Chapter 1.

Polymer fundamentals and bonds

between atoms
1.1. Introduction

Polymers consist of large molecules, i.e. macromolecules. According to the basic IUPAC
definition: ‘A polymer is a substance composed of molecules characterised by the multiple
repetition of one or more species of atoms or groups of atoms (constitutional repeating units)
linked to each other in amounts sufficient to provide a set of properties that do not vary
markedly with the addition of one or a few of the constitutional repeating units’. The word
polymer originates from the Greek words ‘poly’ meaning many and ‘mer’ meaning part. It
was the Swedish chemist Jöns Jacob Berzelius who coined in 1832 the term polymer for any
compound with a molar mass that was a multiple of the molar mass of another compound with
the same elemental composition. Fig. 1.1 shows the structure of polypropylene, an industrially
important polymer. The constitutional repeating units, which are also called simply ‘repeating
units’, are linked by covalent bonds, and so are also the atoms within a repeating unit. A
molecule with only a few constitutional repeating units is called an oligomer. The physical
properties of an oligomer vary with the addition or removal of one or a few constitutional
repeating units to or from its molecules. A monomer is the substance that the polymer is made
from, which in the case of polypropylene is propylene (propene) (Fig. 1.1).

Figure 1.1. The structure of monomer and Figure 1.2. Anisotropic nature of polymer
polymer (polypropylene). The constitutional crystals. Approximate moduli for
repeating unit is shown between the brackets. polyethylene parallel (Ec) and transverse
(Et) to the chain axis are shown.

1
 The polymers dealt with in this chapter are exclusively carbon-based organic polymers.
Other common elements in the organic polymers are hydrogen, oxygen, nitrogen, sulphur and
silicon. The covalent bonds that link the atoms of the polymer chains are very strong with
dissociation energies between 300 and 500 kJ mol-1. The intermolecular bonds, sometimes
denoted secondary bonds, are much weaker with dissociation energies of a few to 50 kJ mol-1.

The large difference in dissociation energy and bond force constant (‘stiffness’) between
the covalent bonds and the weak secondary intermolecular bonds is of great importance for the
properties. The identity of the molecules, i.e. the entities linked by covalent bonds, is largely
preserved during melting, while the secondary bonds are broken. There are many examples of
polymers that degrade early at low temperatures but where the degradation involves only a
few of the existing primary bonds. Melting involves mainly the rupture and partial re-
establishment of a great many secondary bonds.

Polymer crystals show very direction-dependent (anisotropic) properties. The Young’s

modulus of a polyethylene single crystal at room temperature is approximately 300 GPa in the
chain axis direction and only 3 GPa in the transverse directions (Fig. 1.2). This considerable
difference in modulus is due to the presence of two types of bonds connecting the different
atoms in the crystals: strong and stiff covalent bonds along the chain axis and weak and soft
secondary bonds acting in the transverse directions (Fig. 1.2). A whole range of other
properties, e.g. the refractive index, also shows strong directional dependence. The orientation
of the polymer molecules in a material is enormously important. The Young's modulus of a
given polymer can be changed by a factor of one hundred by changing the degree of chain
orientation.

1.2. The covalent bonds

Organic polymers are based on carbon (always), hydrogen (almost always) and
occasionally oxygen, nitrogen, sulphur, halogens, and a few other elements. These atoms are
in the case of polymers connected by covalent bonds. A covalent bond is a chemical bond
formed when two atoms share a pair of electrons. Primary bond is an often-used synonymous
expression to covalent bond. The electronic structure of the elements determines the
characteristics of their covalent bonds to other atoms. Fig. 1.3 shows schematically the
electronic structures of the aforementioned elements. Electrons located in different electron
shells surround the positively charged nucleus. The number of electrons is equal to the number
of protons in the nucleus of an uncharged atom. Both theory and experiment indicate that the
electronic structures of the rare gases (e.g. helium, neon and argon) are especially stable; these
atoms are said to contain ‘filled shells’. The way in which the other elements forms covalent
bonds can be understood by their wish to attain filled-shell conditions. The first shell holds
only 2 electrons, whereas the second shell holds 8 electrons. The third can hold 18 electrons,

2
but a very stable configuration is reached when a shell of 8 electrons is filled (argon structure).
Hydrogen needs only 2 electrons to fill its outermost shell. This can be achieved by forming a
covalent bond between two hydrogen atoms (Fig. 1.4). The two hydrogen atoms share an
electron pair and simulate in this respect the helium configuration with a filled outer shell.
Carbon has 4 electrons in the outermost shell (valence electrons) and it wishes to attain filled
shell conditions, 8 valence electrons. Forming covalent bonds with four hydrogen atoms, as is
shown in Fig. 1.4, simulates the electronic structure of neon. The covalent bonds are very
strong and the atoms are not readily separated. Let us take a look at a few other important
elements. Nitrogen has 5 valence electrons and therefore binds three other atoms as in
ammonia (NH3) to attain filled shell conditions. Oxygen has 6 valence electrons and forms two
covalent bonds with the two hydrogen atoms in water (H2 O) to attain the neon structure.

First
+1 +2
electron
shell
H He
Second
electron +8
+6 +7 +9 +10
shell

C N O F Ne

Figure 1.3. Electronic structures of common elements in organic polymers.

+1 + +1 +1 +1

H H H2

+1

+6 + 4 +1 +1 +6 +1

H
C +1

CH4

Figure 1.4. Formation of covalent bonds: H2 and CH4.

The energies of the electrons can take only certain, specific values (quantum theory). The
result of the quantum theory is a series of solutions referred to as wave functions and also
called atomic orbitals, which describe the probability of finding an electron at a certain
location with respect to the nucleus under the precondition of a certain specific energy.
According to the Pauli exclusion principle, one or two electrons may occupy each atomic
orbital. The orbital with the lowest energy is the s orbital. The electron cloud of the s orbital is

3
spherical (Fig. 1.5). The next higher energy level is the p orbital, which consists of two
symmetrical lobes (Fig. 1.5). The d orbital consists of four lobes, all in a plane at angles of 90°
to each other (Fig. 1.5). The first shell contains only the s orbital with maximum two electrons.
The second shell has one s and three p orbitals, each orbital having maximum 2 electrons. The
highest number of electrons in the second shell is thus 8. A covalent bond is formed when two
atoms (e.g. H atoms) approach each other. The atomic orbitals overlap and are fused into a
molecular orbital. The nuclei attract the electron cloud of the other atom, but very strong
repulsive forces act on the atoms when the two nuclei come very close. The energy is at a
minimum at a certain interatomic distance, i.e. the bond length (Fig. 1.6). Maximum overlap
of the atomic orbitals affords the strongest bond. The s orbitals with their spherical shape
overlap less than the p orbitals with their stronger directionality.

Figure 1.5. Schematic drawing of s, p and Figure 1.6. Bond energy as a function of
d orbitals. interatomic distance for H2.

