Chemistry Project Report:

“Polymers”

By:

Name: Dhruv Shrivastava

Class: XII Genius 30 C
Roll No: 4
 Polymer
Appearance of real linear polymer chains as recorded using an atomic force
microscope on surface under liquid medium. Chain contour length for this
polymer is ~204 nm; thickness is ~0.4 nm.
A polymer 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
many 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 DNA (in phosphodiester bonds).

Polymers are studied in the fields of polymer chemistry, polymer physics, and
polymer science.

Overview
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 as 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. By 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.

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. 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 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.

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 development
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 as 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 1920s 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 1974 to Paul Flory,
whose extensive work on polymers included the kinetics of step-growth
polymerization 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.

Describing polymers
Molecular description

In many instances a polymer molecule may be described using the same

terminology used to describe any molecule. Molecular structure may be
described in terms of bond lengths and angles; mass may 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 mass of a polymer molecule may 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 mass 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(Mw). 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 as proteins, may 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 may 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, may 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 degree of crystallinity may 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 some polymers in which chirality in the monomer is
retained following polymerization. In other polymers a chiral center may 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 as ethylene-vinyl acetate. Some
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 ionomer 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 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, 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 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.

Macroscopic description

The macroscopic physical properties of polymers in many cases reflect that of

any other molecular substance. Polymer materials may be transparent,
translucent, or opaque, and may be insulators, conductors, or
semiconductors. Other properties, however, especially those governing phase
transitions, may 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". Among
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 assumed 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 may 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 may be lost from each monomer. This is the case, for
example, in the polymerization of PET polyester. The monomers are
terephthalic acid (HOOC-C6H4-COOH) and ethylene glycol (HO-CH2-CH2-OH)
but the repeating unit is -OC- C 6H4-COO-CH2-CH2-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.

Laboratory synthesis

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 may combine with one another directly.
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. Laboratory synthesis of biopolymers, especially
of proteins, is an area of intensive research.

Biological synthesis
Microstructure of part of a DNA double helix biopolymer Main
article: Biopolymer
There are three main classes of biopolymers: polysaccharides, polypeptides,
and polynucleotides. In living cells, they 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 to RNA and
subsequently translate that information to synthesize the specified protein
from amino acids. The protein may be modified further following translation in
order to provide appropriate structure and functioning.

Modification of natural polymers

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 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.

Monomers and 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 as a homopolymer. Ethylene-vinyl acetate, on the
other hand, contains more than one variety of repeat unit and is thus a
copolymer. Some biological polymers are composed of a variety of different
but structurally related monomer residues; for example, polynucleotides such
as DNA 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
may exhibit different durability, even though their molecules comprise the
same monomers.

Polymer architecture

Branch 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 may 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, may reduce
polymer strength due to disruption of organization and may 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 as the number of reaction sites at which may 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 Tg and increase strength and toughness. Among other applications,
this process is used to strengthen rubbers in a process known as
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 may lead to
the formation of an infinite network, also known as a gel, in which networks of
chains are of unlimited extent—essentially all chains have linked into one
molecule.

Chain length

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, as does the viscosity, or resistance to
flow, of the polymer in its melt state. Chain length is related to melt viscosity
roughly as 1:103.2, 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 (T g). 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 may 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. Common 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.
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: [AB...]n (2).
· Periodic copolymers have monomer residue types arranged in a
repeating sequence: [AnBm...] m being different from n .
· Statistical copolymers 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 may be referred to as a truly random copolymer
(3).
· Block copolymers 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 grafted copolymers 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 same side), atactic (random placement of substituents),
and syndiotactic (alternating placement of substituents).
Polymer morphology

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 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, may 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 may 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 may consist of both crystalline and
amorphous regions; the degree of crystallinity may 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
many polymers, reduced crystallinity may also be associated with increased
transparency.
Chain conformation

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 mass 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.

Mechanical 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 strength

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.

Young's modulus 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.

Transport 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.

Phase behavior

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. Though
abbreviated as simply Tm, the property in question is more properly called the
crystalline melting temperature. Among synthetic polymers, crystalline melting
is only discussed with regards to thermoplastics, as thermosetting polymers
will decompose at high temperatures rather than melt.

Glass 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
may be engineered by altering the degree of branching or crosslinking in the
polymer or by the addition of plasticizer.

Mixing 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.

Inclusion 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 unplasticized
polyvinylchloride, 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.

Chemical 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 as 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.

Standardized polymer nomenclature

There are multiple conventions for naming polymer substances. Many
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)[32] and IUPAC [33] have
proposed standardized naming conventions; the ACS 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
ethanediyloxycarbony Poly(oxyetheneoxyterephthalo
terephthalate)
l-1,4- yl)
or PET phenylenecarbonyl)
Nylon 6 Poly[amino(1-oxo-1,6- Poly[amino(1-oxohexan-1,6-
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:

Polymer 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, 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.
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, as a tool for reaction optimization at the
bench and pilot plant level and, eventually, for feedback control of full-scale
reactors. ACOMP measures in a model-independent fashion the evolution of
average molar mass 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

MRTHODS
POLYSTYRENE, An Addition Polymer
Polystyrene is used to make many 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.
Safety Precautions
· 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.

Materials needed
· Styrene casting resin
· Casting resin catalyst, methyl ethyl ketone
· Half of a small petri dish
· Stirring rod
· Optional: A clean dry coin, such as a penny

Procedure
· 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.
BAKELITE, The First Synthetic 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, many types of molded plastic containers
forradios and electronic instruments, and more.

Safety Precautions
· 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.
Materials needed
· Phenol-formaldehyde reaction mixture (freshly prepared solution should
be available. Thereaction mixture is made by mixing 25 g 36-40%
formaldehyde + 20 g phenol + 55 mL glacialacetic acid.)

· Hydrochloric acid, HCl, concentrated ·

150-mL beaker
· stirring rod
Procedure
· 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.

RUBBER, A Natural Polymer
Natural latex is found in the inner bark of many 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 mass 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.

NYLON, A Condensation Polymer

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.

Safety Precautions
· 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.
Materials needed
· Hexamethylenediamine (1,6- hexanediamine), 5% aqueous
solutionSebacoyl chloride (or adipyl chloride), 5% solution in
cyclohexaneSodium hydroxide, NaOH, 20% aqueous solution
· Beaker, 50 mL
· Forceps
· Stirring rod.
Procedure
· Pour 10 mL of hexamethylenediamine solution into a 50 mL beaker.

· Add 10 drops of 20% 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 mass 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.
SODIUM POLYACRYLATE, A Copolymer
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. Some 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 as "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 many 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.

Some Inorganic Polymers

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.

Polymeric Sulfur
Materials Needed
Sulfur
Safety Precautions
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.

Procedure
· 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
mass of the polymer.
Although such changes are frequently undesirable, in some cases, such as
biodegradation and recycling, they may 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 as 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 may be facilitated by the
use of the Resin identification codes developed by the Society of the Plastics
Industry to identify the type of plastic.

Product 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
many serious floods in domestic properties, especially in the USA 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 gas 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.