POLYMERS

An Introduction

POLYMER SCIENCE
POLYMER CHEMISTRY
3.1.1 Polymers & Macromolecules
3.1.2 Polymer Synthesis
3.1.3 Physical Polymer Chemistry

POLYMER PHYSICS

POLYMER SCIENCE
Most polymer research may be categorized as
polymer science, a sub-discipline of materials science

which includes researchers in chemistry (especially

organic chemistry), physics, and engineering. Polymer
science may be roughly divided into two
subdisciplines:

Polymer chemistry or macromolecular chemistry,

concerned with the chemical synthesis and chemical

properties of polymers.

Basic concepts in polymer chemistry

Polymers and macromolecules

In chemistry, the terms "polymer molecule" and
"macromolecule" are used interchangeably. [1]. A
polymer molecule has a high molecular mass and
is comprised of many smaller, repeating subunits
or monomers. Polymers may be found in nature,
such as the DNA and proteins found in living cells,
or created in laboratories or factories.
Polymer molecules come in many shapes and
sizes. A polymer molecule may be a long chain of
a single monomer repeated over and over again
or a complex network containing dozens of
different types of monomers. The identity, variety,
and arrangement of monomers in a polymer
molecule affect the chemical and physical
properties of the polymer molecule.

-Sample of polymers &

macromolecules

Polymer synthesis
An important area of research in polymer
chemistry is finding new or better ways to
prepare a polymer molecule from a stock of
smaller monomers.
In most cases, polymers are prepared using
principles of organic chemistry. Polymer chemists
are especially interested in techniques that allow
them to precisely control the size and structure of
the end product.
Polymer chemists are also investigating
polymerization methods outside the scope of
organic chemistry. One area of interest involves
preparing polymers by imitating the biological
processes used to create biopolymers such as
proteins or cellulose. Other areas of study involve
using plasma or electricity to initiate
polymerization reactions.

 Physical polymer chemistry is the study of how

a polymer molecule's structure relates to the
behavior of the bulk substance.
Physical polymer chemistry is closely related to
the field of polymer physics and also overlaps
with polymer research in materials science.
Physical polymer chemists use analytical
techniques such as light scattering and
spectroscopy to characterize the size and
structure of polymers.
Other areas of interest in physical polymer
chemistry include the study of polymers in
solution, the mechanical properties of polymers,
and understanding phase transitions in polymer
substances. There are also many researchers
using principles of theoretical chemistry to
better understand the structure and properties
of polymer molecules.
* spectroscopy-the science that deals with the use
of the spectroscope and with spectrum analysis.

Polymer physics
Concerned with the bulk properties of polymer
materials and engineering applications. The field of
polymer science is generally concerned with
synthetic polymers, such as plastics, or chemical
treatment and modification of natural polymers.

Polymer physics is the field of physics associated to

the study of polymers, their fluctuations,
mechanical properties, as well as the
kinetics of reactions involving degradation and
polymerisation of polymers and monomers respectively.
While it focuses on an aspect of the study of
condensed matter physics , the field of polymer physics
has developed as a branch of statistical physics.
Polymer physics and polymer chemistry are part of the
wider field of polymer science.

Disordered polymers are too complex to be

described using a deterministic method. However
statistical approaches can yield results and are
often pertinent since large polymers (that is to say,
polymers which contain a large number of
monomers) can be described efficiently as systems
at the thermodynamic limit.
Thermal fluctuations continuously affect the shape
of polymers in liquid solutions, and modelling their
effect requires a recourse to the principles of
statistical mechanics. As a corollary temperature
strongly affects the physical behavior of polymers
in solution.
The statistical approach to polymer physics is
based on an analogy between a polymer and either
a brownian motion, or some other type of
random walk. The simplest possible polymer model
is presented by the ideal chain, corresponds to
homogeneous random walk.

The study of biological polymers, their

structure, function, and method of synthesis is
generally the purview of biology, biochemistry,
and biophysics.
These disciplines share some of the
terminology familiar to polymer science,
especially when describing the synthesis of
biopolymers such as DNA or polysaccharides.
However, usage differences persist, such as
the practice of using the term macromolecule
to describe large non-polymer molecules and
complexes of multiple molecular components,
such as hemoglobin. Substances with distinct
biological function are rarely described in the
terminology of polymer science. For example,
a protein is rarely referred to as a copolymer.

Definition
Polymer literally means many parts.
A polymeric solid material may be
considered to be one that contains
many chemically bonded parts or units
which themselves are bonded together
to form a solid.
Polymers comprise a large class of
natural and synthetic materials with
variety of properties and purposes.

 Natural polymers are found in

many forms such as horns of
animals, tortoise shell, shellac (from
the lac beetle), rosin (from pine
trees), and tar from distillation of
organic material.

Types of Polymers

Two industrially important polymeric

materials are rubbers and plastics.
plastics
As engineering materials, it is
appropriate to divide them into the
following three categories:
1.
2.
3.

Elastomers
Thermoplastic Polymers
Thermosetting Polymers

Where (1) are rubbers and (2) and (3) are plastics

Elastomers

Elastomers or rubbers can be

elastically deformed a large amount
when force is applied to them and
can return to their original shape
when the force is released.

RUBBER, A Natural Polymer

One of the most useful natural polymers was
rubber, obtained from the sap of the hevea
tree.
It has only limited use as it became brittle in
the cold and melted when warmed.
The development of vulcanization later in
the nineteenth century improved the durability
of the natural polymer rubber, signifying the
first popularized semi-synthetic polymer. The
properties were changed making the rubber
more flexible and temperature stable.

 The first wholly synthetic polymer,

BAKELITE,
BAKELITE was introduced in 1909.
Its original use was to make billiard
balls.

Plastics
Plastics are a large and varied group
of synthetic materials which are
processed by forming or molding into
shape.
Plastics can be divided into two classes,
thermoplastics and thermosetting
plastics,
plastics depending on how they are
structurally and chemically bonded.

Thermoplastics vs.
Thermosets
Thermoplastics
-little cross linking
-ductile
-soften when heated
-polyethylene,
polypropylene,
polycarbonate,
polystyrene

Thermosets
-large cross linking
-hard and brittle
-do not soften with
heating
-vulcanized rubber,
epoxies, polyester
resin, phenolic resin

Reason Why Polymers are Important

Plastics can be formed by molding into
intricate part shapes, usually with no
further processing required
Cost competitive with metals
Generally require less energy to
produce than metal
Certain plastics are translucent/
transparent which makes them
competitive with glass in some
applications

Polymers as Engineering
Materials

Advantages
Low density relative to metals and ceramics
Good strength-to-weight ratios for certain polymers
High corrosion resistance
Low electrical and thermal conductivity
Limitations
Low strength relative to metal and ceramics
Low modulus of elasticity
Service temperatures are limited to only few
hundred degrees
Viscoelastic properties, which can be distinct
limitation in load bearing applications
Some polymers degrade when subjected to
sunlight and other forms of radiation

 The technology to mass produce polymers

was not developed until World War II, when
there was a need to develop synthetic rubber
for tires and other wartime applications and
nylon for parachutes.
Today, polymers are commonly used in
thousands of products as plastics, elastomers,
coatings, adhesives, as well as structural
components for products ranging from
childrens toys to aircraft.
They make up 80% of the organic chemical
industry, since most of them are based on
carbon, with products produced at
approximately 150 kg of polymers per person
annually in US.

Industry
Today there are primarily six commodity
polymers in use, namely polyethylene,
polypropylene, polyvinyl chloride,
polyethylene terephthalate, polystyrene
and polycarbonate. These make up
nearly 98% of all polymers and plastics
encountered in daily life.
Each of these polymers has its own
characteristic modes of degradation and
resistances to heat, light and chemicals.

Polyethylene
Polyethylene (IUPAC name
polyethene) is a thermoplastic
commodity heavily used in
consumer products.
Over 60 million tons of the material
are produced worldwide every year.

