Polymer

Appearance of real linear polymer chains a s recorded using an

atomic force microscope on surface under liquid medium. Chain
contour length for this polymer is ~ 2 0 4 nm; thickness is ~ 0 . 4 nm.

A p o lym er is a large molecule (macromolecule) composed of

repeating structural units. These subunits are typically connected by
covalent chemical bonds. Although the term polymer is sometimes
taken to refer to plastics, it actually encompasses a large class of
natural and synthetic materials with a wide variety of properties.

Because of the extraordinary range of properties of polymeric

materials, they play an essential and ubiquitous role in everyday
life. This role ranges from familiar synthetic plastics and elastomers
to natural biopolymers such as nucleic acids and proteins that are
essential for life.

Natural polymeric materials such as shellac, amber, and natural

rubber have been used for centuries. A variety of other natural
polymers exist, such as cellulose, which is the main constituent of
wood and paper. The list of synthetic polymers includes synthetic
rubber, Bakelite, neoprene, nylon, PVC, polystyrene, polyethylene,
polypropylene, polyacrylonitrile, PVB, silicone, and m an y more.

Most commonly, the continuously linked backbone of a polymer

used for the preparation of plastics consists mainly of carbon atoms.
A simple example is polyethylene, whose repeating unit is based on
ethylene monomer. However, other structures do exist; for example,
elements such as silicon form familiar materials such as silicones,
examples being silly putty and waterproof plumbing sealant.
Oxygen is also commonly present in polymer backbones, such as
those of polyethylene glycol, polysaccharides (in glycosidic bonds),
and D N A (in phosphodiester bonds).

Polymers are studied in the fields of polymer chemistry, polymer

physics, and polymer science.

Overvi ew
While the term polymer in popular usage suggests "plastic",
polymers comprise a large class of natural and synthetic materials
with a variety of properties and purposes. Natural polymer materials
such as shellac and amber have been in use for centuries. Paper is
manufactured from cellulose, a naturally occurring polysaccharide
found in plants. Biopolymers such as proteins and nucleic acids play
important roles in biological processes.
Henri Braconnot's pioneering work in derivative cellulose
compounds is perhaps the earliest important work in modern
polymer science. 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
first wholly synthetic polymer, Bakelite, was discovered in 1907.

Until the 1920s, most scientists believed that polymers were

clusters of small molecules (called colloids), without definite
molecular weights, held together by an unknown force, a concept
known a s association theory. In 1922, German chemist Hermann
Staudinger proposed that polymers were comprised of
"macromolecules" consisted of long chains of atoms held together
by covalent bonds. Though poorly received at first, experimental
work by Wallace Carothers, Herman Mark, and others provided
further evidence for Staudinger's theory. B y the mid-1930s, the
macromolecular theory of polymer structure was widely accepted.
For this and other work in the field, Staudinger was ultimately
awarded the Nobel Prize. In the intervening century, synthetic
polymer materials such as Nylon, polyethylene, Teflon, and silicone
have formed the basis for a burgeoning polymer industry.

Synthetic polymers today find application in nearly every industry

and area of life. Polymers are used in the fabrication of
microprocessors, the development of new pharmaceuticals, and
improving yield in petroleum extraction. Polymers are used as
adhesives and lubricants, as well as structural components for
products ranging from childrens' toys to aircraft. Future applications
include polymeric transistors and substrates for flexible components
and displays, enhanced drug delivery methods, and the
development of smart materials.

P o l y m e r science
Most polymer research m a y be categorized as polymer science, a
sub-discipline of materials science which includes researchers in
chemistry (especially organic chemistry), physics, and engineering.
The field of polymer science includes both experimental and
theoretical research. The IUPAC recommends that polymer science
be roughly divided into two subdisciplines: polymer chemistry (or
macromolecular chemistry) and polymer physics. In practice the
distinction between the two is rarely clearcut.

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 D N A or polysaccharides.
However, usage differences persist, such a s 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 a s a copolymer.

Etymology
The word polymer is derived from the Greek words πολύ- - poly-
meaning "many"; and μέρος - meros meaning "part". The term was
coined in 1833 by Jöns Jacob Berzelius, although his definition of a
polymer was quite different from the modern definition. (see New
chemical terms)

Historical d ev el o p m e n t
Starting in 1811, Henri Braconnot did pioneering work in derivative
cellulose compounds, perhaps the earliest important work in
polymer science. The development of vulcanization later in the
nineteenth century improved the durability of the natural polymer
rubber, signifying the first popularized semi-synthetic polymer. In
1907, Leo Baekeland created the first completely synthetic polymer,
Bakelite, by reacting phenol and formaldehyde at precisely
controlled temperature and pressure. Bakelite was then publicly
introduced in 1909.

