Pamantasan ng Lungsod ng

Maynila
College of Engineering and Technology
Department of Chemical Engineering

BASIC CONCEPTS IN POLYMER

ENGINEERING AND HISTORY,
IMPACT AND FUTURE OF
POLYMERS

SUBMITTED BY:
CONGE, JUSTIN PAUL N.
DE UMANIA, GENESIS JAMES L.
PEDROSA, ALYSSA RIEZLE
SABLAN, ANNA ANGELICA
SANGALANG, KIM PATRICK H.
VELASCO, DIANA ISIS S.
BSCHE V
SUBMITTED TO:
ENGR. KIM BRYAN DUENAS
NOVEMBER 19, 2016

Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology
Department of Chemical Engineering

POLYMER
The word polymer is derived from classical Greek poly meaning many and
meres meaning parts. Thus a polymer is a large molecule (macromolecule) built
up by the repetition of small chemical units.
To illustrate this, the figure below shows the formation of the polymer polystyrene.

The styrene molecule (1) contains a double bond. Chemists have devised
methods of opening this double bond so that literally thousands of styrene
molecules become linked together. The resulting structure, enclosed in square
brackets, is the polymer polystyrene (2). Styrene itself is referred to as a monomer,
which is defined as any molecule that can be converted to a polymer by combining
with other molecules of the same or different type. The unit in square brackets is
called the repeating unit.
Notice that the structure of the repeating unit is not exactly the same as that
of the monomer even though both possess identical atoms occupying similar
relative positions. The conversion of the monomer to the polymer involves a
rearrangement of electrons. The residue from the monomer employed in the
preparation of a polymer is referred to as the structural unit.
In the case of polystyrene, the polymer is derived from a single monomer
(styrene) and, consequently, the structural unit of the polystyrene chain is the same
as its repeating unit. Other examples of polymers of this type are polyethylene,
polyacrylonitrile, and polypropylene. However, some polymers are derived from the
mutual reaction of two or more monomers that are chemically similar but not
identical. For example, poly(hexamethylene adipamide) or nylon 6,6 (5) is made
from the reaction of hexamethylenediamine (3) and adipic acid (4)
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Degree of Polymerization (DP)

The subscript designation, n, indicates the number of repeating units strung
together in the polymer chain (molecule). This is known as the degree of
polymerization (DP). It specifies the length of the polymer molecule. Polymerization
occurs by the sequential reactions of monomers, which means that a successive
series of reactions occurs as the repeating units are linked together.
This can proceed by the reaction of monomers to form a dimer, which in turn
reacts with another monomer to form a trimer and so on. Reaction may also be
between dimers, trimers, or any molecular species within the reaction mixture to
form a progressively larger molecule. In either case, a series of linkages is built
between the repeating units, and the resulting polymer molecule is often called a
polymer chain, a description which emphasizes its physical similarity to the links in
a chain.
Low-molecular-weight polymerization products such as dimers, trimers,
tetramers, etc., are referred to as oligomers.
They generally possess undesirable thermal and mechanical properties. A
high degree of polymerization is normally required for a material to develop useful
properties and before it can be appropriately described as a polymer. Polystyrene,
with a degree of polymerization of 7, is a viscous liquid (not of much use), whereas
commercial grade polystyrene is a solid and the DP is typically in excess of 1000.
The degree of polymerization represents one way of quantifying the
molecular length or size of a polymer. This can also be done by use of the term
molecular weight (MW). By definition, MW (Polymer) = DP x MW (Repeat Unit).
Example is polystyrene (2). There are eight carbon atoms and eight hydrogen atoms
in the repeating unit. Thus, the molecular weight of the repeating unit is 104 (8 x 12
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+ 1 x 8). If, as we stated above, we are considering commercial grade polystyrene,

we will be dealing with a DP of 1000. Consequently, the molecular weight of this
type of polystyrene is 104,000, where molecular weight has a profound effect on the
properties of a polymer.
In case a polymer would have more than one kind of repeat units in its chain
molecular structure, it is called a copolymer. Polymers of the molecular weight
range 1,000 20,000 are commonly called low polymers and those having
molecular > 20,000 are commonly referred to as high polymers.

Length to Diameter (L/D) Ratio

Length to Diameter (L/D) ratio of polymer molecules in general is very high
compared to that of a simple, small molecule (such as the monomer molecule). If a
small molecule such as the styrene molecule is represented by a dot ( ), then the
molecule of a polymer, for example, polystyrene DP of 1000 will be represented by
a line (----) formed by firmly jointing or sticking together of 1000 dots in a linear
fashion. This unique difference in the L/D ratio between a monomer (small)
molecule and a polymer or a high polymer molecule makes all the difference in their
physical and mechanical properties. A long pearl necklace could be viewed as a
model for a polymer molecule.

CLASSIFICATION OF POLYMERS
Polymers can be classified in many different ways. The most obvious classification is
based on the origin of the polymer, i.e., natural vs. synthetic. Other classifications
are based on the polymer structure, polymerization mechanism, preparative
techniques, or thermal behavior.

A. NATURAL VS. SYNTHETIC

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Polymers may either be naturally occurring or purely synthetic. All the

conversion processes occurring in our body (e.g., generation of energy from our
food intake) are due to the presence of enzymes. Life itself may cease if there is a
deficiency of these enzymes. Enzymes, nucleic acids, and proteins are polymers of
biological origin. Their structures, which are normally very complex, were not
understood until very recently. Starch a staple food in most cultures cellulose,
and natural rubber, on the other hand, are examples of polymers of plant origin and
have relatively simpler structures than those of enzymes or proteins. There are a
large number of synthetic (man-made) polymers consisting of various families:
fibers, elastomers, plastics, adhesives, etc. Each family itself has subgroups.
B. POLYMER STRUCTURE
1. Linear, Branched or Cross-linked, Ladder vs. Functionality
A polymer is formed when a very large number of structural units (repeating
units, monomers) are made to link up by covalent bonds under appropriate
conditions. Certainly even if the conditions are right not all simple (small) organic
molecules possess the ability to form polymers. In order to understand the type of
molecules that can form a polymer, let us introduce the term functionality.
The functionality of a molecule is simply its interlinking capacity, or the
number of sites it has available for bonding with other molecules under the specific
polymerization conditions. A molecule may be classified as monofunctional,
bifunctional, or polyfunctional depending on whether it has one, two, or greater
than two sites available for linking with other molecules. For example, the extra pair
of electrons in the double bond in the styrene molecules endows it with the ability
to enter into the formation of two bonds. Styrene is therefore bifunctional. The
presence of two condensable groups in both hexamethylenediamine (NH2) and
adipic acid (COOH) makes each of these monomers bifunctional. However,
functionality as defined here differs from the conventional terminology of organic
chemistry where, for example, the double bond in styrene represents a single
functional group. Besides, even though the interlinking capacity of a monomer is
ordinarily apparent from its structure, functionality as used in polymerization
reactions is specific for a given reaction.
The structural units resulting from the reaction of monomers may in principle
be linked together in any conceivable pattern. Bifunctional structural units can enter
into two and only two linkages with other structural units. This means that the
sequence of linkages between bifunctional units is necessarily linear.
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The resulting polymer is said to be linear. However, the reaction between

polyfunctional molecules results in structural units that may be linked so as to form
nonlinear structures. In some cases the side growth of each polymer chain may be
terminated before the chain has a chance to link up with another chain. The
resulting polymer molecules are said to be branched. In other cases, growing
polymer chains become chemically linked to each other, resulting in a cross-linked
system.

Substituent groups that are attached to the main chain of skeletal atoms are known
as pendant groups.
Their structure and chemical nature can confer unique properties on a
polymer. For example, linear and branched polymers are usually soluble in some
solvent at normal temperatures. But the presence of polar pendant groups can
considerably reduce room temperature solubility. Since cross-linked polymers are
chemically tied together and solubility essentially involves the separation of solute
molecules by solvent molecules, cross-linked polymers do not dissolve, but can only
be swelled by liquids. The presence of cross-linking confers stability on polymers.
Highly cross-linked polymers are generally rigid and high-melting. Cross-links occur
randomly in a cross-linked polymer. Consequently, it can be broken down into
smaller molecules by random chain scission.
Ladder polymers constitute a group of polymers with a regular sequence of
cross-links. A ladder polymer, as the name implies, consists of two parallel linear
strands of molecules with a regular sequence of crosslinks. Ladder polymers have
only condensed cyclic units in the chain; they are also commonly referred to as
double-chain
or
double-strand
polymers.
A
typical
example
is
poly(imidazopyrrolone) (27), which is obtained by the polymerization of aromatic
dianhydrides such as pyromellitic dianhydride (25) or aromatic tetracarboxylic acids
with orthoaromatic tetramines like 1,2,4,5-tetraaminobenzene (26):
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The molecular structure of ladder polymers is more rigid than that of