The atomic orbitals of carbon are modified into hybrid atomic orbitals as they form
covalent bonds. The new set of orbitals (sp3 orbitals) is obtained by a combination of the s and
p orbitals into four orbitals pointing from the centre of a tetrahedron to its corners (Fig. 1.7). In
methane (CH4) the four sp3 hybrid orbitals of the carbon are combined with 1 s orbitals of
hydrogen to four molecular orbitals that are symmetric about the interatomic axes. Such bonds
are referred to as σ bonds. The symmetry allows torsion about these bonds. The sp3 atomic
orbitals are only useful for bonding carbon to four separate atoms.

If bonding is required for only three atoms, one s and two p orbitals are used to form three
sp orbitals. The sp2 orbitals are symmetrically placed in a plane with an angle of 120°
2

between each orbital symmetry axis (Fig. 1.7). If two such atoms meet they form a σ bond and
the two residual p orbital electrons form a so-called π bond. The π bond is not symmetrical
with respect to the interatomic axis and hence no torsion about a double bond can occur
without breakage of the covalent π bond. The two carbon atoms share four electrons in a
double bond. Note that all the atoms in ethene (ethylene) (C2 H4) are located in a single plane.
If a carbon atom is bonded to only two other atoms, only the s and one p orbital electrons are
used to generate two sp hybrid orbitals (Fig. 1.7). The angle between their symmetry axes is

4
180°. The sp hybrid orbitals form σ bonds with another carbon and hydrogen in ethyne (C2H2).
The two remaining p orbital electrons of the carbon atom can combine with another carbon
atom with the same set of p orbital electrons to form two π bonds. Ethyne is a linear molecule
with no torsional mobility of the carbon-carbon triple bond.

Figure 1.7. Hybrid atomic orbitals in carbon: sp3, sp2 and sp.

There are a few important concepts with regard to the potential energy of covalent bonds
that need to be explained. The intrinsic binding energy (E) is the energy difference between
the ground state of the molecule and the valency states at infinite interatomic distance. The
dissociation energy (D) is smaller than E; the difference is due to the energy of vibrations and
the sum of the energies of promotion, hybridisation and polar and steric rearrangements to
attain the valency state. The activation energy for bond dissociation is denoted U0. The
dissociation energies of covalent bonds are typically between 300 and 500 kJ mol-1 (120-
200RT at 300 K). A very weak covalent bond is that between the oxygen atoms in organic
peroxides (-O-O-; D≈ 150 kJ mol-1), which is due to the electrostatic repulsion between the
unshared electron pairs of the oxygen atoms. The bonds become weaker as one proceeds down
columns in the periodic table (e.g. C-F> C-Cl> C-Br). Double bonds are stronger than single
bonds. The bond lengths are between 0.1 and 0.15 nm depending on the atoms involved: 0.11
nm (C-H), 0.135 nm (C=C) and ~0.15 nm (C-C; C-N; C-O).

1.3. Secondary bonds

The interaction between atoms of different molecules (often denoted secondary bonds) is
very important for the properties and the physical behaviour of polymers. The secondary
bonds can be divided into several categories and they are much weaker than the covalent
bonds, a few kJ mol-1 for London dispersion forces to ~50 kJ mol-1 for hydrogen bonds.

We need first to define a few concepts that are important for the further discussion. The
first concept is dipole moment. Two atoms linked with a covalent bond (it can be a single,
double or triple bond) share a number of electrons. The atom with the greater electronegativity
attracts the electrons more and it will become negatively charged (-q; note that q is smaller
than the charge of one electron). The other atom, which is more electropositive, will become

5
positively charged (+q). Note that the charges are equal but that they have different signs. The
electronegativity of an element can be judged from its position in the periodic table: it
increases when going from left to right in the periodic table and it decreases when going
downwards in the periodic table. The dipole moment (u) is simply the product of the charge
and the distance (l) between the charges, i.e. u=ql. The dipole moment is thus a vector. Table
1.1 presents a number of bond moments relevant for polymers.

Table 1.1. Dipole moments of bonds in Debye units (1 D= 3.336 x 10-30 C m)a

C--H+ 0.4 C+-N- 0.22 N+-O- 0.3

- + + - + -
N -H 1.31 C -O 0.74 N =O 2.0
O--H+ 1.51 C+-Cl- 1.6
- + + -
F -H 1.94 C =O 2.5
a
Data collected by Israelachvili (1992).

Symmetrical molecules like methane have dipole moments that point from the carbon atom
to the four hydrogen atoms (Fig. 1.9). The vector sum of the four vectors is zero and hence
methane is a non-polar molecule. Water has two strong dipoles, the vector sum is not zero
(Fig. 1.8) and it is therefore a polar molecule. Polyethylene is an example of a non-polar
polymer. Each methylene unit has a weak dipole moment perpendicular to the chain axis
(Fig. 1.8). The net dipole moment is, however, zero for two adjacent methylene groups.
Poly(vinyl chloride) is a polar polymer because of its strong C-Cl dipole moment and the lack
of symmetry.

Figure 1.8. Drawings of methane, water and a repeating unit of polyethylene isplaying their
net dipole moments with the arrows

Polarisation is another important phenomenon. All atoms and molecules polarise when
they are subjected to an electric field. Non-polar molecules polarise by the displacement of the

6
electronic clouds relative to the positively charged nuclei under the influence of the electric
field. This leads to an induced dipole moment (uind), which is given by:

uind = !E (1.1)

where α is the polarisability and E is the electric field strength. Molecules that are charged or
have dipoles will induce dipoles in otherwise non-polar molecules. Table 1.2 shows a list of
bond polarisabilities. Evidently, double bonds (σ and π bond) are more polarisable than σ
bonds alone. The calculation of molecular polarisability is very easy in some instances; e.g.
the polarisability of methane is simply four times the polarisability of C-H. The additivity
principle fail for molecules that have bonds that are interdependent, e.g. molecules with
delocalised electrons as in benzene.

Table 1.2. Electronic polarisabilities of bonds given in (4πε0) Å3 a

C-C (aliphatic) 0.48 C-O 0.60

C=C (aromatic) 1.07 C=O 1.36
C=C 1.65 N-H 0.74
C-H 0.65 C-Cl 2.60
O-H 0.73 C-Br 3.75
a
Data collected by Israelachvili (1992).

It was established since more than fifty years ago that all intermolecular forces are
basically electrostatic in origin. The Hellman-Feynman theorem states that, once the spatial
distribution of the electron clouds has been determined by solving the Schrödinger equation,
the intermolecular forces may be calculated by classical electrostatics. There is a very serious
‘but’ here, namely that the exact solution of the Schrödinger equation is not attainable, even
for a simple molecule like H2. This is the main reason why the secondary bonds are divided
into different categories despite the fact that they all have the same origin. The interaction
between two ions with charges Q1 and Q2, although not particularly relevant for organic
polymers, is described by the Coulomb law:

Q1 Q2
U( r ) = (1.2)
4!" 0"r

where U is the energy, r is the distance between the charges, ε0 is the dielectric permittivity in
vacuum and ε is the dielectric constant of the surrounding medium. The coulomb forces
(f=∂U/∂r) extend over long distances; these forces decay with respect to r-2.

