POLYMER

A polymer (/ˈpɒlᵻmər/; Greek pol

y-, "many" + -mer, "parts") is a large molecule, or macromolecule, composed
of many repeated subunits. Because of their broad range of properties,[4] both
synthetic and natural polymers play an essential and ubiquitous role in
everyday life. Polymers range from familiar synthetic plastics such
as polystyrene to natural biopolymers such as DNA and proteins that are
fundamental to biological structure and function. Polymers, both natural and
synthetic, are created via polymerization of many small molecules, known
as monomers. Their consequently large molecular mass relative to small
molecule compounds produces unique physical properties,
including toughness, viscoelasticity, and a tendency to
form glasses and semicrystalline structures rather than crystals.
The term "polymer" derives from the ancient Greek word πολύς (polus,
meaning "many, much") and μέρος (meros, meaning "parts"), and refers to
a molecule whose structure is composed of multiple repeating units, from
which originates a characteristic of high relative molecular mass and
attendant properties. The units composing polymers derive, actually or
conceptually, from molecules of low relative molecular mass. The term was
coined in 1833 by Jöns Jacob Berzelius, though with a definition distinct from
the modern IUPAC definition. The modern concept of polymers as covalently
bonded macromolecular structures was proposed in 1920 by Hermann
Staudinger, who spent the next decade finding experimental evidence for this
hypothesis.
Polymers are studied in the fields
of biophysics and macromolecular science, and polymer science (which
includes polymer chemistry and polymer physics). Historically, products
arising from the linkage of repeating units by covalent chemical bonds have
been the primary focus of polymer science; emerging important areas of the
science now focus on non-covalent links. Polyisoprene of latex rubber and
the polystyrene of styrofoam are examples of polymeric natural/biological and
synthetic polymers, respectively. In biological contexts, essentially all
biological macromolecules—i.e., proteins (polyamides), nucleic
acids (polynucleotides), and polysaccharides—are purely polymeric, or are
composed in large part of polymeric components—e.g., isoprenylated/lipid-
modified glycoproteins, where small lipidic molecules and oligosaccharide
modifications occur on the polyamide backbone of the protein.
The simplest theoretical models for polymers are ideal chains.

COMMON
EXAMPLES
Polymers are of two types:
 Natural polymeric materials such as shellac, amber, wool, silk 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, phenol
formaldehyde resin (or Bakelite), neoprene, nylon, polyvinyl chloride
(PVCorvinyl), 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 ('polythene' in British English), 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).
 POLYMER
SYNTHESIS
Polymerization is the process of combining many small
molecules known as monomers into a covalently
bonded chain or network. 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-C6H4-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.

Microstructure of part of a DNA double

helix biopolymer
Laboratory synthetic methods are generally divided into two categories, step-
growth polymerization and chain-growth polymerization.[13] The essential
difference between the two is that in chain growth polymerization, monomers
are added to the chain one at a time only,[14] such as in polyethylene, whereas
in step-growth polymerization chains of monomers may combine with one
another directly,[15] such as in polyester. 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
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. There are other
biopolymers such as rubber, suberin, melanin and lignin.
Modification of natural polymers
Naturally occurring polymers such as cotton, starch and rubber were familiar
materials for years before synthetic polymers such
as polyethene and perspex appeared on the market. 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. Ways in which polymers can
be modified include oxidation, cross-linking and end-capping.
Especially in the production of polymers, the gas separation by membranes
has acquired increasing importance in the petrochemical industry and is now
a relatively well-established unit operation. The process of polymer degassing
is necessary to suit polymer for extrusion and pelletizing, increasing safety,
environmental, and product quality aspects. Nitrogen is generally used for
this purpose, resulting in a vent gas primarily composed of monomers and
nitrogen.

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 repeat units (monomer residues, also known as "mers")
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.[18] 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 of a polymer is its architecture and
shape, which relates to the way branch points lead to a deviation from a
simple linear chain.[19] A branched polymer molecule is composed of a main
chain with one or more substituent side chains or branches. Types of
branched polymers include star polymers, comb polymers, brush
polymers, dendronized polymers, ladders, and dendrimers.[19] There exist
also two-dimensional polymers which are composed of topologically planar
repeat units. A polymer's architecture affects many of its physical properties
including, but not limited to, solution viscosity, melt viscosity, solubility in
various solvents, glass transition temperature and the size of individual
polymer coils in solution. A variety of techniques may be employed for the
synthesis of a polymeric material with a range of architectures, for
example Living polymerization.
Chain length
The physical propertiesof 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.[21] Impact resistance also
tends to increase with chain length, as does the viscosity, or resistance to flow,
of the polymer in its molten state. Melt viscosity is related to polymer

chain length Z roughly as ~ Z, 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 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:
[30]
[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 a particular point in the
chain is independent of the types of surrounding monomer residue may be
referred to as a truly random copolymer.
 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.
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 loosely 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.[33]
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.[34]
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.[35]
Mechanical properties
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.

A polyethylene sample that has necked under tension.

Tensile strength
The tensile strength of a material quantifies how much elongating stress the
material will endure before failure.[36][37] 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. Viscoelasticity describes a complex time-
dependent elastic response, which will exhibit hysteresis in the stress-strain
curve when the load is removed. Dynamic mechanical analysis or DMA
measures this complex modulus by oscillating the load and measuring the
resulting strain as a function of time.
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), at which amorphous polymers undergo
a transition from a rubbery, viscous liquid, to a brittle, glassy amorphous
solid on cooling. The glass transition temperature may be engineered by
altering the degree of branching or crosslinking in the polymer or by the
addition of plasticizer.[38]
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 Tg 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. An 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 in 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
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.
Optical properties
Polymers such as PMMA and HEMA:MMA are used as matrices in the gain
medium of solid-state dye lasers that are also known as polymer lasers. These
polymers have a high surface quality and are also highly transparent so that
the laser properties are dominated by the laser dye used to dope the polymer
matrix. These type of lasers, that also belong to the class of organic lasers, are
known to yield very narrow linewidths which is useful for spectroscopy and
analytical applications.[39] An important optical parameter in the polymer
used in laser applications is the change in refractive index with temperature
also known as dn/dT. For the polymers mentioned here the (dn/dT) ~ −1.4 ×
10−4 in units of K−1 in the 297 ≤ T ≤ 337 K range.
 BIBLIOGRAPHY
 www.google.com
 https://en.wikipedia.org/wiki/Polymer
 https://www.britannica.com/science/polymer

CERTIFICATE
 This is to certify that the project entitled
Polymer by Ms. Ridhi Sharma of Gurukul
International Sen. Sec. School has submitted
his project to Mr. Vineet Ranote under his
supervision.

Teacher’s sign. Examiner sign.

 ACKNOWLEDGEME
NT
I would like to express my
special thanks of gratitude to my teacher Mr. Vineet
Ranote as well as our principal Miss Praveena Jha
who gave me the golden opportunity to do this wonderful
project on the Topic Polymer which also helped me in
doing a lot of Research and I came to know about so
many new things am really thankful to them.
Secondly I would also like to thank my parents
and friends who helped me a lot in finalizing this project
within the limited time frame.

RIDHI SHARMA