conventional linear polymers. Numerous members of this family of polymers display
exceptional thermal, mechanical, and electrical behavior. Their thermal stability is
due to the molecular structure, which in essence requires that two bonds must be
broken at a cleavage site in order to disrupt the overall integrity of the molecule;
when only one bond is broken, the second holds the entire molecule together.
2. Amorphous or Crystalline
Structurally, polymers in the solid state may be amorphous or crystalline.
When polymers are cooled from the molten state or concentrated from the solution,
molecules are often attracted to each other and tend to aggregate as closely as
possible into a solid with the least possible potential energy. For some polymers, in
the process of forming a solid, individual chains are folded and packed regularly in
an orderly fashion. The resulting solid is a crystalline polymer with a long-range,
three-dimensional, ordered arrangement. However, since the polymer chains are
very long, it is impossible for the chains to fit into a perfect arrangement equivalent
to that observed in low-molecular-weight materials. A measure of imperfection
always exists. The degree of crystallinity, i.e., the fraction of the total polymer in the
crystalline regions, may vary from a few percentage points to about 90% depending
on the crystallization conditions.
In contrast to crystallizable polymers, amorphous polymers possess chains
that are incapable of ordered arrangement. They are characterized in the solid state
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by a short-range order of repeating units. These polymers vitrify, forming an

amorphous glassy solid in which the molecular chains are arranged at random and
even entangled.
Solid states of crystalline and amorphous polymers are characterized by a
long-range order of molecular chains and a short-range order of repeating units,
respectively. On the other hand, the melting of either polymer marks the onset of
disorder. There are, however, some polymers which deviate from this general
scheme in that the structure of the ordered regions is more or less disturbed. These
are known as liquid crystalline polymers. They have phases characterized by
structures intermediate between the ordered crystalline structure and the
disordered fluid state. Solids of liquid crystalline polymers melt to form fluids in
which much of the molecular order is retained within a certain range of
temperature. The ordering is sufficient to impart some solid-like properties on the
fluid, but the forces of attraction between molecules are not strong enough to
prevent flow.
Liquid crystalline polymers are important in the fabrication of lightweight,
ultra-high-strength, and temperature-resistant fibers and films such as Duponts
Kevlar and Monsantos X-500. The structural factors responsible for promoting the
above classes of polymers will be discussed when we treat the structure of
polymers.
3. Homopolymer or Copolymer
Polymers may be either homopolymers or copolymers depending on the
composition. Polymers composed of only one repeating unit in the polymer
molecules are known as homopolymers. However, chemists have developed
techniques to build polymer chains containing more than one repeating unit.
Polymers composed of two different repeating units in the polymer molecule are
defined as copolymers. An example is the copolymer formed when styrene and
acrylonitrile are polymerized in the same reactor.

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The repeating units on the copolymer chain may be arranged in various

degrees of order along the backbone; it is even possible for one type of backbone to
have branches of another type. There are several types of copolymer systems:
Random copolymer the repeating units are arranged randomly on the chain
molecule. It we represent the repeating units by A and B, then the random
copolymer might have the structure shown below:
AABBABABBAAABAABBA
Alternating copolymer there is an ordered (alternating) arrangement of the
two repeating units along the polymer chain:
ABABABABABAB
Block copolymer the chain consists of relatively long sequences (blocks) of
each repeating unit chemically bound together:
AAAAA BBBBBBBB AAAAAAAAA BBBB
Graft copolymer Sequences of one monomer (repeating unit) are grafted
onto a backbone of another monomer type:

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4. Fibers, Plastics, or Elastomers

