CHM 316

POLYMER CHEMISTRY
 General Introduction
Polymer science, chemistry and technology form
one of the major areas of materials science. This
field covers nearly all aspects of life ranging from
Engineering, medicine, etc. Polymers are organic
Materials and Polymer Chemistry is the science
of large molecules.
 COURSE CONTENT
• Definitions (monomer, polymer,
copolymers)
• Polymer Nomenclature/Architecture
(structure, conformation of molecular
chain, etc)
• General method of polymerization
• Linear chain growth polymerization
• Linear step growth polymerization
• Characterization techniques
 Recommended Texts
• Polymer Chemistry: The Basic
Concepts by Paul C. Hiemeniz
• Textbook of Polymer Chemistry by
Fred W. Billmeyer
• Polymer Chemistry: An Introduction,
3rd edition by Malcolm P. Stevens
• Introductory Polymer Chemistry by G.
S. Misra
 Definition of Terms
Many of the terms and definitions used in polymer
chemistry are not encountered in conventional
chemistry texts. Therefore, the following
definitions would be necessary.
• Monomers: These are low molecular weight compounds
possessing two or more reactive groups. For example,
CH2=CH2 (ethylene) is a monomer.
• Polymers: These are high molecular weight chemical
substances (macromolecules) made up of large repeating
units of a monomer and usually joined by covalent bonds
(the monomers two or more reactive groups). For example,
(CH2=CH2)n (polyethylene) is a polymer formed from the
monomer unit ethylene.
 Cont’d

Polymers could be linear, branched or cross-linked.

Linear polymers consists of a long chain of skeletal
atoms to which are attached the substituent groups
without branching, e.g. polyethylene (PE), poly (vinyl
chloride) (PVC), etc.
Branched polymers are linear polymers with
branches of the same basic structure as the main chain
Cross-linked polymers are those in which chemical
linkages exist between the chains.
The term 'polymer' and ‘plastic' are often used
interchangeably; polymers are a much larger class of
molecules which includes plastics, plus many other
materials, such as cellulose, amber, and natural rubber.
 Cont’d

• Copolymers: These are long chain polymers composed

of at least two different monomers, joined together in an
irregular sequence. For example, if styrene and
acrylonitrile are polymerized in the same reaction vessel,
a copolymer will be formed which contains both styrene
and acrylonitrile residues.
The sequence of monomer units along a copolymer chain
can vary according to the method of synthesis. Four
different types of sequencing arrangements are commonly
found. If we have two monomers A and B:
a) Random copolymers: In random copolymers, no
definite sequence of monomer units exists. For equal
proportions of A and B, we have
- A – B – B – B –A –A –B –A –A –A –A –B –A –B –B –B -
a) Random copolymers: In random copolymers, no
definite sequence of monomer units exists. For equal
proportions of A and B, we have
- A – B – B – B –A –A –B –A –A –A –A –B –A –B –B –B -
b) Alternating copolymers: As the name implies, a
regular pattern of alternating sequence of the two monomer
repeat units as shown
-A –B –A –B –A –B –A –B –A –B –A –B –A –B –
c) Block copolymers: Block copolymers contain a long,
uninterrupted sequence of each monomer.
-A – A –A –A –A –A –A –A –B –B –B –B –B –B –B –B-
d) Graft copolymers: When chains of a polymer
made of monomer B are grafted onto a polymer
chain of monomer A we have a graft copolymer.
Graft copolymers can be obtained in two ways:1st,
monomer B can be polymerized from sites along the length
of polymer A. 2nd, two performed polymers derived from A
and B can be induced to react with each other to form a
graft structure. Graft copolymers are sometimes produced
when two polymers are mixed and irradiated or subjected
to mechanical shearing.
 Classification of Polymers
Polymers are divided into two classes-Natural and
Synthetic. Natural polymers include wool (a protein
fibre), cotton (a vegetable fibre composed of cellulose),
natural rubber obtained from the trees of Hevea
brasiliensis species. Many commercial synthetic polymers
are copolymers. Synthetic polymers can be divided into
three broad based divisions: fibres (nylon and terylene),
synthetic rubbers which are not produced as substitutes for
natural rubber but may sometimes have properties superior
to the natural product and better suited for specific purposes
(neoprene) and plastics (heat resistant polymers used in
rockets).
Polymers can also be classified according to the types of
reactions involved in their synthesis.
 Polymerization Reactions