Despite significant advances in synthesis and characterization of

polymers, a correct understanding of polymer molecular structure
did not emerge until the 1920s. Before then, scientists believed that
polymers were clusters of small molecules (called colloids), without
definite molecular weights, held together by an unknown force, a
concept known a s association theory. In 1922, Hermann Staudinger
proposed that polymers consisted of long chains of atoms held
together by covalent bonds, an idea which did not gain wide
acceptance for over a decade and for which Staudinger was
ultimately awarded the Nobel Prize. Work by Wallace Carothers in the
1 9 20 s also demonstrated that polymers could be synthesized
rationally from their constituent monomers. An important
contribution to synthetic polymer science was made by the Italian
chemist Giulio Natta and the German chemist Karl Ziegler, who won
the Nobel Prize in Chemistry in 1963 for the development of the
Ziegler-Natta catalyst. Further recognition of the importance of
polymers came with the award of the Nobel Prize in Chemistry in
1 9 74 to Paul Flory, whose extensive work on polymers included the
kinetics of step-growthpolymerization and of addition
polymerization, chain transfer, excluded volume, the Flory-
Huggins solution theory, and the Flory convention.
Synthetic polymer materials such as nylon, polyethylene, Teflon,
and silicone have formed the basis for a burgeoning polymer
industry. These years have also shown significant developments in
rational polymer synthesis. Most commercially important polymers
today are entirely synthetic and produced in high volume on
appropriately scaled organic synthetic techniques. Synthetic
polymers today find application in nearly every industry and area of
life. Polymers are widely used as adhesives and lubricants, as well
as structural components for products ranging from children's toys
to aircraft. They have been employed in a variety of biomedical
applications ranging from implantable devices to controlled drug
delivery. Polymers such as poly(methyl methacrylate) find
application as photoresist materials used in semiconductor
manufacturing and low-k dielectrics for use in high-
performance microprocessors. Recently, polymers have also been
employed as flexible substrates in the development of organic
light-emitting diodes for electronic display.

D e s c r i b i n g p o ly m e r s
Mo lecul ar description

In m an y instances a polymer molecule m a y be described using the

same terminology used to describe any molecule. Molecular
structure m a y be described in terms of bond lengths and angles;
m a s s m a y be described in terms of molecular weight. However, the
size and complexitiy of polymer molecules often require the use of
specialized terminology to precisely describe the nature of the
monomer(s) and how those monomers are connected or arranged.

The m a s s of a polymer molecule m a y be described using standard

conventional for molecular or molar mass. This molecular weight,
expressed in Daltons, is used frequently to describe complex
biopolymers, such as proteins. An altnerate expression for molecular
m a s s is the degree of polymerization (DP), essentially the number of
monomer units which comprise the polymer or block. DP is
especially convenient for homopolymers or block copolymers, and is
used frequency when describing the extent of a polymerization
reaction.

Laboratory syntheses tend to produce polymer samples comprised

of molecules with a variety of different molecular weights. Thus, the
molecular weight of a synthetic polymer is generally expressed in
terms of a summary statistic, such as the number-averaged
molecular weight (M n ) or weight-averaged molecular weight(M w ).
The ratio of these two values is known as the polydispersity index,
which is an indicator of the distribution of molecular weights within
a polymer sample. For commercial polymer samples it is common to
see all three values reported.
The size and complexity of polymer molecules also requires
specialized descriptions of molecular dimensions and ordering.
Globular macromolecules, such a s proteins, m a y have a well-defined
semi-rigid structure where conventional descriptions of atomic
positions, bond lengths, and angles are adequate and appropriate.
On the other hand, structurally simple polymers, such as linear
polymers, possess hundreds or thousands of degrees of rotational
freedom, allowing the polymer chain to adopt multiple
conformations. The size and positions of such molecules are
described statistically, with molecular volume expressed as a
function of the radius of gyration or mean end-to-end distance.
Molecular simulations or light scattering ma y also be used to
determine an energetically favorable "average conformation" for a
collection of polymer molecules.

Describing the crystallinity of a polymer presents some degree of

ambiguity. In some cases, the term crystalline finds identical usage
to that used in conventional crystallography. For example, the
structure of a crystalline protein or polynucleotide, such as a sample
prepared for x-ray crystallography, m a y be defined in terms of a
conventional unit cell comprised of one or more polymer molecules
with cell dimensions of hundreds of angstroms or more.

When applied to a synthetic polymer, however, the term crystalline

implies regions of three-dimensional ordering on atomic (rather than
macromolecular) length scales, usually arising from intramolecular
folding and/or stacking of adjacent chains. Synthetic polymers may
consist of both crystalline and amorphous regions; the d e g r e e of
crystallinity m a y be expressed in terms of a weight fraction or
volume fraction of crystalline material. Few synthetic polymers are
entirely crystalline.

A stereochemical description of a polymer molecule also requires

specialized terminology. There are so me polymers in which chirality
in the monomer is retained following polymerization. In other
polymers a chiral center m a y be created by the polymerization
process.

There is also a large vocabulary used to describe the nature of the

monomers and the precise arrangement of these monomers relative
to one another. A polymer consisting of exactly one type of
monomer, such as poly(styrene), is classifed as a homopolymer .
Polymers with more than one variety of monomer are called
copolymers, such a s ethylene-vinyl acetate. S o me biological
polymers are composed of a variety of different but structurally
related monomers, such as polynucleotides composed of nucleotide
subunits.
A polyelectrolyte molecule is a polymer molecule comprised of
primarily ionizable repeating subunits. An i o n o mer molecule is also
ionizable, but to a lesser degree.

The simplest form of polymer molecule is a straight chain or linear

polymer, composed of a single main chain. A b r a n c he d polymer
molecule is composed of a main chain with one or more substituent
side chains or branches. Special types of branched polymers include
star polymers, comb polymers, and brush polymers. If the polymer
contains a side chain that has a different composition or
configuration than the main chain the polymer is called a graft or
grafted polymer. A cr o s s- link suggests a branch point from which
four or more distinct chains emanate. A polymer molecule with a
high degree of crosslinking is referred to as a po lym er network.