Polymers may also be classified as fibers, plastics, or elastomers. The reason
for this is related to how the atoms in a molecule (large or small) are hooked
together. To form bonds, atoms employ valence electrons. Consequently, the type of
bond formed depends on the electronic configuration of the atoms. Depending on
the extent of electron involvement, chemical bonds may be classified as either
primary or secondary.
In primary valence bonding, atoms are tied together to form molecules using
their valence electrons. This generally leads to strong bonds. Essentially there are
three types of primary bonds: ionic, metallic, and covalent. The atoms in a polymer
are mostly, although not exclusively, bonded together by covalent bonds.
Secondary bonds on the other hand, do not involve valence electrons.
Whereas in the formation of a molecule atoms use up all their valence bonds, in the
formation of a mass, individual molecules attract each other. The forces of
attraction responsible for the cohesive aggregation between individual molecules
are referred to as secondary valence forces. Examples are van der Waals, hydrogen,
and dipole bonds. Since secondary bonds do not involve valence electrons, they are
weak. (Even between secondary bonds, there are differences in the magnitude of
the bond strengths: generally hydrogen and dipole bonds are much stronger than
van der Waals bonds.) Since secondary bonds are weaker than primary bonds,
molecules must come together as closely as possible for secondary bonds to have
maximum effect.
The ability for close alignment of molecules depends on the structure of the
molecules. Those molecules with regular structure can align themselves very closely
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for effective utilization of the secondary intermolecular bonding forces. The result is
the formation of a fiber.
Fibers are linear polymers with high symmetry and high intermolecular
forces that result usually from the presence of polar groups. They are characterized
by high modulus, high tensile strength, and moderate extensibilities (usually less
than 20%).
At the other end of the spectrum, there are some molecules with irregular
structure, weak intermolecular attractive forces, and very flexible polymer chains.
These are generally referred to as elastomers. Chain segments of elastomers can
undergo high local mobility, but the gross mobility of chains is restricted, usually by
the introduction of a few cross-links into the structure. In the absence of applied
(tensile) stress, molecules of elastomers usually assume coiled shapes.
Consequently, elastomers exhibit high extensibility (up to 1000%) from which they
recover rapidly on the removal of the imposed stress. Elastomers generally have
low initial modulus in tension, but when stretched they stiffen.
Plastics fall between the structural extremes represented by fibers and
elastomers. However, in spite of the possible differences in chemical structure, the
demarcation between fibers and plastics may sometimes be blurred. Polymers such
as polypropylene and polyamides can be used as fibers and as plastics by a proper
choice of processing conditions.
C. POLYMERIZATION MECHANISM
Polymers may be classified broadly as condensation, addition, or ringopening polymers, depending on the type of polymerization reaction involved in
their formation.
Condensation polymers are formed from a series of reactions, often of
condensation type, in which any two species (monomers, dimers, trimers, etc.) can
react at any time leading to a larger molecule. In condensation polymerization, the
stepwise reaction occurs between the chemically reactive groups or functional
groups on the reacting molecules. In the process, a small molecule, usually water or
ammonia, is eliminated. A typical condensation polymerization reaction is the
formation of a polyester through the reaction of a glycol and a dicarboxylic acid.

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Addition polymers are produced by reactions in which monomers are added

one after another to a rapidly growing chain. The growing polymer in addition
polymerization proceeds via a chain mechanism. Like all chain reactions, three
fundamental steps are involved: initiation, propagation, and termination. Monomers
generally employed in addition polymerization are unsaturated (usually with carboncarbon double bonds).
As the name suggests, ring-opening polymerization polymers are derived
from the cleavage and then polymerization of cyclic compounds. A broad
generalization of ring-opening polymerization is shown below.

The nature of the cyclic structure is such that in the presence of a catalyst it
undergoes equilibrium ring-opening to produce a linear chain of degree of
polymerization, n. X is usually a heteroatom such as oxygen or sulfur; it may also be
a group such as lactam or lactone. A number of commercially important polymers
are obtained via ring-opening polymerization. Thus, trioxane (33) can be
polymerized to yield polyoxymethylene (34), the most important member of the
family of acetal resins, and caprolactam (35) undergoes ring-opening to yield nylon
6 (36), an important textile fiber used especially for carpets.

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The original classification of polymers as either condensation or addition

polymers as proposed by Carothers does not permit a complete differentiation
between the two classes or polymers, particularly in view of the new polymerization
processes that have been developed in recent years. Consequently, this
classification has been replaced by the terms step-reaction (condensation) and
chain-reaction (addition) polymerization. These terms focus more on the manner in
which the monomers are linked together during polymerization.
D. THERMAL BEHAVIOR
For engineering purposes, the most useful classification of polymers is based
on their thermal (thermomechanical) response. Under this scheme, polymers are
classified as thermoplastics or thermosets. As the name suggests, thermoplastic
polymers soften and flow under the action of heat and pressure. Upon cooling, the
polymer hardens and assumes the shape of the mold (container). Thermoplastics,
when compounded with appropriate ingredients, can usually withstand several of
these heating and cooling cycles without suffering any structural breakdown. This
behavior is similar to that of candle wax. Examples of thermoplastic polymers are
polyethylene, polystyrene, and nylon.

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A thermoset is a polymer that, when heated, undergoes a chemical change to