7
 The interaction between two permanent dipoles can be calculated on the basis of the
Coulomb law. It is important to note that both attractive and repulsive forces result from the
interaction and that the energy-distance relationship differs from the Coulomb law. The energy
also depends on the angles between the r vector and the two dipole moment vectors (θ1, θ2)
and between the two dipole moments (φ):

u1u 2
U(r ,! 1, !2 , ") = # (2 cos!1 cos! 2 # sin !1 sin! 2 cos" ) (1.3)
4$% 0 %r 3

When the dipoles are separated, particularly when they are shielded in a medium with high
dielectric constant, the interaction energy becomes smaller than the thermal energy (RT) and
the dipoles can rotate freely. In this case, often referred to as the Keesom interaction, the
energy (UDD) shows a more rapid increase with r:

u12 u22
UDD ( r ) = ! 2 (1.4)
3( 4"# 0 #) kTr 6

The interaction between permanent dipoles and induced dipoles (of molecules that are
originally non-polar), often referred to as the Debye interaction, is described by the following
equation:

u12" 0
UDID ( r ) = ! (1.5)
(4#$ 0 $ )2 r 6
where α0 is the polarisability of the interacting group (induced dipole).

Finally, there is another type of force, which acts between all atoms and molecules, even
the neutral atoms like the rare gases and hydrocarbons. These forces have been given many
different names: dispersion forces, London forces, charge-fluctuation forces and induced-
dipole-induced-dipole forces. Dispersion forces make a very important contribution to the total
van der Waals force, which is thus the sum of the dispersion forces and the forces originating
from interactions between two permanent dipoles, and between permanent and induced
dipoles. Dispersion forces are quantum mechanical in origin, but they can be explained more
intuitively by simple electrostatics. The electrons in an atom are moving around their nucleus.
At any given time, there will be a small dipole moment (this will average out to zero over a
longer time period), which will generate a small electric field that will in turn induce a dipole
moment in a nearby atom. The interaction between these two temporary dipoles gives rise to
an attractive force between the two atoms. London derived in 1937 an expression for the
energy (UDISP) of a bond between two identical atoms:

8
 3 2
" 0h#
UDISP ( r ) = ! 4 (1.6)
(4$% 0 )2 r 6

where h is the Planck constant and ν is the orbiting frequency of the electron. London also
derived an expression for two dissimilar atoms and it has the same distance dependence as in
Eq. (1.6), i.e. UDISP is proportional to r-6. The strength of the dispersion forces is of the order of
one to a few RT (<5 kJ mol-1) at room temperature.

It is striking that Eqs. (1.4-1.6) express the same distance dependence,U α r-6. The total van
der Waals energy (UVDW) is the sum of the three contributions:

"CVDW
U VDW = U DD + U DID + U DISP = (1.7)
r6

A few important facts can be stated about the van der Waals forces. The dispersion forces
! are generally dominant. However, all three terms in Eq. (1.7) make contributions to UVDW in
polar systems, whereas for unpolar systems only the third term contributes. Hence, the van der
Waals energies are greater for polar molecules than for non-polar molecules. The van der
Waals energy of A-B can be calculated as the geometric mean value of A-A and B-B. This
simple method is, however, not valid for interactions involving highly polar molecules e.g.
water.

Eqs. (1.4-1.7) suggest that the energy would be at a minimum for r= 0, but this is obviously
not correct. At very small interatomic distances the electron clouds of atoms overlap and very
strong repulsive forces arise. These forces are sometimes referred to as exchange repulsion,
hard core repulsion or steric repulsion. Atoms behave in a sense like table tennis balls with a
certain radius, which is obvious from X-ray diffraction data. This is expressed in the so-called
van der Waals radius. The repulsive potential (UR) is conveniently described by the power-law
expression:

+A
U R ( r) = (1.8)
rn

where A is a constant and n is an integer between 9 and 16. The well-known Lennard-Jones
! potential brings together the repulsive (with n= 12) and the attractive potential functions:

A B
U ( r) = " (1.9)
r12 r 6

9
where A and B are constants. Fig. 1.9 shows schematically the full pair potential function as a
function of the interatomic distance. The slope is very steep indeed for r-values less than the
bond length.
These potential functions are used as input data for molecular dynamics (MD)
simulation. In this case, the Coulomb law describes the electrostatic interaction:

Q1Q2
UQ = (1.10)
4!"r

where the dielectric constant (ε) is dependent on r; for very short interatomic distances it
approach unity and it gradually increases with increasing r to finally reach the dielectric
constant of the material.

Alternatively, the electrostatic interaction may be described by the mutual induction

method. The van der Waals interaction is described by the Lennard-Jones potential [Eq. (1.9)].
Dipole-dipole interaction is thus considered by applying the Coulomb law directly.

Figure 1.9. Energy as a function of Figure 1.10. Hydrogen bond established

interatomic distance according to the between two water molecules.
Lennard-Jones potential.

Hydrogen bonds are exceptionally strong intermolecular bonds. They are developed
between hydrogen covalently bound to a strongly electronegative atom (e.g. O, N, F and Cl)
and an electronegative atom of similar type. It is now accepted that the hydrogen bond is
predominantly a strong electrostatic interaction. The strength of the hydrogen bond is between
10 and 50 kJ mol-1, which is greater by an order of magnitude than the van der Waals bonds
but smaller than the strength of the covalent bonds. Hydrogen bonds are very important for
biological systems. The DNA helices are stabilised by hydrogen bonds. The structure and the
very high heat of vaporisation of water are direct consequences of the strong hydrogen bonds
(Fig. 1.10). The intramolecular O-H distance is 0.10 nm. The intermolecular O-H distance is
only 0.176 nm, which is much shorter than the sum of the two van der Waals radii, 0.26 nm.
The energy of a hydrogen bond is often described by the 10-12 potential:

10
 $C D'
U H ( r," ) = & 12 # 10 ) cos4 " (1.11)
%r r (

where C and D are constants and θ is the angle between the hydrogen bond and the covalent
! bond between the hydrogen and the attached atom. The hydrogen bond has three features that
make it different from the van der Waals bonds: (a) high strength; (b) strong directional
dependence, which is evident from the cosine factor in Eq. (1.11); (c) short action range,
which is evident from the high exponent (n= 10) of the attractive term in Eq. (1.11).