Ma c r o s c o p i c description

The macroscopic physical properties of polymers in m an y cases

reflect that of any other molecular substance. Polymer materials
m a y be transparent, translucent, or opaque, and m a y be insulators,
conductors, or semiconductors. Other properties, however,
especially those governing phase transitions, m a y have distinct
meanings (or no meaning at all) when applied to polymers.

The "melting point" of a polymer, for example, refers not a solid-

liquid phase transition but a transition from a crystalline or semi-
crystalline phase to a solid amorphous phase. Though abbreviated
as simply "T m ", the property in question is more properly called the
"crystalline melting temperature". A mo n g synthetic polymers,
crystalline melting is only discussed with regards to thermoplastics,
as thermosetting polymers will decompose at high temperatures
rather than melt.

The boiling point of a polymer substance is never defined, in that

polymers will decompose before reaching assu med boiling
temperatures.

A parameter of particular interest in synthetic polymer

manufacturing is the glass transition temperature (Tg), which
describes the temperature at which amorphous polymers undergo a
second order phase transition from a rubbery, viscous amorphous
solid to a brittle, glassy amorphous solid. The glass transition
temperature m a y be engineered by altering the degree of branching
or cross-linking in the polymer or by the addition of plasticizer.

Polymer synthesis
The repeating unit of the polymer polypropylene

Polymerization is the process of combining many small molecules

known as monomers into a covalently bonded chain. During the
polymerization process, some chemical groups m a y be lost from
each monomer. This is the case, for example, in the polymerization
of PET polyester. The monomers are terephthalic acid (HOOC-C 6 H 4 -
COOH) and ethylene glycol (HO-CH 2 -CH 2 -OH) but the repeating unit
is -OC-C 6 H 4 -COO-CH 2 -CH 2 -O-, which corresponds to the combination
of the two monomers with the loss of two water molecules. The
distinct piece of each monomer that is incorporated into the
polymer is known as a repeat unit or monomer residue.

La bor a tory s y nt hes i s

Laboratory synthetic methods are generally divided into two

categories, step-growth polymerization and chain-growth
polymerization. The essential difference between the
two is that in chain growth polymerization, monomers are added to
the chain one
at a time only, whereas in step-growth polymerization chains of
monomers m a y combine with one another directly. However, some
newer methods such as plasma polymerization do not fit neatly into
either category. Synthetic polymerization reactions m a y be carried
out with or without a catalyst. Laboratory synthesis of biopolymers,
especially of proteins, is an area of intensive research.

Biological s y n th es i s
Microstructure of part of a D N A double helix biopolymer
Main article: Biopolymer

There are three main classes of biopolymers: polysaccharides,

polypeptides, and polynucleotides. In living cells, they m a y be
synthesized by enzyme-mediated processes, such as the formation
of D N A catalyzed by D N A polymerase. The synthesis of proteins
involves multiple enzyme-mediated processes to transcribe genetic
information from the D N A to RN A and subsequently translate that
information to synthesize the specified protein from amino acids.
The protein m a y be modified further following translation in order to
provide appropriate structure and functioning.

Modifica tion of natural pol y mers

Man y 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.

P o l y m e r properties
Polymer properties are broadly divided into several classes based on
the scale at which the property is defined as well as upon its
physical basis. The most basic property of a polymer is the identity
of its constituent monomers. A second set of properties, known as
microstructure, essentially describe the arrangement of these
monomers within the polymer at the scale of a single chain. These
basic structural properties play a major role in determining bulk
physical properties of the polymer, which describe how the polymer
behaves as a continuous macroscopic material. Chemical properties,
at the nano-scale, describe how the chains interact through various
physical forces. At the macro-scale, they describe how the bulk
polymer interacts with other chemicals and solvents.

M o n o m e r s a n d repeat units

The identity of the monomer residues (repeat units) comprising a

polymer is its first and most important attribute. Polymer
nomenclature is generally based upon the type of monomer
residues comprising the polymer. Polymers that contain only a
single type of repeat unit are known as homopolymers, while
polymers containing a mixture of repeat units are known as
copolymers. Poly(styrene), for example, is composed only of styrene
monomer residues, and is therefore classified a s a homopolymer.
Ethylene-vinyl acetate, on the other hand, contains more than one
variety of repeat unit and is thus a copolymer. S o m e biological
polymers are composed of a variety of different but structurally
related monomer residues; for example, polynucleotides such as
D N A are composed of a variety of nucleotide subunits.

A polymer molecule containing ionizable subunits is known as a

polyelectrolyte or ionomer.

Microstructure

The microstructure of a polymer (sometimes called configuration)

relates to the physical arrangement of monomer residues along the
backbone of the chain. These are the elements of polymer structure
that require the breaking of a covalent bond in order to change.
Structure has a strong influence on the other properties of a
polymer. For example, two samples of natural rubber m a y exhibit
different durability, even though their molecules comprise the same
monomers.

P o lym er architecture

B r a n c h point in a polymer

An important microstructural feature determining polymer

properties is the polymer architecture. The simplest polymer
architecture is a linear chain: a single backbone with no branches. A
related unbranching architecture is a ring polymer. A branched
polymer molecule is composed of a main chain with one or more
substituent side chains or branches. Special types of branched
polymers include star polymers, comb polymers, brush polymers,
dendronized polymers, ladders, and dendrimers.