Polypropylene
Polypropylene or polypropene
(PP) is a thermoplastic polymer,
made by the chemical industry

applications
used in a wide variety of applications,
including food packaging, ropes, textiles,
plastic parts and reusable containers of
various types, laboratory equipment,
loudspeakers, automotive components,
and polymer banknotes. Additionally it is
used commonly in New Zealand and by
the US Military as Thermal Underwear.

Polyvinyl chloride
Polyvinyl chloride, (IUPAC
Polychloroethene) commonly
abbreviated PVC, is a widely used
thermoplastic polymer.

applications
There are many uses for PVC. As a hard
plastic, it is used as vinyl siding,
magnetic stripe cards, window profiles,
gramophone records (which is the source
of the name for vinyl records), pipe,
plumbing and conduit fixtures. The
material is often used in
Plastic Pressure Pipe Systems for pipelines
in the water and sewer industries because
of its inexpensive nature and flexibility

Polyethylene terephthalate

Polyethylene terephthalate (aka

PET, PETE or the obsolete PETP or
PET-P) is a thermoplastic polymer
resin of the polyester family

applications
used in synthetic fibers; beverage,
food and other liquid containers;
thermoforming applications; and
engineering resins often in
combination with glass fiber. It is one
of the most important raw materials
used in man-made fibers.

Polystyrene
Polystyrene is a polymer made from
the monomer styrene, a liquid
hydrocarbon that is commercially
manufactured from petroleum by the
chemical industry. At room
temperature, polystyrene is normally a
solid thermoplastic, but can be melted
at higher temperature for molding or
extrusion, then re-solidified.

Polycarbonate

Polycarbonates are a particular

group of thermoplastic polymers.
They are easily worked, molded, and
thermoformed;

applications
Plastics are very widely used in the
modern Chemical industry.
Their interesting features
(temperature resistance, impact
resistance and optical properties)
position them between
commodity plastics and engineering

Cracking of polymers
Cracking is the process by which a
polymer is divided into its
subcomponents or monomers. The
resulting subcomponents are more
viscous than the original polymer.

Polymer Degradation
Change in properties of a polymer
Polymer based product under the
influence of one or more environmental
factors
It is often due to the hydrolysis of the
bonds connecting the polymer chain,
which in turn leads to decrease in the
molecular mass of the polymer.
Changes may be undesirable or desirable

Cont

Degradation of polymers to form

smaller molecules may proceed:
- by random scission
- by specific scission
Degradation process can be useful
to prevent environmental pollution
- Polylactic acid and Polyglycolic,
acidused for biomedical application

The characterization of a polymer

requires several parameters which need to
be specified. This is because a polymer
actually consists of a statistical distribution
of chains of varying lengths, and each
chain consists of monometer residues
which affect its properties.

A variety of lab techniques are used to

determine the properties of polymers.
Techniques such as
wide angle X-ray scattering,
small angle X-ray scattering, and
small angle neutron scattering are used to
determine the crystalline structure of
polymers. Gel permeation chromatography
is used to determine the number average
molecular weight, weight average
molecular weight, and polydispersity.

FTIR, Raman and NMR can be used to

determine composition. Thermal properties
such as the glass transition temperature
and melting point can be determined by
differential scanning calorimetry and
dynamic mechanical analysis. Pyrolysis
followed by analysis of the fragments is one
more technique for determining the
possible structure of the polymer.

Morphological
Properties
Crystallinity
The state where in a periodic and
repeating atomic arrangement is
achieved by molecular chain
alignment or ordered atomic array.
It may exist in polymeric materials.
Its atomic arrangements will be more
complex for polymers.

 When applied to polymers, the term

crystalline has a somewhat
ambiguous/unclear usage.
Its crystals structure may be specified in
terms of unit cells which are quite
complex.
In addition to being entirely amorphous
polymers may also exhibit varying
degrees of crystallinity.

Amorphous having a non-crystal line

structure.

 Interdispersed / bury dissolved within

amorphous areas.
Polymers single crystals may be grown
from dilute solutions as thin platelets
and having chain-folded structures.
Many semi-crystalline polymers form
spherulites; each spherulites consists
of a collection of ribbon-like chainfolded (lamellar) crystallites that
radiate outward from its center.