produce a cross-linked, solid polymer. Thermosets usually exist initially as liquids
called prepolymers; they can be shaped into desired forms by the application of
heat and pressure, but are incapable of undergoing repeated cycles of softening and
hardening. Examples of thermosetting polymers include ureaformaldehyde,
phenol formaldehyde, and epoxies.
The basic structural difference between thermoplastics and thermosets is
that thermoplastic polymers are composed mainly of linear and branched
molecules, whereas thermosets are made up of cross-linked systems. Recall from
our previous discussion that linear and branched polymers consist of molecules that
are not chemically tied together. It is therefore possible for individual chains to slide
past one another. For cross-linked systems, however, chains are linked chemically;
consequently, chains will not flow freely even under the application of heat and
pressure.
The differences in the thermal behavior of thermoplastics and thermosets are
best illustrated by considering the change in modulus with temperature for both
polymers. At low temperatures, a thermoplastic polymer (both crystalline and
amorphous) exists as a hard and rigid glass. As the temperature is increased, it
changes from a glass to a rubbery elastomer to a viscous melt that is capable of
flowing hence this phase is also known as the flow region. (The transitions
between the different phases or regions of thermal behavior are characterized by
drops in the magnitude of the modulus usually two to three orders. For the
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thermosetting polymer, on the other hand, the modulus remains high in the rubbery
region, while the flow region disappears.
E. TACTICITY
A vinyl and related polymer ( CH2 CHR ) is characterized by an asymmetric
carbon atom (marked with a little asterisk on it) in each of the repeat units of its
chain molecules and a type of stereochemical difference that may arise in the
segments of the chain is d , l isomerism. Considering head to tail linkage of the
repeat units, the stereo sequences may be all d or all l sequences, identified
in terms of tacticity or spatial disposition of the substituent group, R as isotactic

For alternate appearance of d and l sequences, the relevant polymer is called

syndiotactic. The syndiotactic sequence or stereoisomer may be represented as

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A third distinguishable long chain sequence called atactic sequence would be

given by a random spatial disposition of the substituent R groups, also exemplified
by a random mix of isotactic and syndiotactic sequences, viz.

Isotactic sequence is distinctive as being very regular, while atactic sequence

is one that is highly irregular. Syndiotactic sequence may be viewed as regularly
irregular or vice versa. Isotactic and syndiotactic polymers are considered as
stereospecific or stereoregular while atactic polymers are viewed as random or
stereoirregular. The overall molecular symmetry and crystallinity are in the order
isotactic > syndiotactic >> atactic. Isotactic polymers are generally characterized
by high melting temperature (Tm) and high mechanical properties with relatively
high resistance to solvents and chemicals.
F. PREPARATIVE TECHNIQUE
Polymers can be classified according to the techniques used during the
polymerization of the monomer. In bulk polymerization, only the monomer (and
possibly catalyst and initiator, but no solvent) is fed into the reactor. The monomer
undergoes polymerization, at the end of which a (nearly) solid mass is removed as
the polymer product. Bulk polymerization is employed widely in the manufacture of
condensation polymers, where reactions are only mildly exothermic and viscosity is
mostly low thus enhancing ready mixing, heat transfer, and bubble elimination.
Solution polymerization involves polymerization of a monomer in a solvent in
which both the monomer (reactant) and polymer (product) are soluble.
Suspension polymerization refers to polymerization in an aqueous medium
with the monomer as the dispersed phase. Consequently, the polymer resulting
from such a system forms a solid dispersed phase.
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Emulsion polymerization is similar to suspension polymerization but the

initiator is located in the aqueous phase (continuous phase) in contrast to the
monomer (dispersed phase) in suspension polymerization. Besides, in emulsion
polymerization the resulting polymer particles are considerably smaller (about ten
times smaller) than those in suspension polymerization.
G. END USE
Finally, polymers may be classified according to the end use of the polymer.
In this case, the polymer is associated with a specific industry (end use): diene
polymers (rubber industry); olefin polymer (sheet, film, and fiber industries); and
acrylics (coating and decorative materials).

SUMMARY OF CLASSIFICATION OF POLYMERS

Basis of Classification

Polymer Types
(a) Natural (as available
in nature)

(b) Semisynthetic
(Man made)
1. Origin

(c) Synthetic
(Man made)

2. Thermal response

(a) Thermoplastics (they

soften or melt on heating
and harden on cooling
over many cycles of
heating and cooling and
retain solubility and
fusibility).

Examples
Natural rubber, natural
silk, cellulose, proteins,
starch etc.
Hydrogenated,
halogenated and cyclo
(natural) rubber;
cellulosics (cellulose
esters/ethers), etc.
Polyethylene,
polypropylene, polystyrene, polybutadiene,
nylon poly-amides,
polycarbonates,
phenolics, amino resins,
epoxy resins etc.
Polyethylene,
polypropylene, polystyrene, nylon
polyamides, linear
polyester [poly (ethylene
terephthalate)] , etc.
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(b) Thermosetting (they

usually soften or melt
initially on heating, but
fast undergo chemical
changes to finally turn
insoluble and infusible).
3. Mode of formation
(a) Chain growth or
addition

(b) Step growth or

condensation

4. Line Structure
(a) Linear
(having no branches)

(b) Branched
(having branches)