Branching of polymer chains affects the ability of chains to slide

past one another by altering intermolecular forces, in turn affecting
bulk physical polymer properties. Long chain branches m a y increase
polymer strength, toughness, and the glass transition temperature
(Tg) due to an increase in the number of entanglements per chain.
The effect of such long-chain branches on the size of the polymer in
solution is characterized by the branching index. Random length
and atactic short chains, on the other hand, m a y reduce polymer
strength due to disruption of organization and m a y likewise reduce
the crystallinity of the polymer.

A good example of this effect is related to the range of physical

attributes of polyethylene. High-density polyethylene (HDPE) has a
very low degree of branching, is quite stiff, and is used in
applications such as milk jugs. Low-density polyethylene (LDPE), on
the other hand, has significant numbers of both long and short
branches, is quite flexible, and is used in applications such as plastic
films.

Dendrimer and dendron

Dendrimers are a special case of polymer where every monomer

unit is branched. This tends to reduce intermolecular chain
entanglement and crystallization. Alternatively, dendritic polymers
are not perfectly branched but share similar properties to
dendrimers due to their high degree of branching.

The architecture of the polymer is often physically determined by

the functionality of the monomers from which it is formed. This
property of a monomer is defined a s the number of reaction sites at
which m a y form chemical covalent bonds. The basic functionality
required for forming even a linear chain is two bonding sites. Higher
functionality yields branched or even crosslinked or networked
polymer chains.

An effect related to branching is chemical crosslinking - the

formation of covalent bonds between chains. Crosslinking tends to
increase T g and increase strength and toughness. A m on g other
applications, this process is used to strengthen rubbers in a process
known a s vulcanization, which is based on crosslinking by sulfur. Car
tires, for example, are highly crosslinked in order to reduce the
leaking of air out of the tire and to toughen their durability. Eraser
rubber, on the other hand, is not crosslinked to allow flaking of the
rubber and prevent damage to the paper.

A cross-link suggests a branch point from which four or more

distinct chains emanate. A polymer molecule with a high degree of
crosslinking is referred to as a polymer network. Sufficiently high
crosslink concentrations m a y lead to the formation of an infinite
network, also known a s a gel, in which networks of chains are of
unlimited extent—essentially all chains have linked into one
molecule.

C ha i n len gt h

The physical properties of a polymer are strongly dependent on the

size or length of the polymer chain. For example, as chain length is
increased, melting and boiling temperatures increase quickly.
Impact resistance also tends to increase with chain length, a s does
the viscosity, or resistance to flow, of the polymer in its melt state.
Chain length is related to melt viscosity roughly a s 1:10 3 . 2 , so that a
tenfold increase in polymer chain length results in a viscosity
increase of over 1000 times. Increasing chain length furthermore
tends to decrease chain mobility, increase strength and toughness,
and increase the glass transition temperature (Tg). This is a result of
the increase in chain interactions such as Van der Waals attractions
and entanglements that come with increased chain length. These
interactions tend to fix the individual chains more strongly in
position and resist deformations and matrix breakup, both at higher
stresses and higher temperatures.

A common means of expressing the length of a chain is the degree

of polymerization, which quantifies the number of monomers
incorporated into the chain. As with other molecules, a polymer's
size m a y also be expressed in terms of molecular weight. Since
synthetic polymerization techniques typically yield a polymer
product including a range of molecular weights, the weight is often
expressed statistically to describe the distribution of chain lengths
present in the same. C o mm o n examples are 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 distribution. A final
measurement is contour length, which can be understood as the
length of the chain backbone in its fully extended state.
The flexibility of an unbranched chain polymer is characterized by
its persistence length.

M o n o m e r a r r a n g e m e n t in c o po lymer s

Monomers within a copolymer may be organized along the

backbone in a variety of ways.

 Alt ern at i ng c o p o l y m e r s possess regularly alternating

monomer residues: [AB...]n (2).
 Periodic c o po l ym e r s have monomer residue types arranged
in a repeating sequence: [AnBm...] m being different from n .
 Stat isti cal c o p o l y m e r s have monomer residues arranged
according to a known statistical rule. A statistical copolymer in
which the probability of finding a particular type of monomer
residue at an particular point in the chain is independent of
the types of surrounding monomer residue m a y be referred to
as a truly r a n d o m co po lymer (3).
 Blo c k c o p o l ym er s have two or more homopolymer subunits
linked by covalent bonds (4). Polymers with two or three
blocks of two distinct chemical species (e.g., A and B) are
called diblock copolymers and triblock copolymers,
respectively. Polymers with three blocks, each of a different
chemical species (e.g., A, B, and C) are termed triblock
terpolymers.
 Graft or g r a f t ed c o p o l ym er s contain side chains that have a
different composition or configuration than the main chain.
(5)

Tacticity

Tacticity describes the relative stereochemistry of chiral centers in

neighboring structural units within a macromolecule. There are
three types: isotactic (all substituents on the sa me side), atactic
(random placement of substituents), and syndiotactic (alternating
placement of substituents).
P o l y m er m o r p h o l o g y

Polymer morphology generally describes the arrangement and

microscale ordering of polymer chains in space.

Crystallinity

When applied to polymers, the term crystalline has a somewhat

ambiguous usage. In so me cases, the term crystalline finds identical
usage to that used in conventional crystallography. For example,
the structure of a crystalline protein or polynucleotide, such as a
sample prepared for x-ray crystallography, m a y be defined in terms
of a conventional unit cell composed of one or more polymer
molecules with cell dimensions of hundreds of angstroms or more.

