service temperatures

• Plastics are further subdivided into thermoplastics and thermosets

# Rubbers are flexible, low modulus materials which exhibit long-range elasticity.
Thermoplastics and Thermosets Polymers
 Glass-Transition Temperature

Temperature at which a polymer transitions from crystalline to amorphous

Elastomers (such as rubber) have relatively low TG and are amorphous
under standard conditions
Range of Polymers

Another way of classifying polymers is in terms of their form or function

Synthesis of Polymers

There are a number different methods of preparing polymers from

suitable monomers, these are

Addition polymerization
Condensation polymerization
Insertion polymerisation.
Addition polymerization

Chain-growth polymers, also known as addition polymers, are made by

chain reactions
 Condensation polymerization

Step-growth polymers, also called condensation polymers, are made by

combining two molecules by removing a small molecule
Addition Vs. Condensation Polymerization
Thermodynamics

# Thermodynamics of polymerization determines the position of the

equilibrium between polymer and monomer(s).

# The well known thermodynamic expression:

G = H - TS

# For polymerization to occur (i.e., to be thermodynamically feasible),

the Gibbs free energy of polymerization Gp < 0.
If Gp > 0, then depolymerization will be favored.
 Thermodynamics

# Standard enthalpy and entropy changes, Hop and Sop are reported
for reactants and products in their appropriate standard states.
Generally:
• Temperature = 25oC = 298K
• Monomer – pure, bulk monomer or 1 M solution
• Polymer – solid amorphous or slightly crystalline

# Polymerization is an association reaction such that many monomers

associate to form the polymer
Sp < 0 for nearly all polymerization processes
 Thermodynamics

# Since depolymerization is almost always entropically favored, the Hp

must then be sufficiently negative to compensate for the unfavorable
entropic term.

Only then will polymerization be thermodynamically favored

resulting negative Gp

In practice:
Polymerization is favored at low temperatures: TSp is small
Depolymerization is favored at high temperatures: TSp is large
 Thermodynamics

# Therefore, thermal instability of polymers results when TSp overrides Hp

and thus Gp > O; this causes the system to spontaneously depolymerize (if
kinetic pathway exists).
Ceiling temperature

The temperature at which the propagation and depropagation

reaction rates are exactly equal at a given monomer concentration

5
kdp
-1 4

3
k, sec
kp[M]
2
kp[M] - kdp
1
Tc
0
300 350 400 450 500 550 600
o
Temperature, K
Types of Addition Polymerization

Free Radical Polymerization

Cationic Polymerization
Ionic Polymerization
Anionic Polymerization
 Free Radical Polymerization

Usually, low molecular weight alkenes undergo rapid polymerization

reactions when treated with small amounts of a radical initiator.

Example, the polymerization of ethylene

Free Radical Polymerization

Step 1: Initiation
Free Radical Polymerization

Step 2: Propagation
Free Radical Polymerization

Step 3: Termination
Chain growth
Activation energy for chain growth much lower than for initiation.
i.e. Growth velocity less temperature dependent than initiation
Anionic Polymerization of Styrene
Anionic Polymerization of Styrene
Anionic Polymerization of Styrene
Cationic Polymerization
Cationic Polymerization

(ii) Propagation : Chain growth takes place through the repeated

addition of a monomer in a head-to-tail manner to the ion with
retention of the ionic character throughout
Cationic Polymerization

(iii) Termination
Cationic Polymerization

The kinetics of these reactions is not well understood, but

they proceed very rapidly at extremely low temperatures.
Polymerization Techniques

• Bulk Polymerization
• Solution Polymerization
• Suspension Polymerization
• Emulsion Polymerization
 Bulk Polymerization

• The simplest technique

• Gives the highest-purity polymer
• Only monomer, a monomer soluble initiator and perhaps a chain
transfer agent are used
• This process can be used for many free radical polymerizations and
some step-growth (condensation) polymerisation.
 Bulk Polymerization

Advantages:
• High yield per reactor volume
• Easy polymer recovery
• The option of casting the polymerisation mixture into final product form

Limitations:
• Difficulty in removing the last traces of monomer
• The problem of dissipating heat produced during the polymerization
Solution Polymerization

A polymerization process in which the monomers and the

polymerization initiators are dissolved in a nonmonomeric liquid
solvent at the beginning of the polymerization reaction. The liquid
is usually also a solvent for the resulting polymer or copolymer.
 Solution Polymerization
• Solvent Requirements:
• Both the initiator and the monomer be soluble in it
• The solvent have acceptable chain transfer characteristics and
suitable melting and boiling points for the conditions of the
polymerization and subsequent solvent-removal step.
• Solvent choice may be influenced by other factors such as flash point,
cost and toxicity
Disadvantages:
small yield per reactor volume
The requirements for a separate solvent
recovery step
Suspension Polymerization
A polymerization process in which the monomer, or mixture of
monomers, is dispersed by mechanical agitation in a liquid phase,
usually water, in which the monomer droplets are polymerized while
they are dispersed by continuous agitation. Used primarily for PVC
polymerization
• If the monomer is insoluble in water, bulk polymerization can be
carried out in suspended droplets, i.e., monomer is mechanically
dispersed.
• The water phase becomes the heat transfer medium.
• In this system, the monomer must be either
1) insoluble in water or
2) only slightly soluble in water, so that when it polymerizes it
becomes insoluble in water.
Suspension Polymerization

• The behavior inside the droplets is very much like the behavior of
bulk polymerization
• Since the droplets are only 10 to 1000 microns in diameter, more
rapid reaction rates can be tolerated (than would be the case for bulk
polymerization) without boiling the monomer.

Emulsion polymerization is a type of radical polymerization that

usually starts with an emulsion incorporating water, monomer, and
surfactant.
 Emulsion Polymerization
Advantages Continued:
• Since polymer molecules are contained within the particles, viscosity
remains close to that of water and is not dependent on molecular
weight.
• The final product can be used as is and does not generally need to be
altered or processed.

Disadvantages of emulsion polymerization include:

• For dry (isolated) polymers, water removal is an energy-intensive process
• Emulsion polymerizations are usually designed to operate at high conversion of
monomer to polymer. This can result in significant chain transfer to polymer.