1.4. Configuration and conformation

The term configuration refers to the ‘permanent’ stereostructure of a polymer. The

configuration is defined by the polymerisation method. A change in configuration requires the
rupture of covalent bonds. Different configurations exist in polymers with stereocentres
(tacticity) and double bonds (cis and trans forms). A polymer with the constitutional repeating
unit –CH2-CHX- exhibits two different stereoforms (configurational base units) for each
constitutional repeating unit. The following convention is adopted to distinguish between the
two stereoforms: One of the chain ends is first selected as the near one. The asymmetric
carbon atom (the one with the attached X atom (group of atoms)) is then placed so that its H-
and X-linkages are pointing upwards. The term dextro (d) form is then given to the
arrangement with the X group pointing to the right (from the observer at the near end). The
levo (l) form is the mirror image of the d form, i.e. the X-group in this case points to the left.
This convention is not however absolute. If the near and far chain ends are reversed, i.e. if the
chain is viewed from the opposite direction, the d and l notation is reversed for a given chain.
When writing a single chain down on paper, the convention is that the atoms on the left-hand
side of the paper are assumed to be nearer to the observer than the atoms on the right-hand
side.

Tacticity is an indication of the orderliness of the succession of configurational base units

in the main chain of a polymer molecule. An isotactic polymer is a regular polymer consisting
of only one species of configurational base unit, i.e. only the d or the l form (Fig. 1.11). These
can be converted into each other by simple rotation of the whole molecule. Thus, in practice
there is no difference between an all-d chain and an all-l chain. A small mismatch in the chain
ends does not alter this fact. A syndiotactic polymer consists of an alternating sequence of the
different configurational base units, i.e. ...dldldldldldl... (Fig. 1.11). An atactic polymer has
equal numbers of randomly distributed configurational base units.

Polymers with double bonds in the main chain, e.g. polydienes, show different
stereostructures. Fig. 1.12 shows the two stereoforms of 1,4-polybutadiene: cis and trans. The
double bond is rigid and allows no torsion and the cis and trans forms are not readily
transferable into each other. Polyisoprene is a well-known example: natural rubber consists

11
almost exclusively of the cis-form whereas gutta-percha is composed of the trans form. Both
polymers are naturally abundant, and this shows that stereoregularity was achieved in nature
much earlier than the discovery of coordination polymerisation by Ziegler and Natta.

Figure 1.11. Regular tactic chains of [-CH2 -CHX-]n, where X is indicated by a filled circle

Figure 1.12. Stereoforms of 1,4-polybutadiene showing only the constitutional repeating unit
with the rigid central double bond

Vinyl polymers (-CH2-CHX-) may show different configurations with respect to the head
(CHX) and tail (CH2), viz. head-to-head i.e. -CHX bonded to CH2-, and head-to-head--tail-to-
tail, i.e. -CHX bonded to -CHX followed by –CH2 bonded to -CH2 (Fig. 1.13).

12
Figure 1.13. Head-to-tail configuration (upper chain) and a chain with a head-to-head
junction followed by a tail-to-tail sequence (lower chain)

The configurational state determines the low-temperature physical structure of the polymer.
A polymer with an irregular configuration, e.g. an atactic polymer, will with very few
exceptions, never crystallise and it freezes to a glassy structure at low temperatures, whereas a
polymer with a regular configuration, e.g. an isotactic polymer, may crystallise at some
temperature to form a semi-crystalline material. There is a spectrum of intermediate cases in
which crystallisation occurs but to a significantly reduced level.

A conformational state refers to the stereostructure of a molecule defined by its sequence of

bonds and torsion angles. The change in shape of a given molecule due to torsion about single
(σ) bonds is referred to as a change in conformation (Fig. 1.14). Double and triple bonds,
which in addition to the rotationally symmetric sigma bond also consist of one or two
rotationally asymmetric π bonds, permit no torsion. There are only small energy barriers, from
a few to 20 kJ mol-1, involved in these torsions. The multitude of conformations available for
polymers is very important for their properties.

Figure 1.14. Examples of conformational states of C7H16. The right-hand form is generated
from the left-hand form by 120° torsion about the σ bond indicated by the arrow.

13
 The rapid change in conformation is responsible for the sudden extension of a rubber
polymer on loading and for the extraordinarily high ultimate extensibility of the network. This
is the topic of Chapter 8. The high segmental flexibility of the molecules at high temperatures
and the low flexibility at low temperatures are very useful signatures of polymers.

1.5. Homopolymers and copolymers

A homopolymer consists of only one type of constitutional repeating unit (A). A

copolymer, on the other hand, consists of two or more constitutional repeating units (A,B,
etc). Several classes of copolymers are possible: block copolymers, alternating copolymers,
graft copolymers and statistical copolymers (Fig. 1.15).

Figure 1.15. Homopolymer and different classes of copolymers. Unit A: ❍; unit B: ●

The different copolymers with constitutional repeating units A and B are named according
to the source-based nomenclature rules as follows: unspecified type: poly(A-co-B); statistical
copolymer: poly(A-stat-B); alternating copolymer: poly(A-alt-B); graft copolymer: poly(A-
graft-B). The major constituent (A) is given first. Note that the constitutional repeating unit of
the backbone chain of the graft copolymer is specified first.

A random copolymer is a special type of statistical copolymer. The probability of finding

a given constitutional repeating unit at any given site in a random copolymer is independent of
the nature of the adjacent units at that position. A statistical copolymer may however obey
known statistical laws, e.g. Markovian statistics. The term random copolymer is occasionally
used for polymers with the additional restriction that the constitutional repeating units are
present in equal amounts. The notation for a random copolymer is poly(A-ran-B).
Copolymerisation provides a route for making polymers with special, desired property
profiles. A statistical copolymer consisting of units A and B, for instance, has in most cases
properties intermediate between those of the homopolymers (polyA and polyB). An important
deviation from this simple rule arises if either polyA or polyB is semi-crystalline. The

14
statistical copolymer (poly(A-stat-B)) is for most compositions fully amorphous. Block and
graft copolymers form in most cases a two-phase morphology and the different phases exhibit
properties similar to those of the respective homopolymers. Di-block (A-B) and tri-block (A-
B-A) copolymers are often made by so-called living polymerisation. These polymers have
found applications as thermoplastic elastomers and as compatibilisers to increase the adhesion
between the phases in polymer blends. Terpolymers consist of three different repeating units:
A, B and C.

1.6. Molecular architecture

Molecular architecture deals with the shape of a polymer molecule. Examples of polymers
with different molecular architectures are shown in Fig. 1.16.

Figure 1.16. Schematic representation of structures of polymers with different molecular

architectures.

A short-chain branch has an oligomeric nature whereas a long-chain branch is of

polymeric length. A network polymer consists of many inter-connected chain segments and
many different molecular paths exist between any two atoms. A dendrimer (exact structure)
and a hyperbranched (dendritic polymer with structural irregularities) polymer consist of a
constitutional repeating unit including a branching group. The number of branches increases
according to a power law expression with the number of the "generation" of the polymer. The
molecular architecture is important for many properties. Short-chain branching tends to reduce
crystallinity. Long-chain branches have profound effects on the rheological properties.
Ladder polymers are typically thermally stable and mechanically strong. Dendrimers consist
of molecules with an approximately spherical shape, and it has been shown that their melt
viscosity is significantly lower than that of their linear analogue with the same molar mass.
Crosslinked polymers are thermosets, i.e. they do not melt. They also show little creep under
constant mechanical loading.