A synthetic polymer m a y be lightly described as crystalline if it

contains regions of three-dimensional ordering on atomic (rather
than macromolecular) length scales, usually arising from
intramolecular folding and/or stacking of adjacent chains. Synthetic
polymers m a y consist of both crystalline and amorphous regions;
the degree of crystallinity m a y be expressed in terms of a weight
fraction or volume fraction of crystalline material. Few synthetic
polymers are entirely crystalline.

The crystallinity of polymers is characterized by their degree of

crystallinity, ranging from zero for a completely non-crystalline
polymer to one for a theoretical completely crystalline polymer.
Polymers with microcrystalline regions are generally tougher (can
be bent more without breaking) and more impact-resistant than
totally amorphous polymers.

Polymers with a degree of crystallinity approaching zero or one will

tend to be transparent, while polymers with intermediate degrees of
crystallinity will tend to be opaque due to light scattering by
crystalline or glassy regions. Thus for ma n y polymers, reduced
crystallinity m a y also be associated with increased transparency.

Ch a i n co nfo rmatio n

The space occupied by a polymer molecule is generally expressed in

terms of radius of gyration, which is an average distance from the
center of m a s s of the chain to the chain itself. Alternatively, it may
be expressed in terms of pervaded volume, which is the volume of
solution spanned by the polymer chain and scales with the cube of
the radius of gyration.

Mec h a n i c a l properties
A polyethylene sample necking under tension.

The bulk properties of a polymer are those most often of end-use

interest. These are the properties that dictate how the polymer
actually behaves on a macroscopic scale.

Tensile s t r en gt h

The tensile strength of a material quantifies how much stress the

material will endure before suffering permanent deformation. This is
very important in applications that rely upon a polymer's physical
strength or durability. For example, a rubber band with a higher
tensile strength will hold a greater weight before snapping. In
general, tensile strength increases with polymer chain length and
crosslinking of polymer chains.

Y o u n g ' s m o d u l u s of elasticity

Young's Modulus quantifies the elasticity of the polymer. It is

defined, for small strains, as the ratio of rate of change of stress to
strain. Like tensile strength, this is highly relevant in polymer
applications involving the physical properties of polymers, such as
rubber bands. The modulus is strongly dependent on temperature.

Tra nsport properties

Transport properties such as diffusivity relate to how rapidly

molecules move through the polymer matrix. These are very
important in many applications of polymers for films and
membranes.

P h a s e behavior

M e l t i n g 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. Though
abbreviated as simply Tm, the property in question is more properly
called the crystalline melting temperature. A mo n g synthetic
polymers, crystalline melting is only discussed with regards to
thermoplastics, as thermosetting polymers will decompose at high
temperatures rather than melt.

G l a s s transition temperature

A parameter of particular interest in synthetic polymer

manufacturing is the glass transition temperature (Tg), which
describes the temperature at which amorphous polymers undergo a
transition from a rubbery, viscous amorphous solid, to a brittle,
glassy amorphous solid. The glass transition temperature m a y be
engineered by altering the degree of branching or crosslinking in
the polymer or by the addition of plasticizer.

M i x i n g behavior

Phase diagram of the typical mixing behavior of weakly interacting

polymer solutions.

In general, polymeric mixtures are far less miscible than mixtures of

small molecule materials. This effect results from the fact that the
driving force for mixing is usually entropy, not interaction energy. In
other words, miscible materials usually form a solution not because
their interaction with each other is more favorable than their self-
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. Since polymeric molecules are
much larger and hence generally have much higher specific
volumes than small molecules, the number of molecules involved in
a polymeric mixture is far smaller than the number in a small
molecule mixture of equal volume. The energetics of mixing, on the
other hand, is comparable on a per volume basis for polymeric and
small molecule mixtures. This tends to increase the free energy of
mixing for polymer solutions and thus make solvation less favorable.
Thus, concentrated solutions of polymers are far rarer than those of
small molecules.

Furthermore, the phase behavior of polymer solutions and mixtures

is more complex than that of small molecule mixtures. Whereas
most small molecule solutions exhibit only an upper critical solution
temperature phase transition, at which phase separation occurs
with cooling, polymer mixtures commonly exhibit a lower critical
solution temperature phase transition, at which phase separation
occurs with heating.

In dilute solution, the properties of the polymer are characterized by

the interaction between the solvent and the polymer. In a good
solvent, the polymer appears swollen and occupies a large volume.
In this scenario, intermolecular forces between the solvent and
monomer subunits dominate over intramolecular interactions. In a
bad solvent or poor solvent, intramolecular forces dominate and the
chain contracts. In the theta solvent, or the state of the polymer
solution where the value of the second virial coefficient becomes 0,
the intermolecular polymer-solvent repulsion balances exactly the
intramolecular monomer-monomer attraction. Under the theta
condition (also called the Flory condition), the polymer behaves like
an ideal random coil. The transition between the states is known as
a coil-globule transition.

Inclu si on of plasticizers

Inclusion of plasticizers tends to lower T g and increase polymer

flexibility. Plasticizers are generally small molecules that are
chemically similar to the polymer and create gaps between polymer
chains for greater mobility and reduced interchain interactions. A
good example of the action of plasticizers is
related to polyvinylchlorides or PVCs. A uPVC, or
polyvinylchloride,
unplasticized
is used for things such as pipes. A pipe has no
plasticizers in it, because it needs to remain strong and heat-
resistant. Plasticized PVC is used for clothing for a flexible quality.
Plasticizers are also put in some types of cling film to make the
polymer more flexible.

