CH3E03.

Polymer Chemistry (Elective)

UNIT I: Methods of Polymerization (9 hr):

 Step reaction (Condensation) Polymerization:

Mechanism, types and Kinetics of condensation polymerization
Interfacial condensation
Ring verses chain formation
Bifunctional and Polyfunctional step reaction polymerization- gelation
Gel point- experimental observation, Molecular weight distribution
Ring scission polymerization

 Radical Chain (Addition) Polymerization:

Vinyl polymerization, Vinyl monomers
Mechanism of Vinyl polymerization
Experimental methods in vinyl polymerization
Kinetics of free radical polymerization
Degree of polymerization
Chain transfer
Molecular weights and its distribution
Effect of temperature and pressure on chain polymerization

 Ionic Polymerization:
Anionic polymerization- Initiation and Propagation Mechanisms, Kinetics
Living polymerization, Ionic equilibrium
Molar mass distribution
Transfer and termination, stereo-control
Cationic polymerization- Mechanism, Kinetics
Radiation activated polymerization

UNIT II: Method of Polymerization II (9 hr):

 Suspension and emulsion polymerization of mono and hetro-disperse polymers
 Co-ordination Chain Polymerization: Ziegler- Natta Catalysis Mechanism, Kinetics
 Ring opening polymerization
 Co-polymerization:
Different types of copolymers
Kinetics of copolymerization (Free radial and Ionic)
The co-polymerization equations, composition of copolymers
Mechanism of co-polymerization
Monomer reactivity ratios and co-polymerisation parameters
Chemistry of copolymerization
Reactivity and structure of monomers and radicals
 Polymerization in homogenous and heterogeneous systems
 Gas phase polymerization
 Bulk polymerization and polymer precipitate
 Polymers are long-chain molecules of very high molecular weight and are frequently referred as
“macromolecules” They are built up by joining together of a large number of much smaller
molecules/units. The small molecules that combine with each other to form polymer molecules are
termed monomers, and the reactions by which they combine are termed polymerizations.

The first polymers used were natural products, especially cotton, starch, proteins, and wool. Then
came several semi-synthetic polymers, which were natural polymers modified in some way. One of the
first to attain commercial importance was cellulose nitrate plasticized with camphor, popular around
1885 for stiff collars and cuffs as celluloid, later most notably used in Thomas Edison’s motion picture film.
Cellulose nitrates were also sold as lacquers, used to coat wooden staircases, and so on. The first truly
synthetic polymer was a densely cross-linked material based on the reaction of phenol and formaldehyde.
The product, called Bakelite, was manufactured from 1910 onward for applications ranging from electrical
appliances to phonograph records. All of these materials were made on a more or less empirical basis;
trial and error has been the basis for very many advances in history, including polymers. However, in the
late 1920s and 1930s, a DuPont chemist by the name of Wallace Carothers succeeded in establishing the
reality of the Macromolecular Hypothesis by bringing the organic-structural approach back to the study of
polymers, resulting in the discovery of nylon and neoprene. Actually the first polymers that Carothers
discovered were polyesters. He reasoned that if the Macromolecular Hypothesis was correct, then if one
mixed a molecule with dihydroxide end groups with a another molecule with diacid end groups and
allowed them to react, a long, linear chain should result if the stoichiometry was one-to-one. The problem
with the aliphatic polyesters made at that time was their low melting point, making them unsuitable for
clothing fibers because of hot water washes and ironing. When the ester groups were replaced with the
higher melting amide groups, the nylon series was born. In the same time frame, Carothers discovered
neoprene, which was a chain-polymerized product of an isoprene-like monomer with chlorine replacing
the methyl group.

Plastics identification code

TYPES OF POLYMERS AND POLYMERIZATIONS

There are mainly two types of classifications. One classification is based on polymer structure and
divides polymers into condensation and addition polymers. The other classification is based on
polymerization mechanism and divides polymerizations into step and chain polymerizations. The terms
condensation and step are often used synonymously, as are the terms addition and chain because most
condensation polymers are produced by step polymerizations and most addition polymers are produced
by chain polymerizations, this is not always the case. The condensation–addition classification is based on
the composition or structure of polymers. The step–chain classification is based on the mechanisms of the
polymerization processes.
Polymers were originally classified by Carothers [1929] into condensation and addition polymers
on the basis of the compositional difference between the polymer and the monomer(s) from which it was
synthesized. Condensation polymers were those polymers that were formed from polyfunctional
monomers by the various condensation reactions of organic chemistry with the elimination of some small
molecule such as water. An example of such a condensation polymer is the polyamides formed from
diamines and diacids with the elimination of water according to