15
1.7. Common polymers

A list of common polymers with their constitutional repeating units is presented in Table
1.3. Most polymers are named polyx. If ‘x’ is a single word, the name of the polymer is
written out directly, as in the case of polystyrene. However, if ‘x’ consists of two or more
words, parentheses should be used, as in the case of poly(methyl methacrylate). There are two
different systems for naming polymers. The structure-based names are rigorous but seldom
used in practice. They are simply given as poly(constitutional repeating unit) and the rules of
nomenclature for the constitutional repeating unit are no different from those of any other
organic substance. The source-based names attach ‘poly’ to the name of the monomer.
Polystyrene is a source-based name. Its structure-based equivalent is poly(1-phenylethylene).
Polyethylene (source-based name) is denoted polymethylene according to the structure-based
system. The names of polymers treated in this book are almost exclusively related to the
source-based system. Most polymers have abbreviated names, which are also presented in
Table 1.3. It is clearly acceptable to use abbreviations in scientific papers and technical
reports, but the full name of the polymer should be given the first time it appears in the text.
There are numerous other names of polymers that are frequently used. ‘Nylon’, ‘Kevlar’ and
‘Vectra’ are a few well-known examples. The source-based or structure-based names are
preferred over these truly trivial names.

Table 1.3. Constitutional repeating units of common polymers

Polymer name, abbreviation Constitutional repeating unit

Polyethylene, PE

Polypropylene, PP

Poly(vinyl chloride), PVC

Polystyrene, PS

16
Poly(vinyl alcohol), PVAL

Poly(vinyl acetate), PVAC

Poly(4-methyl-1-pentene)

Poly(1,4-butadiene), PBD

Polyisoprene

Poly(dimethyl siloxane), PDMS

Polyacrylonitrile, PAN

Poly(methyl methacrylate), PMMA

Poly(alkyl methacrylate)s

Poly(alkyl acrylate)s

17
Poly(ethylene terephthalate), PETP

Poly(butylene terephthalate), PBTP

Polytetrafluoroethylene, PTFE

Polyamide 6, PA 6

Polyamides n, PA n

Polyamide 6,10, PA 6,10

Polyoxymethylene, POM

Poly(ethyleneoxide), PEO

Poly(vinylidene dichloride), PVDC

Poly(vinylidene difluoride), PVDF

1.8. Molar mass

The enormous size of polymer molecules gives them unique properties. Fig. 1.17 shows the
influence of molar mass on the melting point of polyethylene.

Low molar mass substances (oligomers) show a strong increase in melting point with
increasing molar mass, whereas a constant melting point is approached in the polymer molar
mass range. Other polymers show a similar behaviour. Properties such as fracture toughness and
Young's modulus show a similar molar mass dependence with almost constant values being
approached in the high molar mass region. The polymer properties are often obtained in the

18
molar mass range from 10 000 to 30 000 g mol-1. Rheological properties like melt viscosity
show a progressive strong increase with increasing molar mass even at high molar masses. High
molar mass polymers are therefore difficult to process but they yield final products with very
good mechanical properties.

There is currently no polymerisation method available that yields a polymer with molecules
of a single size. Variation in molar mass among the different molecules is characteristic of all
synthetic polymers. The molar mass distribution ranges over three to four orders of magnitude
for many polymers. Monodisperse polymers can however be found in the nature. A full
representation of the molar mass distribution is currently achieved only with size exclusion
chromatography, naturally with a number of experimental limitations. Other methods yield
different averages.

Figure 1.17. Molar mass dependence of the equilibrium melting point of oligo- and
polyethylene.

The most commonly used averages are defined as follows. The number-average is given
by:

! N iM i (1.12)
i
Mn = = ! n iM i
! Ni i
i

where Ni is the number of molecules of molar mass Mi, and ni is the number fraction of those
molecules. The weight-average is given by:

! Ni M i2 ! Wi Mi (1.13)
i i
Mw = = = ! wi Mi
! Ni Mi ! Wi i
i i

19
where Wi is the mass of the molecules of molar mass Mi, and wi is the mass fraction of those
molecules. The z-average is given by:

! N i Mi 3 (1.14)
i
Mz =
! N i Mi2
i

The viscosity-average is given by:

1
" ! N M 1+a % a (1.15)
i i
$ '
Mv = $ i '
N M
$ ! i i '
# i &

where a is the exponent in the Mark-Houwink equation. It takes values between 0.5 and 0.8
depending on the combination of polymer and solvent.
All these averages are equal only for a perfectly monodisperse polymer. In all other cases,
the averages are different: Mn < M v < Mw < Mz . The viscosity average is often relatively close
to the weight average.

Table 1.4. Experimental techniques for molar mass determination

Method Result Comments

End group analysis Mn Absolute method,
restricted to low M

Colligative methods: Mn Absolute methods

ebulliometry, cryoscopy
and osmometry

Viscometry Mv Relative method,

easy to use

Light scattering Mw Absolute method

Ultracentrifugation Mw ; Mz Absolute method,

requires long time

Size exclusion Molar mass distribution Relative method,

chromatography (SEC) requires calibration

MALDI-TOF-MS Molar mass distribution Absolute method,

Restricted to
M<300 000 g mol-1

20
1.9. Thermal transitions and physical structures

It is useful to divide the polymers into two main classes: the fully amorphous and the
semicrystalline. The fully amorphous polymers show no sharp crystalline Bragg reflections in
the X-ray diffractograms taken at any temperature. The reason why these polymers are unable
to crystallise is commonly their irregular chain structure. Atactic polymers, statistical
copolymers and highly branched polymers belong to this class of polymer.

The semicrystalline polymers show crystalline Bragg reflections superimposed on an

amorphous background. Thus, they always consist of two components differing in degree of
order: a crystalline component composed of thin (10 nm) lamella-shaped crystals and an
amorphous component. The degree of crystallinity can be as high as 90% for low molar mass
linear polyethylene and as low as 5% for poly(vinyl chloride).

The differences in crystallinity lead to differences in physical properties. Fig. 1.18 shows,
for example, the temperature dependence of the relaxation modulus for different polystyrenes.
The relaxation modulus is defined as the stress divided by the strain as recorded after 10 s of
constant straining, a so-called stress relaxation experiment.

Figure 1.18. The logarithm of the relaxation modulus (10 s) as a function of temperature for
semicrystalline (isotactic) polystyrene and fully amorphous (atactic) polystyrene in three
"versions": crosslinked and uncrosslinked low and high molar mass uncrosslinked. Drawn
after data from Tobolski (1960).