Bulk Properties/Mechanical
Properties
The bulk properties of a polymer
are those most often of end-use
interest. These are the properties
that dictate how polymer
actually behaves on a
macroscopic scale.

Tensile Strength (Ultimate

Strength)

The Tensile Strength of a material

quantifies how much stress the
material will endure before failing.
EXAMPLE:
a rubber band with higher tensile
strength will hold a greater weigh
before snapping.

In general, tensile strength increases

with polymer chain length.

Mechanical Characteristics of
Polymers
Highly sensitive:
1. to the rate of deformation (strain
rate)
2. Temperature
3. Chemical Nature of the
environment (presence of water,
oxygen, organic solvent etc.)

Young Modulus of Elasticity

The parameter quantifies the elasticity
of the polymers.
The ratio of stress (stress it is
instantaneous load applied to a
specimen divided by cross sectional
area before any deformation) to strain
when a deformation is totally elastic. It
is also a measure of the stiffness of a
material.

Transport Properties
Diffusivity relate to how rapidly molecules
move through the polymer matrix.

Pure Component Phase Behavior

Diffusivity relate to how rapidly molecules
move through the polymer matrix.

Melting point
The term melting point when applied
to polymers suggests not a solid
liquid phase transition but a
transition from a CRYSTALLINE OR
SEMI-CRYSTALLINE PHASE to a SOLID
AMORPHOUS PHASE. It is also known
as crystalline melting temperature.

ex. Among synthetic polymers, crystalline

melting is only discussed with regards to
thermoplastics, as thermosetting
polymers will decompose at high
temperature rather than melt.

Boiling Point
The boiling point of a polymer
substance is never defined due to
the fact that polymers will
decompose before reaching
theoretical boiling temperatures.

Glass Transition Temperature

The temperature at which, upon
cooling, a non-crystalline ceramics or
polymer transforms from a super
cooled liquid to a rigid/inflexible glass.

POLYMER SOLUTION BEHAVIOR

In general, polymeric mixtures are far less
miscible than mixtures of small molecule
materials. This effect is a result of the fact
that the driving force for mixing is usually
entropic, not energetic.
In other words, MISCIBLE MATERIALS
usually form a solution not because their
interaction but because of an increase in
entropy and hence free energy associated
with increasing the amount of volume
available to each component. This
increase in entropy scales with the number
of particles (or moles) being mixed.

CHEMICAL PROPERTIES OF
POLYMERS
The attractive forces between chains play a
large part in determining a polymers properties.
Because polymer chains are so long, these
interchain forces are amplified far beyond the
attractions between conventional molecules.
Different side groups o the polymer can lend the
polymer to ionic bonding or hydrogen bonding
between its own chains. These stronger forces
typically result in higher tensile strength and
melting point.

The intermolecular forces in polymers

can be affected by dipoles in the monomer
units. Polymers containing amide or
carbonyl groups can form hydrogen bonds
between adjacent chains; the partially
positively charged hydrogen atoms in N-H
groups of one chain are strongly attracted
to the partially negatively charged oxygen
atoms in C=O groups on another. The
strong hydrogen bonds, for example, result
in the high tensile strength and melting
point of polymers containing urethane or
urea linkages. Polyester have dipole-dipole
bonding between the oxygen atoms in C=O
groups and the hydrogen bonding, so a
polyesters melting point and strength are

Ethene, however, has no permanent dipole.

The attractive forces between polyethylene chains arise
from weak Van der Waals forces.
Molecules can be thought of as being surrounded by a
cloud of negative electrons.
As two polymer chains approach, their electron clouds
repel one another. This has the effect of lowering the
electron density on one side of a polymer chain, creating
a slight positive dipole on this side. This charge is
enough to actually attract the second polymer chain.
Van der Waals forces are quite weak, however, so
polyethene can have a lower melting temperature
compared to other polymers.

The Three Primary Methods

of Polymer Synthesis

 Polymers are synthesized by three

primary methods: organic synthesis
in a laboratory or factory, biological
synthesis in living cells and
organisms, or by chemical
modification of naturally occurring
polymers.