Chemi cal properties

The attractive forces between polymer chains play a large part in
determining a polymer's properties. Because polymer chains are so
long, these interchain forces are amplified far beyond the
attractions between conventional molecules. Different side groups
on 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 higher crystalline melting
points.

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. These strong hydrogen bonds, for
example, result in the high tensile strength and melting point of
polymers containing urethane or urea linkages. Polyesters have
dipole-dipole bonding between the oxygen atoms in C = O groups
and the hydrogen atoms in H-C groups. Dipole bonding is not as
strong a s hydrogen bonding, so a polyester's melting point and
strength are lower than Kevlar's (Twaron), but polyesters have
greater flexibility.

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 attract the
second polymer chain. Van der Waals forces are quite weak,
however, so polyethylene can have a lower melting temperature
compared to other polymers.

S t a n d a r d i z e d p o l y m e r no menclature
There are multiple conventions for naming polymer substances.
Man y commonly used polymers, such as those found in consumer
products, are referred to by a common or trivial name. The trivial
name is assigned based on historical precedent or popular usage
rather than a standardized naming convention. Both the American
Chemical Society (ACS) [ 3 2 ] and IUPAC[ 3 3 ] have proposed standardized
naming conventions; the A C S and IUPAC conventions are similar but
not identical.[34] Examples of the differences between the various
naming conventions are given in the table below:

Common
ACS name IUPAC name
name
Poly(ethylene Poly(oxyethylene) Poly(oxyethene)
oxide) or PEO
Poly(oxy-1,2-
Poly(ethylene
terephthalate)
ethanediyloxycarbony Poly(oxyetheneoxyterephthalo
l-1,4- yl)
or PET
phenylenecarbonyl)
Poly[amino(1-oxo-1,6- Poly[amino(1-oxohexan-1,6-
Nylon 6
hexanediyl)] diyl)]

In both standardized conventions, the polymers' names are

intended to reflect the monomer(s) from which they are synthesized
rather than the precise nature of the repeating subunit. For
example, the polymer synthesized from the simple alkene ethene is
called polyethylene, retaining the -ene suffix even though the
double bond is removed during the polymerization process:

P o l y m e r characterization
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 monomer 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, Ra ma n and N M R 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.
Thermogravimetry is a useful technique to evaluate the thermal
stability of the polymer. Detailed analyses of TG curves also allow us
to know a bit of the phase segregation in polymers. Rheological
properties are also commonly used to help determine molecular
architecture (molecular weight, molecular weight distribution and
branching)as well as to understand how the polymer will process,
through measurements of the polymer in the melt phase. Another
Polymer characterization technique is Automatic Continuous Online
Monitoring of Polymerization Reactions (ACOMP) which provides
real-time characterization of polymerization reactions. It can be
used as an analytical method in R&D, a s a tool for reaction
optimization at the bench and pilot plant level and, eventually, for
feedback control of full-scale reactors. AC OMP measures in a model-
independent fashion the evolution of average molar m a ss and
intrinsic viscosity, monomer conversion kinetics and, in the case of
copolymers, also the average composition drift and distribution. It is
applicable in the areas of free radical and controlled radical homo-
and copolymerization, polyelectrolyte synthesis, heterogeneous
phase reactions, including emulsion polymerization, adaptation to
batch and continuous reactors, and modifications of polymers.

EXAMPLES OF POLYMERS WITH THEIR

PREPARATION MRT HODS
P O L Y S T Y R E N E , A n Additi on Po lymer
Polystyrene is used to make ma n y types of containers such
asvideocassette cases, compact disk jewel boxes,tableware (forks,
knives and spoons), and cafeteria trays. A foamed formof
polystyrene is used to make coffee
cups, grocery store meat trays, and building insulation.
To minimize fumes in the laboratory, this procedure uses a
styrene casting resin.

S a f et y P recautio n s
 Wear safety goggles at all times in the laboratory.
 Styrene is harmful by inhalation. It is an irritant to the eyes
and respiratory system. Work in awell ventilated area.
 Methyl ethyl ketone is an irritant. Work in a well ventilated
area.

M a t e r i al s n eed ed
 Styrene casting resin
 Casting resin catalyst, methyl ethyl ketone
 Half of a small petri dish
 Stirring rod
 Optional: A clean dry coin, such a s a penny

Pro cedure
 Measure 15 mL of styrene casting resin into a paper cup.
 Add 5 drops of catalyst to the resin. Stir well.
  Pour the resin mixture into a clean half of a petri dish. Allow
the mixture to sit, undisturbed, forapproximately one hour or
until hard.
 If desired, a clean, dry penny can be added to the resin after it
has set for about 5 minutes. Toavoid air bubbles, coat the
penny with a small amount of the mixed resin before adding it
to theresin mixture in the petri dish.