At 100°C, the fully amorphous polystyrenes show a drop in modulus by a factor of 1000.
This "transition" is called the glass transition. All fully amorphous polymers show a similar
modulus-temperature curve around the glass transition temperature (Tg). The material is said
to be "glassy" at temperatures below Tg (region I). Under these conditions, they are hard

21
plastics with a modulus close to 3 GPa. The glassy polymer is believed to show very little
segmental mobility. Conformational changes are confined to small groups of atoms. The
deformation is predominantly due to stretching of secondary bonds and bond angle
deformation ("frozen spaghetti deformation"). The glass transition shows many kinetic
peculiarities and it is not a true thermodynamic phase transition as in the melting of a crystal.
In region II, the transitional region, the polymer shows damping. Such materials are referred to
as "leather-like". Materials in region II are lossy; the work done on such a polymer is to a
significant extent converted into heat. Such materials can be useful to extinguish vibrations.

At temperatures above Tg, the materials are rubber-like with a modulus of a few MPa
(region III). Above the glass transition temperature relatively large groups of atoms, of the
order of 100 main chain atoms, can change their conformation. Crosslinked materials show
elastic properties in this temperature region. The rate at which the conformational changes
occur is so high that the strain response to a step change in stress is instantaneous.

Uncrosslinked polymers show a pronounced drop in modulus at higher temperatures. The

temperature region at which the modulus remains practically constant, the so-called rubber
plateau, is much longer for the high molar mass material than for the low molar mass material
(Fig. 1.18). This indicates that the low modulus characteristic of materials in region V is due
to sliding motions of molecules which occur more readily in low molar mass polymers with
few chain entanglements. Crosslinked polymers show no region V behaviour because the
crosslinks prevent the sliding motion.

Semicrystalline polystyrene shows a weak glass transition at 100°C (Fig. 1.18), due to a
softening of the amorphous component of this two-phase polymer. The author did not report
the fraction of crystalline component but it was probably about 20%. The crystalline
component remains unchanged through the glass transition region. The crystallites act as
crosslinks and the rubber modulus of the amorphous component is higher than that of the
wholly amorphous polystyrene. The glass transition is hardly visible in high-crystalline
polymers like polyethylene. The pronounced drop in modulus occurring at 230°C is due to the
melting of the crystalline component of the material.

1.10. Polymeric materials

It is common to divide plastic materials into thermoplastics and thermosets.

Thermoplastics are composed of linear or branched polymer molecules and for that reason
they melt. Thermoplastics are first synthesised and then at a later stage moulded. Thermosets
are cross-linked polymers that do not melt. An uncrosslinked prepolymer is given the desired
final shape and then crosslinked to produce the detail.

The structure of the polymers used, the additives and the processing methods and
conditions determine the properties of a polymer material. It is for example possible to make

22
an extremely stiff and strong fibrous material from polyethylene. Conventionally processed
polyethylene has a stiffness of only about 1 GPa, whereas fibrous polyethylene may exhibit a
longitudinal modulus of 100 GPa. Some polymer materials are almost pure with only a small
content of additives, whereas others consist of predominantly non-polymeric constituents.
Fibre-reinforced composites consist of reinforcing fibres in a polymer matrix and the
function of the polymer is merely to provide the shape of the product and to transfer forces
from one fibre to another. The reinforcing fibres give the composites their high strength and
stiffness (Fig. 1.19). Composites can also be based on particles of other shapes: spheres and
plates. Nanocomposites refer to materials containing a ultrafine particles; at least one of the
dimensions should be in the nanometer-size range (1-50 nm).

Fig. 1.19. Carbon-fibre reinforced sports product

Polymers would not be used to the extent that they are if it were not for the additives.
Some polymers like polyethylene may contain only a small portion of antioxidant to prevent
the polymer from oxidising. Other polymeric materials, particularly rubbers, contain both
large numbers and large amounts of additives, e.g. antioxidants, carbon black, oil, fillers,
reinforcing fibres, initiators, an accelerator for vulcanisation, and an inhibitor in order to avoid
early crosslinking.

An increasingly important field is to reduce the risk of fire without using halogen-
containing polymers. This is accomplished with the use of flame-retardants. Some polymers
like poly(vinyl chloride) are used with plasticizers, i.e. miscible low molar mass liquids.
Numerous polymeric materials contain large fractions of fillers. The purpose of using fillers
can be cost-reduction, reduced mould-shrinkage, promotion of crystal nucleation or
improvement of the mechanical properties. The list of additives used in polymers can be made
longer but for our purposes the list presented here is sufficient.

23
1.11. Short polymer history

It is intended in this section to give only a very short presentation of the development of
polymer materials and ideas in polymer science in this section. Morawetz (1985) and Rånby
(1993) give a detailed presentation of this field.
The first polymers used were all obtained from natural products. Natural rubber from the
Hevea trees was being used by the American Indians when Columbus arrived in 1492. Cellulose
in different forms, starch and collagen in leather are other examples of natural polymers.
Modification of native polymers started in the mid-nineteenth century and the first wholly
synthetic polymer was made in the beginning of the 20th century. The science of polymers
began in the 1920s.
The development of polymer science and technology has occurred primarily during the last
80 years and the commercial introduction of new polymers had proceeded through three time-
stages giving rise to three generations of polymers:
The first generation was introduced before 1950 and includes polystyrene, poly(vinyl
chloride), low-density polyethylene, polyacrylates, polymethacrylates, glass-fibre-reinforced
polyesters, aliphatic polyamides, styrene-butadiene rubber and the first synthetic paints (alkyds).
The second generation of polymers was introduced during 1950-1965 and includes a number
of commodity and engineering plastics like high-density polyethylene, isotactic polypropylene,
polycarbonates, polyurethanes, epoxy resins, polysulphones and aromatic polyesters, also used
for films and fibres. New rubber materials, acrylic fibres made of polyacrylonitrile and latex
paint were also introduced.
The third generation, introduced since 1965, consists mainly of speciality polymers with a
more complex chemical structure. The signatures of these polymers can be very high thermal
and chemical stability and high strength/stiffness. Examples of these materials are
poly(phenylene sulphide) (Ryton®), polyaryletherketone (PEEK®), polyimides (Kapton®),
aromatic polyesters (Ekonol® and Vectra®), aromatic polyamides (Nomex® and Kevlar®) and
fluor-containing polymers (Teflon® and Viton®). Parallel to this development of new polymers,
existing polymers such as polyethylene have undergone significant improvement. Crosslinked
polyethylene and new fracture-tough thermoplastic polyethylenes are examples of the more
recently introduced materials.

A "polymer calender" is presented below with the important progress steps indicated. Many
important accomplishments have however been omitted to keep the list reasonably short.

1839: Charles Goodyear (USA) discovered that sulphur-containing natural rubber turned elastic
after heat-treatment. Vulcanisation was discovered and utilised.

1848: Thomas Hancock (USA) made polymer blends based on natural rubber and gutta percha.

24
1861: Thomas Graham, a British chemist, found that starch and cellulose could not pass through
fine filters. He proposed that these substances represented a different organisation of matter,
colloids (after kolla, the Greek word for glue). He believed that these substances consisted of
relatively small molecules held together by association forces.

1862: Alexander Parks (USA) modified cellulose with nitric acid to form cellulose nitrate and
by mixing this polymer with a plasticiser he made a material named ‘Parkesine’. A few years
later, John and Isaiah Hyatt patented a similar material named ‘celluloid’ (cellulose nitrate
plasticised with camphor).

