A 

polymer (/ˈpɒlɪmər/;[4][5] Greek poly-, "many" + -mer, "part") is a substance or material consisting of

very large molecules, or macromolecules, composed of many repeating subunits.[6] Due to their
broad spectrum of properties,[7] both synthetic and natural polymers play essential and ubiquitous
roles in everyday life.[8] 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,
high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures
rather than crystals.
The term "polymer" derives from the Greek word πολύς (polus, meaning "many, much") and μέρος
(meros, meaning "part"). The term was coined in 1833 by Jöns Jacob Berzelius, though with a
definition distinct from the modern IUPAC definition.[9][10] The modern concept of polymers as
covalently bonded macromolecular structures was proposed in 1920 by Hermann Staudinger,[11] who
spent the next decade finding experimental evidence for this hypothesis.[12]
Polymers are studied in the fields of polymer science (which includes polymer
chemistry and polymer physics), biophysics and materials science and engineering. Historically,
products arising from the linkage of repeating units by covalent chemical bonds have been the
primary focus of polymer science. An emerging important area now focuses on supramolecular
polymers formed by non-covalent links. Polyisoprene of latex rubber is an example of a natural
polymer, and the polystyrene of styrofoam is an example of a synthetic polymer. 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.

Cartoon schematic of polymer molecules

Contents

 1Common examples
o 1.1Natural
o 1.2Synthetic
 2History
 3Synthesis
o 3.1Biological synthesis
o 3.2Modification of natural polymers
 4Structure
o 4.1Monomers and repeat units
o 4.2Microstructure
 4.2.1Polymer architecture
 4.2.2Chain length
  4.2.3Monomer arrangement in copolymers
 4.2.4Tacticity
o 4.3Morphology
 4.3.1Crystallinity
 4.3.2Chain conformation
 5Properties
o 5.1Mechanical properties
 5.1.1Tensile strength
 5.1.2Young's modulus of elasticity
o 5.2Transport properties
o 5.3Phase behavior
 5.3.1Crystallization and melting
 5.3.2Glass transition
 5.3.3Mixing behavior
 5.3.4Inclusion of plasticizers
o 5.4Chemical properties
o 5.5Optical properties
o 5.6Electrical properties
 6Applications
 7Standardized nomenclature
 8Characterization
 9Degradation
o 9.1Product failure
 10See also
 11References
 12Bibliography
 13External links

Common examples
See also: Polymer classes

Structure of a styrene-butadiene chain, from a molecular simulation.

Polymers are of two types: naturally occurring and synthetic or man made.

Natural
Natural polymeric materials such as hemp, 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.

Synthetic
The list of synthetic polymers, roughly in order of worldwide demand,
includes polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol
formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, and many more.
More than 330 million tons of these polymers are made every year (2015).[13]
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 repeat unit or monomer is ethylene. Many 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).

History
See also: Polymer science
Polymers have been essential components of commodities since the early days of humankind. The
use of wool (keratin), cotton and linen fibres (cellulose) for garments, paper reed (cellulose)
for paper are just a few examples of how our ancestors exploited polymer-containing raw materials
to obtain artefacts. The latex sap of “caoutchouc” trees (natural rubber) reached Europe in the 16th
century from South America long after the Olmec, Maya and Aztec had started using it as a material
to make balls, waterproof textiles and containers.[14]
The chemical manipulation of polymers dates back to the 19th century, although at the time the
nature of these species was not understood. The behaviour of polymers was initially rationalised
according to the theory proposed by Thomas Graham which considered them as colloidal
aggregates of small molecules held together by unknown forces.
Notwithstanding the lack of theoretical knowledge, the potential of polymers to provide innovative,
accessible and cheap materials was immediately grasped. The work carried out
by Braconnot, Parkes, Ludersdorf, Hayard and many others on the modification of natural polymers
determined many significant advances in the field.[15] Their contributions led to the discovery of
materials such as celluloid, galalith, parkesine, rayon, vulcanised rubber and, later, Bakelite: all
materials that quickly entered industrial manufacturing processes and reached households as
garments components (e.g., fabrics, buttons), crockery and decorative items.
In 1920, Hermann Staudinger published his seminal work “Über Polymerisation”,[16] in which he
proposed that polymers were in fact long chains of atoms linked by covalent bonds. His work was
debated at length, but eventually it was accepted by the scientific community. Because of this work,
Staudinger was awarded the Nobel Prize in 1953.[17]
After the 1930s polymers entered a golden age during which new types were discovered and quickly
given commercial applications, replacing naturally-sourced materials. This development was fuelled
by an industrial sector with a strong economical drive and it was supported by a wide academic
community that contributed with innovative synthesis of monomers from cheaper raw materials,
more efficient polymerisation processes, improved techniques for polymer characterisation and
advanced theoretical understanding of polymers.[15]
Since 1953, six Nobel prizes were awarded in the area of polymer science, excluding those for
research on biological macromolecules. This further testifies its impact on modern science and
technology. As Lord Todd summarised it in 1980, “I am inclined to think that the development of
polymerization is perhaps the biggest thing that chemistry has done, where it has had the biggest
effect on everyday life”.[19]

Synthesis
Main article: Polymerization

A classification of the polymerization reactions

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 happens 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.
Synthetic methods are generally divided into two categories, step-growth polymerization and chain
polymerization.[20] The essential difference between the two is that in chain polymerization,
monomers are added to the chain one at a time only,[21] such as in polystyrene, whereas in step-
growth polymerization chains of monomers may combine with one another directly,[22] such as
in polyester. Step-growth polymerization can be divided into polycondensation, in which low-molar-
mass by-product is formed in every reaction step, and polyaddition.

Example of chain polymerization: Radical polymerization of styrene, R. is initiating radical, P. is another

polymer chain radical terminating the formed chain by radical recombination
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
Main article: Biopolymer

Microstructure of part of a DNA double helix 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. 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 endcapping.

Structure
The structure of a polymeric material can be described at different length scales, from the sub-nm
length scale up to the macroscopic one. There is in fact a hierarchy of structures, in which each
stage provides the foundations for the next one.[23] The starting point for the description of the
structure of a polymer is the identity of its constituent monomers. Next, the microstructure essentially
describes the arrangement of these monomers within the polymer at the scale of a single chain. The
microstructure determines the possibility for the polymer to form phases with different arrangements,
for example through crystallization, the glass transition or microphase separation.[24] These features
play a major role in determining the physical and chemical properties of a polymer.
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. A polymer which contains only a single type of repeat
unit is known as a homopolymer, while a polymer containing two or more types of repeat units is
known as a copolymer.[25] A terpolymer is a copolymer which contains three types of repeat units.[26]
Polystyrene is composed only of styrene-based repeat units, and is classified as a
homopolymer. Polyethylene terephthalate, even though produced from two
different monomers (ethylene glycol and terephthalic acid), is usually regarded as a homopolymer
because only one type of repeat unit is formed. Ethylene-vinyl acetate contains more than one
variety of repeat unit and is 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 four types of nucleotide subunits.

Homopolymers and copolymers (examples)

Homopolymer p Homopolymer polydim The

olystyrene ethylsiloxane, homopolymer polyethyl
a silicone. The main ene terephthalate has
chain is formed of only one repeat u
silicon and oxygen
atoms.