(c) Cross linked or

network (having a
complex network
structure)
5. Application and
Physical properties
(a) Rubbers
(showing long range
elasticity)

(b) Plastics
(shapable under pressure,

Phenolic resin, amino

resins, epoxy resins,
diene rubbers
(vulcanized), unsaturated
polyesters.
Polyethylene and other
polyolefins, Polystyrene
and related vinyl
polymers etc.
Polyesters and
polyamides,
polycarbonates, phenol
(urea, melamine)
formaldehyde resins,
epoxy resins etc.
High density polyethylene
(HDPE), polyvinyls,
bifunctional (polyesters
and polyamides) etc.
Low density polyethylene
(LDPE), higher poly (olefins), phenolic resoles
and resitols, poly (3hydroxy alkanoates) etc.
Phenolic C-stage (resite)
resin, C-stage amino
(urea / melamine-formaldehyde) resins, cured
epoxy resin and
unsaturated polyester
resin etc.
Natural rubber, (1, 4 cis
poly isoprene) synthetic
rubbers (polybuta-diene,
SBR, nitrile rubber,
polychlo-roprene rubber,
polylacrylate rubber,
polyurethane rubbers,
silicone rubbers etc.)
Polyethylenes,
polypropylene (isotactic),
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aided by heat)

(c) Fibres
(available in fibrillar or
filamentous form)

6. Tacticity

(a) Isotactic
(stereoregular)
(b) Syndiotactic ( do )
(c) Atactic (stereo
irregular)

(a) Crystalline
(crystallinity, > 50%)

7. Crystallinity

(b) Semi crystalline

(crystallinity, 30 50%)

(c) Amorphous or noncrystalline

(crystallinity < 25%)

polystyrene, poly (vinyl

chloride), nylon
polyamides linear
aromatic polyesters and
polyamides,
polycarbonates, acetal
resins etc.
Cotton (cellulose), natural
silk, artificial silk (rayons),
poly (ethylene
terephthalate) fibre,
nylon polyamide fibres
etc.
Poly (-olefins) and all
vinyl and related
polymers.
Polyethylene (HDPE and
LDPE), polypropylene
(isotactic), stretched
nylon polyamides,
polyoxymethylene etc.
cellulose (cotton) fibre.
Polybutene, cellulosics
(cellulose esters (rayons)
particularly if stretched),
Gutta percha (1, 4 trans
polyisoprene) etc.
Natural rubber and most
synthetic rubbers,Nalkylated(>15%
alkylation) nylon
polyamides, poly
(methacry-lates and
acrylates) poly (vinyl
acetate), polystyrene etc.

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HISTORY, IMPACT AND FUTURE OF POLYMERS

History of Polymer
Polymers have long existed on Earth even before it was known to mankind.
But through different researches and breakthroughs, polymers are now diverse and
have countless of usage. To briefly discuss the historical development of polymers
refer to the timeline below.
YEAR

1751

1802

1832

DESCRIPTION
French geographer Charles-Marie de la Condamine described the
collection and use of rubber in Ecuador which was the first complete
account of rubber technology.

British natural philosopher John Gough discovered that natural rubber

produced heat when stretched and became hard (crystallized) when
cooled under extension.

Swedish chemist Jns Jacob Berzelius used the term polymeric (parallel
to isomeric) to describe two compounds with the same empirical formula
but different molecular weights. Although his example was incorrect, the
word polymer gradually came into use.
French physicist and chemist Victor Regnault observed the
polymerization of vinylidene chloride that was probably the first published
account of polymerization, although he did not recognize it as such.

1838

1839

German pharmacist Eduard Simon reported the conversion of liquid

styrene to solid meta-styrene, which he took to be an oxide of styrene.

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1839

1845

American
inventor,
Charles
Goodyear
began
experiments on the hardening of rubber by heating it
with sulfur. This process, which Goodyear called
vulcanization, made hardly usable rubber gum into a
major article of commerce. Independent experiments on
vulcanization were carried out in Britain in the early
1840s by Thomas Hancock, who worked on the
processing of rubber for over twenty years and may be
fairly described as the first rubber technologist.

German chemist August Wilhelm von Hofmann with John Blyth

showed that meta-styrene had the same empirical formula as styrene and
correctly described it as a styrene polymer.

1845
German chemist Christian Schnbein discovered both nitrocellulose
(cellulose dinitrate) and guncotton (cellulose trinitrate). Schnbein
spilled a mixture of concentrated nitric and sulfuric acids, powerful
mineral acids that dissolve copper and other metals and readily destroy
organic tissues. Because the mixture was corrosive, he grabbed the
nearest item, his wifes cotton apron, to wipe up the mess. After washing
it out, he put the apron in front of the fire to dry. It flared brightly, almost
explosively and disappeared.