B AK ELITE , The First Syn thet ic Polymer

Bakelite, a phenol-formaldehyde polymer, was the first completely
synthetic plastic, first made by Leo Baekeland in1907. Baekeland
and an assistant started their research in 1904 looking for a
synthetic substitute for shellac.Bakelite was commercially
introduced in 1909. Bakelite was first used to make billiard balls,
but, later, was used tomake molded insulation, valve parts, knobs,
buttons, knife handles, ma n y types of molded plastic containers
forradios and electronic instruments, and more.
S a f e t y Precauti o ns
 Wear safety goggles at all times in the laboratory.
 Formalin is an irritant to the skin, eyes, and
mucous membranes.
 Phenol is toxic via skin contact. It is listed as a carcinogen.
 Glacial acetic acid is an irritant and can cause burns on
contact.
 Work under a hood and wear gloves and protective clothing
when working with these materials.
M a t e r i al s n eed ed
 Phenol-formaldehyde reaction mixture (freshly prepared
solution should be available. Thereaction mixture is made by
mixing 25 g 36-4 0 % formaldehyde + 20 g phenol + 55 mL
glacialacetic acid.)
 Hydrochloric acid, HCl, concentrated
 150-mL beaker
 stirring rod
Pro cedure
 Under a hood, measure 25 mL of the phenol-formaldehyde
reaction mixture into a 150-mL beaker.Place the beaker on a
white paper towel.
 Add 10 mL of concentrated hydrochloric acid, slowly, with
stirring.
 Add additional hydrochloric acid, dropwise, with stirring. (You
will need approximately 2 mL ofHCl.) As the polymerization
point is reached, a white precipitate will form and dissolve. At
thepoint where polymerization begins, the white precipitate
will not dissolve.
 Continue to stir as the plastic forms and becomes pink in
color.
 Wash the plastic well before handling.
R U B B E R , A N at u r al Po lymer
Natural latex is found in the inner bark of man y trees, especially
thosefound in Brazil and the Far East. The whitesticky sap of plants
such as milkweed and dandelions is also a latex. Latex will turn into
a rubbery m a s s within 12hours after it is exposed to the air. The
latex protects the tree or plant by covering the wound with a
rubberymaterial like a bandage.
CH3
CH2=C-CH=CH2
2-methyl-1,3-butadiene

Natural rubber is a polymer of isoprene (2-methyl-1,3-

butadiene, seeFigure 1) in the form of folded polymeric chains which
are joined in a
network structure and have a high degree of flexibility
(See Figure 2).
Upon application of a stress to a rubber material, such as
blowing up a
balloon or stretching a rubber band, the polymer
chain, which israndomly oriented, undergoes bond rotations
allowing the chain to beextended or elongated (See Figure 3). The
fact that the chains are joinedin a network allows for elastomeric
recoverability since the cross-linked chains cannot irreversibly
slide over oneanother. The changes in arrangement are not
constrained by chain rigidity due to crystallization or high viscosity
due
to a glassy state.
Since latex will solidify in air, a stabilizer is added to
preventpolymerization if the latex is to be stored or shipped inliquid
form. The stabilizer is usually 0.5 to 1 % ammonia. When the
ammonia is removed by evaporation or byneutralization, the latex
will solidify into rubber.

N Y L O N , A C o n d en s at i o n P olymer
Nylon was the result of research directed by Wallace Hume
Carothers at du Pont. The research team was interestedin
duplicating the characteristics of silk. Nylon gained rapid
acceptance for use in stockings and in makingparachutes.
Carothers, however, was subject to bouts of depression and in 1937,
shortly before du Pont placednylon stockings on the market,
Carothers committed suicide by drinking cyanide.

S a f e t y Precauti o ns
 Wear safety goggles at all times in the laboratory.
  The materials in this experiment are considered toxic. They
are irritants to the eyes and mucousmembranes. Wear gloves
and work in a well ventilated area.

M a t e r i al s n eed ed
 Hexamethylenediamine (1,6-hexanediamine), 5 % aqueous
solutionSebacoyl chloride (or adipyl chloride), 5 % solution in
cyclohexaneSodium hydroxide, NaOH, 2 0 % aqueous solution
 Beaker, 50 mL
 Forceps
 Stirring rod.
Pro cedure
 Pour 10 mL of hexamethylenediamine solution into a 50 mL
beaker.
 Add 10 drops of 2 0 % sodium hydroxide solution. Stir.
 Carefully add 10 mL of sebacoyl chloride solution by pouring it
down the wall of the tilted beaker.Two layers should be
evident in the beaker and there should be an immediate
formation of apolymer film at the interface between the two
liquids.
 Using forceps, pick up the m a s s at the center and slowly draw
out the nylon, allowing a “rope” tobe formed. Use a stirring
rod to wrap the rope and continue to pull it slowly from the
mixture interface.
 Wash the nylon well with water before handling.
 Stir any remaining solutions left in the beak to form additional
polymer. Wash the nylon wellwith water.
 Commercially, nylon is made by mixing the components in
bulk. Nylon thread, rod, and sheet aremade by melting and
forming or extruding the polymer.

S O D I U M P OL Y ACR Y LAT E , A Co po lymer

Superabsorbants were originally developed by the United States
Department of Agriculture in 1966. This materialconsisted of a
grafted copolymer of hydrolyzed starch-polyacrylonitrile
(polyacrylonitrile is commonly known asAcrilan, Orion, or Creslan).
The intended use was for additives for drilling fluid in off-shore
secondary oil recoveryoperations and as agricultural thickeners.
These materials were followed by synthetic superabsorbants that
arepolyacrylic and polyacrylonitrile based. S o m e of these materials
are capable of absorbing up to 2000 times theirweight of distilled
water.
When a starch-hydrolyzed polyacrylonitrile superabsorbant is
mixed with glycerin or ethylene glycol, the resultingfirm gel has a
rubbery texture and is very strong and resilient. This material can
absorb about 300 to 400 times itsweight in distilled water and can
“grow” many times its original size. This material was formed into
various shapesand sold under names such a s "Grow Creatures". The
process is reversible and, on standing in air, the grow creaturewill
shrink almost to its original size on drying. It can be grown and dried
ma n y times.
A useful application of "Super Slurper" is in the liners of Pampers
and other disposable diapers. Under thisapplication, the polymer gel
can absorb up to 90 times its weight in liquid.Super-absorbent
material, sold under the name "Water Grabber" or "Water Lock" is
available from garden supplystores and can be found in the garden
department of some variety stores.