Addition polymers were classified by Carothers as those formed from monomers without the loss
of a small molecule. Unlike condensation polymers, the repeating unit of an addition polymer has the same
composition as the monomer. The major addition polymers are those formed by polymerization of
monomers containing the carbon–carbon double bond. Such monomers will be referred to as vinyl
monomers.

where Y can be any substituent group such as hydrogen, alkyl, aryl, nitrile, ester, acid, ketone, ether, and
halogen.
The development of polymer science with the study of new polymerization processes and polymers
showed that the original classification by Carothers was not entirely adequate and left much to be desired.
Thus, for example, consider the polyurethanes, which are formed by the reaction of diols with
diisocyanates without the elimination of any small molecule:
 Using Carothers’ original classification, one would classify the polyurethanes as addition polymers,
since the polymer has the same elemental composition as the sum of the monomers. However, the
polyurethanes are structurally much more similar to the condensation polymers than to the addition
polymers. The urethane linkage (-NH-CO-O-) has much in common with the ester (-CO-O-) and amide
(-NH-CO-) linkages.
To avoid the obviously incorrect classification of polyurethanes as well as of some other polymers
as addition polymers, polymers have also been classified from a consideration of the chemical structure of
the groups present in the polymer chains. Condensation polymers have been defined as those polymers
whose repeating units are joined together by functional units of one kind or another such as the ester,
amide, urethane, sulfide, and ether linkages. Thus the structure of condensation polymers has been
defined by

where R is an aliphatic or aromatic grouping and Z is a functional unit such as –OCO-, -NHCO-, -S-,
-OCONH-, -O-, -OCOO-, and -SO2-. Addition polymers, on the other hand, do not contain such functional
groups as part of the polymer chain. Such groups may, however, be present in addition polymers as
pendant substituents hanging off the polymer chain. According to this classification, the polyurethanes are
readily and more correctly classified as condensation polymers.
It should not be taken for granted that all polymers that are defined as condensation polymers by
Carothers’ classification will also be so defined by a consideration of the polymer chain structure. Some
condensation polymers do not contain functional groups such as ester or amide in the polymer chain. An
example is the phenol–formaldehyde polymers produced by the reaction of phenol (or substituted
phenols) with formaldehyde

These polymers do not contain a functional group within the polymer chain but are classified as
condensation polymers, since water is split out during the polymerization process.
 In summary, a polymer is classified as a condensation polymer if its synthesis involves the
elimination of small molecules, or it contains functional groups as part of the polymer chain, or its
repeating unit lacks certain atoms that are present in the (hypothetical) monomer to which it can be
degraded. If a polymer does not fulfill any of these requirements, it is classified as an addition polymer.

STEP POLYMERIZATION
Step polymerizations are of two types depending on the nature of monomer(s) employed. The first
involves two different bifunctional monomers in which each monomer possesses only one type of
functional group. The second involves a single monomer containing both types of functional groups. The
synthesis of polyamides illustrates both groups of polymerization reactions. Thus polyamides can be
obtained from the reaction of diamines with diacids or from the reaction of amino acids with themselves:
The two groups of reactions can be represented in a general manner by the equations

Basis for Analysis of Polymerization Kinetics

The kinetics of polymerization are of prime interest from two viewpoints. The practical synthesis
of high polymers requires knowledge of the kinetics of the polymerization reaction. From the theoretical
viewpoint the significant differences between step and chain polymerizations reside in large part in their
respective kinetic features. Step polymerization proceeds by a relatively slow increase in molecular
weight of the polymer. Consider the synthesis of a polyester from a diol and a diacid. The first step is the
reaction of the diol and diacid monomers to form dimer:

The dimer then forms trimer by reaction with diol monomer, etc. as
Monomer + monomer → dimer
Dimer + monomer trimer
Dimer + dimer tetramer
Trimer + monomer tetramer
Trimer + dimer pentamer
Trimer + trimer hexamer
Tetramer + monomer pentamer
Tetramer + dimer hexamer
Tetramer + trimer heptamer
Tetramer + tetramer octamer
Pentamer + trimer octamer
Pentamer + tetramer nonamer ð2-8aÞ
which can be expressed as the general reaction
n-mer + m-mer (n + m)-mer