Thophile-Jules Pelouze had reported the reaction of cellulose with

nitric acid in 1838, but Schnbein discovered the importance of adding
sulfuric acid to the nitric acid. He made articles out of nitrocellulose but
afterwards concentrated, unsuccessfully, on the development of
guncotton. The first useful explosive from guncotton (cordite) was
invented by the English chemist Sir Frederick Abel with Sir James
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Dewar in 1889.

1863

French chemist Marcelin Berthelot gave the first general

discussion of polymers and polymerization as part of a
lecture on isomerism.
French chemist Paul Schtzenberger prepared cellulose
acetate.

1865

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British inventor Alexander Parkes experimented with nitric acid/sulfuric

acid mixtures and succeeded in making a partially nitrated cellulose that
was still soluble in a variety of solvent but far less flammable called
pyroxyline. After removal of the acid and the washing, the pyroxyline
was mixed with a variety of solvents to make a viscous mass that could
be molded into different shapes. A typical formula for Parkesine was 100
parts pyroxline (moistened with naphtha), 1050 parts nitrobenzole (or
aniline or camphor) and 150-200 parts vegetable oil.

1865

1869

He took out a patent for Parkesine, a plastic made from a solution of

nitrocellulose in wood naphtha. Parkes had displayed Parkesine at the
1862 International Exhibition in London. In 1867 Parkess coworker Daniel
Spill, produced a more tractable material from a mixture of nitrocellulose,
camphor, and castor oil. After several commercial failures, this material
(Xylonite) was successfully developed by Spill and an American, Levi
Merriam, in the late 1870s.
American inventor John Wesley Hyatt perfected Parkess nitrocellulosecamphor mixture and developed celluloid, the first commercially
successful plastic. Hyatt and his brother were awarded a patent for the
preparation and molding of a plastic material that was based upon a
mixture of cellulose nitrate and camphor. By incorporating the plasticizer
(camphor) to facilitate the molding of cellulose nitrate, the Hyatt brothers
had removed volatile solvents from the mixture, which essentially
eliminated the shrinking and warping of articles as these solvents
evaporated. Hyatt formed the Celluloid Manufacturing Company.
Celluloids applications included combs, dentures, knife handles, toys, and
spectacle frames.

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1878

1884

German chemist Eugene Baumann studied the photopolymerization of

vinyl chloride. The action of sunlight remained the standard method for
polymerizing vinyl compounds, despite the obvious drawback, until the
mid-1920s.
French chemist Hilaire Bernigaud, Comte de Chardonnet deposited a
sealed envelope with the French Academy of Sciences which described his
method of producing artificial silk from nitrocellulose by removing the
nitrate groups by hydrolysis with nitric acid. The denitrification was later
carried out with sulfide solutions. Chardonnet established a factory in
Besanon in 1891, and Chardonnet silk enjoyed moderate success
before it was supplanted in the early 20 th century by the cheaper viscose
rayon.

1889
American chemist Henry Reichenbach worked for three years on the
development of celluloid film for Eastman Kodak. He was one of the first
trained chemists to be hired full-tie by an American company. Celluloid
and films became synonymous, even after the introduction of cellulose
acetate safety film by Eastman Kodak in 1908.

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1892

1894

British chemists Charles Cross, Edward Bevan and Clayton Beadle

developed viscose rayon. The British silk firm of Courtaulds, anxious to
move out of the morning crepe business, obtained the British rights to the
viscose process of rayon manufacture and built a factory in Coventry in
1905. The American Viscose Company, established by Courtaulds at
Marcus Hook, Pennsylvania, in 1910, was for a decade one of the most
profitable companies in America.

Charles Cross and Edward Bevan patented first industrial process for
the manufacture of cellulose acetate. Cellulose acetate was further
developed by Arthur Eichengrn of Farbenfabriken Bayer in Germany
and the American chemist George Miles. Two Swiss brothers, Henri and
Camille Dreyfus, began production of acetate lacquer and film at Basel
in 1910. World War I and the consequent demand for aircraft dope
brought about the establishment of the British and American Celanese
companies. Celanese introduced acetate fiber in 1925.

1900
Ivan Kondakov polymerized dimethylbutadiene, a synthetic compound
derived from acetone, to produce the first truly synthetic rubber. He
added a small seed of polymer to a batch of monomer, which was then
left to polymerize for several weeks.

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The oldest recorded synthetic plastic is fabricated by Leo Bakeland.