Polymerization is the process whereby low

molecular weight compounds (monomers)
are converted to high molecular weight
Compounds (polymers). Polymerization
processes fall into three main groups:
• Condensation Polymerization
• Addition Polymerization
• Ring Opening Polymerization
 Condensation Polymerization
This polymerization process is also known as step-growth polymerization and it
involves the reaction of two or more molecules with each other with the
elimination of loss of water, ammonia or other small molecules such as methanol.
This process is used as a basis for the synthesis of many important polymers, such
as nylon, polyesters, phenol-formaldehyde and urea-formaldehyde resins.
Nylon is a condensation polymer formed by the reaction of a diamine with a
dicarboxylic acid
n NH2 – R –NH2 + n HOOC – R’ – COOH
diamine dicarboxylic acid

(2n – 1) H2O + NH2 ( R – NH.CO –R’ CO )n OH

polyamide
For example, nylon 6,6 is made by the condensation of hexa-methylenediamine
with adipic acid.
The polymerization process proceeds by individual reactions of the functional
groups of the monomers. The two monomers react to form a dimer which reacts
with more monomer to form the trimer and so on until a high molecular weight
polymer is obtained. The formation of the polymer proceeds by only one
mechanism
 Addition Polymerization
This is the successive addition of monomer molecules onto
the reactive ends of a growing polymer. This process,
is called chain-growth polymerization or addition
polymerization. Chain growth polymerization is most
commonly applied to vinyl monomers (that is, monomers
containing carbon-carbon double bonds) and to certain types
of cyclic monomers (that is, monomers in which the double
bond is contained in ring-shaped molecules). There is no
loss of small molecules and unlike condensation polymers,
the repeating unit of an addition polymer has the same
composition as the original monomer.
The formation of a polymer by addition polymerization is
an example of a chain reaction. Once a chain reaction gets
started, it is able to keep itself going. The three steps of this
reaction involves: how the reaction gets started
(INITIATION); how the reaction keeps going
(PROPAGATION) and how the reaction stops
(TERMINATION).
 Cont’d
For example,
a) Initiation: Ṙ + CH2 = CHY R – CH2 –ĊHY,
Here a free-radical, Ṙ, attaches itself to the olefin
to produce a new radical and the monomer unit.

b) Propagation: This step is very rapid and leads

to high molecular weight products. No low
polymers are formed.
R–CH2–ĊHY + nCH2=CHY R(CH2–ĊHY)n + 1

c) Termination: This occurs in several ways:

Coupling by combining two growing chain radicals or
by disproportionation involving the transfer of a
hydrogen atom from one growing chain radical to
another.
 Cont’d

2R(CH2–ĊHY)n R(CH2–CHY)n - (CH2-CHY)n-R

Ring Opening Polymerization
The treatment of some cyclic compounds with
catalysts brings about reactions involving ring
opening followed by polymerization to yield high
molecular weight polymers. Some typical examples
involve cyclic ethers, cyclic anhydrides, lactones etc
The polymerization of these compounds can have
features of both addition and condensation reactions
in their kinetics and mechanism.
Polymerization mechanism
• FREE-RADICAL INITIATION
• Chain-growth polymerization reactions require the presence
of an initiator, a compound that reacts with the monomer to
form another reactive compound, which begins the linking
process. The most widely used initiators are compounds such
asperoxides that break down to an unstable species called a
radical (or free radical). A radical is a reactive compound that
contains an unpaired electron; in chemical formulas it is
commonly given the generic designation R · . As shown in the
reaction diagram below, the most commonly used peroxide
initiator, benzoyl peroxide, can produce benzoyloxy radicals by
cleaving at ... (100 of 4657 words
• Vinyl monomers may also be polymerized by ionic
initiators, although these are used less widely in the
polymer industry than their radical or organometallic
counterparts. Ionic initiators may be cationic (positively
charged) or anionic (negatively charged). Cationic
initiators are most commonly compounds or
combinations of compounds that can transfer a
hydrogen ion, H+, to the monomers, thereby converting
the monomer into a cation. Polymerization of styrene
(CH2=CHC6H5) with sulfuric acid (H2SO4) typifies this
process: