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.

 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

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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

 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-

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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 (Mn) 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.

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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 solidliquid phase transition but a
transition from a crystalline or semicrystalline 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.
The boiling point of a polymer substance is never defined, in that polymers will decompose
before reaching assumed boiling temperatures.

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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-C6H4COOH) 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.

 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

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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.

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 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

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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

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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: [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

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 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.

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 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

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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 selfinteraction,
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.

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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. 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 heatresistant. 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.

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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.