S o m e I n o r g an i c P o l ymer s
Some examples of-Inorganic Polymers: (Ref.: H. R. Allcock,
Scientific American , 230, 66, March 1974)

Glass: made of rings and chains of repeating silicate units. Glass

fibers (fiberglass) are used in textiles and in manyconstruction
materials.

Bricks, concrete and ceramics are three-dimensional polymers.

Polyphosphazenes: general formula (NPCl2) n . Formed from

reactingNH4Cl with PCl5 at 250°C for several hours.Can be
substituted to alter properties.

Po lymeric Sulfur
M a t e r i al s N e ed e d
Sulfur
Safety
Precauti o ns
It is recommended that a hot plate be used in heating the sulfur in
this preparation. This will prevent thesulfur from igniting and
burning to form toxic sulfur dioxide, a strong irritant. Keep the
beaker of sulfurcovered with a watch glass to minimize sulfur vapors
escaping from the beaker.

Pro cedure
 Heat ordinary sulfur to a temperature between 140-170°C.
The sulfur will turn red and become viscous above159°C. At
175°C, the viscosity of the molten sulfur begins to decrease.

 Pour the hot melt into water in a thin stream. When cool, it
forms rubbery fibers of the Polymeric sulfur. Thepolymer is not
stable at room temperature and it will eventually harden,
returning to its normal yellow color, whenthe molecules
reform into eight-membered rings.
Polymer degradation

A plastic item with thirty years of exposure to heat and cold, brake
fluid, and sunlight. Notice the discoloration, swollen dimensions, and
tiny splits running through the material

Polymer degradation is a change in the properties—tensile strength,

color, shape, molecular weight, etc.—of a polymer or polymer-based
product under the influence of one or more environmental factors,
such as heat, light, chemicals and, in some cases, galvanic action. It
is often due to the scission of polymer chain bonds via hydrolysis,
leading to a decrease in the molecular m a s s of the polymer.

Although such changes are frequently undesirable, in some cases,

such as biodegradation and recycling, they m a y be intended to
prevent environmental pollution. Degradation can also be useful in
biomedical settings. For example, a copolymer of Polylactic acid and
polyglycolic acid is employed in hydrolysable stitches that slowly
degrade after they are applied to a wound.

The susceptibility of a polymer to degradation depends on its

structure. Epoxies and chains containing aromatic functionality are
especially susceptible to UV degradation while polyesters are
susceptible to degradation by hydrolysis, and some other polymers
are especially susceptible to ozone cracking. Carbon based
polymers are more susceptible to thermal degradation than
inorganically bound polymers such a s polydimethylsiloxane and are
therefore not ideal for most high temperature applications.

The degradation of polymers to form smaller molecules may

proceed by random scission or specific scission. The degradation of
polyethylene occurs by random scission—a random breakage of the
linkages (bonds) that hold the atoms of the polymer together. When
heated above 450 °C it degrades to form a mixture of hydrocarbons.
Other polymers—like polyalphamethylstyrene—undergo specific
chain scission with breakage occurring only at the ends. They
literally unzip or depolymerize to become the constituent monomer.
The sorting of polymer waste for recycling purposes m a y be
facilitated by the use of the Resin identification codes developed by
the Society of the Plastics Industry to identify the type of plastic.

Pr oduct failure

Chlorine attack of acetal resin plumbing joint

In a finished product, such a change is to be prevented or delayed.

Failure of safety-critical polymer components can cause serious
accidents, such as fire in the case of cracked and degraded polymer
fuel lines. Chlorine-induced cracking of acetal resin plumbing joints
and polybutylene pipes has caused ma n y serious floods in domestic
properties, especially in the U SA in the 1990s. Traces of chlorine in
the water supply attacked vulnerable polymers in the plastic
plumbing, a problem which occurs faster if any of the parts have
been poorly extruded or injection molded. Attack of the acetal joint
occurred because of faulty molding, leading to cracking along the
threads of the fitting which is a serious stress concentration.

Ozone-induced cracking in natural rubber tubing

Polymer oxidation has caused accidents involving medical devices.

One of the oldest known failure modes is ozone cracking caused by
chain scission when ozone g as attacks susceptible elastomers, such
as natural rubber and nitrile rubber. They possess double bonds in
their repeat units which are cleaved during ozonolysis. Cracks in fuel
lines can penetrate the bore of the tube and cause fuel leakage. If
cracking occurs in the engine compartment, electric sparks can
ignite the gasoline and can cause a serious fire.

Fuel lines can also be attacked by another form of degradation:

hydrolysis. Nylon 6,6 is susceptible to acid hydrolysis, and in one
accident, a fractured fuel line led to a spillage of diesel into the
road. If diesel fuel leaks onto the road, accidents to following cars
can be caused by the slippery nature of the deposit, which is like
black ice.