Organic synthesis
In 1907, Leo Baekeland created the first
completely synthetic polymer, called Bakelite,
by reacting phenol and formaldehyde at
precisely controlled temperature and pressure.
Subsequent work by Wallace Carothers in the
1920s demonstrated that polymers could be
synthesized rationally from their constituent
monomers.
Most commercially important polymers today
are entirely synthetic and produced in high
volume, on appropriately scaled organic
synthetic techniques.

 Laboratory synthetic methods are

generally divided into two categories,
condensation polymerization and
addition polymerization. However,
some newer methods such as plasma
polymerization do not fit neatly into
either category.
Synthetic polymerization reactions
may be carried out with or without a
catalyst.

Biological synthesis
Natural polymers and biopolymers formed in living
cells may be synthesized by enzyme-mediated
processes, such as the formation of DNA catalyzed
by DNA polymerase. The synthesis of proteins
involves multiple enzyme-mediated processes to
transcribe genetic information from the DNA and
subsequently translate that information to
synthesize the specified protein. The protein may
be modified further following translation in order
to provide appropriate structure and function.

Modification of natural
polymers/ Chemical
Modification
Many commercially important polymers
are synthesized by chemical
modification of naturally occurring
polymers. Prominent examples include
the reaction of nitric acid and cellulose
to form nitrocellulose and the formation
of vulcanized rubber by heating natural
rubber in the presence of sulfur.

Polymer Structure and

Properties
Types of polymer 'properties' can be
broadly divided into several categories
based upon scale. At the nano-micro scale
are properties that directly describe the
chain itself. These can be thought of as
polymer structure. At an intermediate
mesoscopic level are properties that
describe the morphology of the polymer
matrix in space. At the macroscopic level

Structure
The structural properties of a polymer relate
to the physical arrangement of monomers
along the backbone of the chain. Structure
has a strong influence on the other
properties of a polymer. For example, a linear
chain polymer may be soluble or insoluble in
water depending on whether it is composed
of polar monomers (such as ethylene oxide)
or nonpolar monomers (such as styrene). On
the other hand, two samples of natural
rubber may exhibit different durability even
though their molecules comprise the same
monomers. Polymer scientists have
developed terminology to precisely describe
both the nature of the monomers as well as

Monomer identity
The identity of the monomers comprising the
polymer is generally the first and most
important attribute of a polymer. Polymer
nomenclature is generally based upon the
type of monomers comprising the polymer.
Polymers that contain only a single type of
monomer are known as homopolymers, while
polymers containing a mixture of monomers
are known as copolymers. Poly(styrene), for
example, is composed only of styrene

Tacticity in polymers with chiral

centers
This property describes the relative
stereochemistry of chiral centers in
neighboring structural units within a

Chain size
Polymer bulk properties may be strongly dependent on
the size of the polymer chain. Like any molecule, a
polymer molecule's size may be described in terms of
molecular weight or mass. In polymers, however, the
molecular mass may be expressed in terms of degree of
polymerization, essentially the number of monomer
units which comprise the polymer. For synthetic
polymers, the molecular weight is expressed statistically
to describe the distribution of molecular weights in the
sample. This is because of the fact that almost all
industrial processes produce a distribution of polymer
chain sizes. Examples of such statistics include the
number average molecular weight and weight average
molecular weight. The ratio of these two values is the
polydispersity index, commonly used to express the
"width" of the molecular weight.
The space occupied by a polymer molecule is generally
expressed in terms of radius of gyration or excluded
volume.

Monomer arrangement in
copolymers
Monomers within a copolymer may be organized
along the backbone in a variety of ways.
Alternating copolymers possess regularly
alternating monomer residues
Periodic copolymers have monomer residue
types arranged in a repeating sequence
Random copolymers have a random sequence of
monomer residue types
Statistical copolymers have monomer residues
arranged according to a known statistical rule
Block copolymers have two or more homopolymer
subunits linked by covalent bonds. Block
copolymers with two or three distinct blocks are
called diblock copolymers and triblock copolymers,

Tacticity in polymers

This property describes the relative

stereochemistry in neighboring
structural units within a
macromolecule.