1880: The French chemist Gustave Bouchardat created a rubber-like substance from isoprene.
Isoprene had been obtained some 20 years earlier by Greville Williams (UK) by distillation
from natural rubber.

1904: Carl Harries (Germany) proposed that the rubber-like substances made from isoprene
formed a ring structure that remained closely packed by strong association forces.

1907: The Belgium-born Leo Baekeland (USA) made "Bakelite", the first wholly synthetic
polymer. Bakelite is a thermoset made from phenol and formaldehyde.

1911: PS was made by Matthews (UK) but it took almost 20 years before it came into
commercial use (IG Farben, Germany).

1912: PVC was first synthesised by the Russian Ostromislensky. It took another 25 years before
it became commercial (B. F. Goodrich, USA).

1920: Hermann Staudinger, a German organic chemist, formulated the macromolecular concept.
Staudinger based his idea on results obtained by studies of materials derived from the compound
ketene. Staudinger presented the idea at a lecture already in 1917. Despite the fact that the
general view at this time was that these materials (including rubbers) consisted of relatively
small molecules held together by association forces, the concept of large molecules was not
new. Peter Klason, a Swedish chemist reported already in 1897 that lignin in wood was formed
mainly from coniferyl alcohol units connected to ‘large molecules’, mainly by ether bonds.
During the 1920s the macromolecular idea was under debate with Staudinger in favour and a
relatively large group of scientists against the new idea. A statement of a German chemist after a
debate in 1926: ‘We are shocked like zoologists would be if they were told somewhere in Africa
an elephant was found who was 1600 feet long and 300 feet high’. Staudinger received the
Nobel Prize in chemistry in 1953. Staudinger proposed incorrectly, however, that the polymer
molecules were rigid rods. Herman Mark, a German chemist that moved to USA, opposed to
this view and suggested correctly that the polymer molecules had a considerable flexibility.

1925: Theodor Svedberg (Sweden; Nobel Laureate in chemistry in 1926) constructed the
ultracentrifuge and was the first to make an unambiguous determination of a very high molar
mass.

25
1929: Styrene-butadiene rubber (Buna-S) was made by I. G. Farben, Germany.

1930s: Carl Marvel at the University of Illinois (USA) contributed strongly to the US Synthetic
Rubber Project. This giant project that involved 1000 chemists was largely motivated by World
War II. In 1942 production of synthetic rubber in USA reached 20 000 tons.

1930s: Werner Kuhn, Herman Mark and Eugene Guth found evidence that polymer chains in
solution were flexible and that the viscosity in solution was related to the molar mass of the
polymer.

1934-: The statistical mechanical theory for rubber elasticity was first qualitatively formulated
by Werner Kuhn, Eugene Guth and Herman Mark. The entropy-driven elasticity was explained
on the basis of conformational states. The initial theory dealt only with single molecules, but
later development by these pioneers and by other scientists formulated the theory also for
polymer networks. Eugene Guth and Hubert James formulated the first stress-strain equation
based on statistical mechanics in 1941.

1930s: Wallace Hume Carothers, a brilliant research chemist at DuPont Experimental Station,
USA, studied polycondensation reactions first synthesising aliphatic polyesters, and later and
more importantly polyamide 6,6 (nylon). Later work with radical polymerisation led to the
synthesis of polychloroprene. Carothers' research not only supported the macromolecular
concept but also showed the industrial importance of synthetic polymers.

1930s: Paul Flory, at one time a team member of Carothers research group, derived and
experimentally confirmed the Gaussian molar mass distribution for polymers made by step-
growth polymerisation. Later Flory showed that polymers made by anionic polymerisation
adapted to the narrower Poisson distribution of chain lengths. Flory also postulated the
existence of chain-transfer reactions in chain-growth polymerisation. Flory received the Nobel
Prize in chemistry in 1974 for these and later fundamental achievements in the physical
chemistry of macromolecules.

1933: Low-density polyethylene was made by Eric William Fawcett (ICI, UK). This is how the
story is told in most textbooks. In fact, many more scientists and practitioners were greatly
involved. The story is beautifully told by Harmar-Brown [1954) and Gibson (1980): On 27th
March1933, E. W. Fawcett and R. O. Gibson, two UK chemists at ICI performed the experiment
that yielded the white, waxy solid. They attempted to examine the possibility to react
benzaldehyde and ethylene gas at very high pressure, a suggestion made by Professor Robert
Robinson, UK. Elemental analysis of the substance showed however no presence of oxygen and
Fawcett and Gibson correctly concluded that the substance was a polymer based on ethylene.
Several explosions occurred in later experiments and the work was stopped. This grand
discovery was however preceded by very important work on high-pressure apparatus, which
originated from Antonius Michels in the Netherlands. A few years later, after Vigars, Manning

26
and Colbeck development of new safer equipment, Paton, Williams and Bebbington made 8 g
low-density polyethylene in a reactor at 200 MPa. The date was 20th December 1935. Michels
continuous gas compressor and a pressure vessel designed by Manning was used for pilot plant
work in 1938 and the first ton of polyethylene was made this year. In 1938, Mr. J. N. Dean of
Submarine Cables Ltd., UK learned about polyethylene and recognized its potential value for
insulating submarine cables. ICI delivered 150 tons of polyethylene for the two Scotland-
Norway cables during the period 1939-1940. This was the birth of the commercial success of
polyethylene.
1936: Epoxy resins were made by Pierre Castan (Switzerland)
1938: Silicone rubbers were made by Eugene Rochow (USA).
1939: Polytetrafluoroethylene (Teflon®) was made by Roy Plunkett (USA).
1942: Paul Flory and Maurice Huggins (USA) presented, independently, the thermodynamic
theory for polymer solutions.
1940s: Flory was very active in many areas during this decade. He made his contribution to
rubber elasticity together with Rehner, developed a theory for gelation, by which the gel point
can be predicted from the degree of "conversion", and developed a theory for the excluded
volume effect of polymer molecules in solution. Flory introduced the theta solvent concept.
Under theta conditions, the polymer molecules have unperturbed dimensions. Flory also
predicted that the shape of molecules in a pure melt should be the same as under theta
conditions.
1940s: Glass-fibre reinforced polyester was made in Germany.
1954: Karl Ziegler (Germany) and Guilio Natta (Italy) discovered that polymerisation in the
presence of certain metal-organic catalysts yielded stereoregular polymers. Both were awarded
the Nobel Prize in chemistry in 1963. Their work led to the development of linear polyethylene
and isotactic polypropylene. The preparation of linear polyethylene using chromium oxide
catalyst by Paul Hogen and coworkers at Phillips Petroleum Co, USA occurred also during the
1950s.
1949-56: Theories for liquid crystals of rod-like polymers were proposed by Lars Onsager in
1949 and by Paul Flory in 1956.
1955: Malcolm Williams, Robert Landel and John Ferry (USA) presented an empirical but very
general equation (WLF equation) describing the viscoelasticity of amorphous polymers.
1956: Michael Szwarz, USA, discovered living anionic polymerisation. This technique
permitted the preparation of narrow molar mass fractions and ‘exact’ di- and tri-block
copolymers. Thermoplastic elastomers, like Kraton ® (Shell Chemical Co, USA) are prepared by
living anionic polymerisation.

27
1957: Andrew Keller, Bristol, UK, found that polymer molecules were folded at the large
surfaces of lamella shaped single-crystals of polyethylene. The general shape of the single
crystals and the crystal axes orientation but without the explicit expression about the chain
folding was also reported by Erhart Fischer (Germany) and Paul Till (USA) in 1957. The first
suggestion about chain folding goes back however to Keith Storks in 1938 dealing with gutta-
percha but it passed largely unnoticed by the scientific community.
1960: Polyoxymethylene (Delrin®) was made by DuPont Co, USA.
1961: Aromatic polyamide (Nomex®) was made by DuPont Co, USA.
1962: Blends of poly(phenylene oxide) (PPO) and polystyrene with the commercial name
Noryl ® (General Electric Co, USA) were first made.
1968: Stefanie Kwolek and Paul Morgan, research chemists at DuPont reported that solutions of
poly(phenylene terephthalamide) could be spun to super-strong and stiff fibers. They showed
that the solutions possessed liquid crystalline order. The fibres were later commercialised under
the name Kevlar®.
1970-1985: Ultra-oriented polyethylene with mechanical properties approaching those of metals
was made by solid-state processes, in some cases combined with solution processes. A number
of scientists were active in the field: Ian Ward (UK), Roger Porter (USA), Albert Pennings, Piet
Lemstra and Paul Smith (Netherlands), and Dusan Prevorsek (USA). The pioneering work of
elucidating the mechanisms of transformation from the isotropic to the fibrous polymer is due to
Anton Peterlin (USA).
1971: Pierre-Gilles deGennes, a French physicist who was awarded the Nobel Prize in physics
in 1992, presented the reptation model which describes the diffusion of chain molecules in a
matrix of similar chain molecules. Masao Doi and Sam Edwards later further developed the
reptation model.
1972-: The first melt-processable, later categorised as thermotropic, liquid crystalline polymer,
based on p-hydroxybenzoic acid and bisphenol terephthalate, was reported by Steven Cottis in
1972. This polymer is now available on the market under the name Xydar®. In 1973, Herbert
Kuhfuss and W. Jerome Jackson, Eastman Kodak Co, USA patented the first well-characterised
thermotropic polymer, a copolyester of p-hydroxybenzoic acid and ethylene terephthalate. They
reported the discovery of liquid crystalline behaviour in this polymer in 1976. In the beginning
of the 1980's, the Celanese Company developed a family of processable thermotropic liquid
crystalline polymers based on p-hydroxybenzoic acid and p-hydroxynaphthoic acid, later named
Vectra®.
Mid 1970's-: Theories for the crystallisation of polymers were introduced by John Hoffman
(USA) and coworkers and later in the 1980's by David Sadler (UK).
1976: The research group of Frisch (USA) published the first report on interpenetrating polymer
networks (IPN).

28
1977: The first electrically conductive polymer was prepared by doping of polyacetylene by
Alan MacDiarmid (USA), Alan Heeger (USA) and Hideka Shirikawa (Japan). These scientists
received in 2000 the Nobel Prize in chemistry.
1978: The German scientists Heino Finkelmann, Michael Happ, Michael Portugall and Hellmut
Ringsdorf suggested that a decoupling of the main chain and the mesogen motion was possible
through the insertion of a flexible spacer in side-chain liquid crystalline polymers. After this
breakthrough, an abundance of side-chain polymers have been synthesised and the combinations
of main chains, spacers and mesogens appear to be infinite.
1980s: The molecular interpretation of relaxation processes in polymers developed strongly
using molecular mechanics modelling particularly due to the work of Richard Boyd, USA.
David Bassett and associates at the University of Reading, UK introduced the permanganic
etching technique, which led to a strong development in the understanding of the morphology of
polymers.
1984: Dendrimers were first synthesised by Donald Tomalia and coworkers (USA).
Hyperbranched polymers were made a few years later at the DuPont Experimental Station
(USA).
1990s: Polyolefins with uniform molecular structure and a narrow molar mass distribution were
made by a new polymerisation technique using metallocene catalysts. The technological start-up
with a demonstration plant was by Exxon in 1991. The scientific foundation was provided by
the pioneering work of Walter Kaminsky (Germany) dating back to the late 1970s.

1.12. Exercises

1.1 When was the first synthetic polymer made? What polymer was it?
1.2. Plot the potential energy as a function of the interatomic distance for a pair of atoms
assuming London forces and hydrogen bond.
1.3. Calculate the net dipole moment for dimethyl ketone using the bond dipole moments
provided in Table 1.1.
1.4. Write the constitutional repeating unit structures of the following polymers: PE, PP, PMMA
and PA8
1.5. Explain briefly the difference between the concepts of configuration and conformation.
1.6. Why can atactic polystyrene not crystallize?
1.7. What kind of branches is obtained in a copolymer of ethylene and 1-octene?

1.13. References

Berzelius, J. (1832) Jahres-Bericht Fortschr. Phys. Wissensch., 11, 44.

Boyd, R. H. and Phillips, P. J. (1993) The Science of Polymer Molecules, Cambridge University
Press, Cambridge.

29
Brandrup, J., Immergut, E. H. and Grulke, E. A. (eds.) (1999) Polymer Handbook, 4th ed.,
Wiley, New York.
Gibson, R. O. (1980) Chemistry and Industry, 16 August, 635.
Harmar-Brown, F. M. S. (1954) ICI Magazine, September, 258.
Hogan, J. P. and Banks, R. L. (Phillips Petroleum Co.) (1958) U.S. Patent 2,825,721.
Houwink, R. (1940) J. Prakt. Chem., 157, 15.
Israelachvili, J. (1992) Intermolecular and Surface Forces, 2nd ed., Academic Press, London.
Kausch, H. H. (1987) Polymer Fracture, Springer-Verlag, Berlin.
Kuhn, W. (1934) Kolloid Z., 68, 2.
London, F. (1937) Trans. Faraday Soc., 33, 8.
Mark, H. (1938) in Der Feste Körper, Sänger, R. (ed.), Hirzel, Leipzig.
Metanomski, W. V. (ed.) (1991) Compendium of Macromolecular Nomenclature, Blackwell
Scientific, Oxford.
Morawetz, H. (1985) Polymers: The Origins and Growth of a Science, Wiley, New York.
Rånby, B. (1993) Background- polymer science before 1977, in Nobel Symposium 81,
Conjugate Polymers and Related Structures, Oxford University Press .
Staudinger, H. and Nodzu, R. (1930) Ber., 63, 721.
Tobolski, A. V. (1960) Properties and Structure of Polymers, Wiley, New York.

30