Bakelites hardness and high heat resistivity made it an excellent choice
as an electrical insulator

1910

Hermann
Staudinger
demonstrated
the
existence
of macromolecules, which he characterized as polymers. Staudinger
proposed in a landmark paper published in 1920 that rubber and
other polymers such as starch, cellulose and proteins are long chains of
short repeating molecular units linked by covalent bonds.
1920

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1933

R.O Gibson and E.W. Fawcett set off a reaction between ethylene and
benzaldehyde, in an autoclave. It seems their testing container sprang a
leak and all of the pressure escaped. There was the white, waxy
substance that greatly resembled plastic. Upon carefully repeating and
analyzing the experiment, the scientists discovered that the loss of
pressure was only partly due to a leak; the major reason was the
polymerization process that had occurred leaving behind polyethylene.

W. Carothers obtained some super-polymers that became viscous solids at

high temperatures, and the observation was made that filaments could be
made from this material if a rod were dipped in the molten polymer and
withdrawn. These filaments are named Nylon

1938

FUTURE TRENDS IN POLYMER ENGINEERING

Rapid developments in technology have triggered the creation of a variety of

plastic materials, which in turn has radically increased the consumption of plastics.
From 2000 to 2010, the worlds yearly consumption of plastics registered a massive
growth from around 350 billion pounds to over 550 billion pounds. In fact, the
development of new products have led to additional demand and enhanced
consumerism in emerging economies like China, India as well as developed
economies like the United States.
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As the world focuses on plastic engineering and plastics increasingly become

a commodity, there is a natural shift towards more productive manufacturing
methodologies that will lower the production cost. So far, plastics can be broadly
classified into elastomers, thermosets and thermoplastics. Elastomers are known for
their flexibility and include substances like silicones and neoprene. Melamines,
polyurethanes, phenolics, and epoxy-based materials, which have a soft consistency
and are resistant to re-melting, fall under the category of thermosets.
Thermoplastics, soft in consistency with re-melting and recycling capabilities, are
the most widely used type of plastic. Polystyrene, nylon, polypropylene and
polyethylene fall under this category.
BIOPLASTICS
Bioplastics are plastics derived from renewable biomass sources, such as
vegetable fats and oils, corn starch, or microbiota. Bioplastic can be made from
agricultural by-products and also from used plastic bottles and other containers
using microorganisms. Common plastics, such as fossil-fuel plastics (also called
petrobased polymers), are derived from petroleum or natural gas. Production of
such plastics tends to require more fossil fuels and to produce more greenhouse
gases than the production of biobased polymers (bioplastics). Some, but not all,
bioplastics are designed to biodegrade. Biodegradable bioplastics can break down in
either anaerobic or aerobic environments, depending on how they are
manufactured. Bioplastics can be composed of starches, cellulose, biopolymers, and
a variety of other materials.
Starch Based Bioplastics Thermoplastic starch currently represents the most
widely used bioplastic, constituting about 50 percent of the bioplastics market.
Simple starch bioplastic can be made at home. Pure starch is able to absorb
humidity, and is thus a suitable material for the production of drug capsules by the
pharmaceutical sector. Starch-based bioplastics are often blended with
biodegradable polyesters to produce starch/polycaprolactone or starch/Ecoflex
(polybutylene adipate-co-terephthalate) blends. These blends are used for industrial
applications and are also compostable. These blends are not biodegradable, but
have a lower carbon footprint than petroleum-based plastics used for the same
applications.
Cellulose Based Bioplastics. Cellulose bioplastics are mainly the cellulose esters,
(including cellulose acetate and nitrocellulose) and their derivatives, including
celluloid.
Polylactic Acid. Polylactic acid (PLA) is a transparent plastic produced from corn or
dextrose. Its characteristics are similar to conventional petrochemical-based mass
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plastics (like PET, PS or PE), and it can be processed using standard equipment that
already exists for the production of some conventional plastics.
Polyhydroxyalkanoates. Polyhydroxyalkanoates are linear polyesters produced in
nature by bacterial fermentation of sugar or lipids. They are produced by the
bacteria to store carbon and energy. In industrial production, the polyester is
extracted and purified from the bacteria by optimizing the conditions for the
fermentation of sugar. More than 150 different monomers can be combined within
this family to give materials with extremely different properties. PHA is more ductile
and less elastic than other plastics, and it is also biodegradable. These plastics are
being widely used in the medical industry.
Polyamide 11. PA 11 is a biopolymer derived from natural oil. PA 11 belongs to the
technical polymers family and is not biodegradable. Its properties are similar to
those of PA 12, although emissions of greenhouse gases and consumption of
nonrenewable resources are reduced during its production. Its thermal resistance is
also superior to that of PA 12. It is used in high-performance applications like
automotive fuel lines, pneumatic airbrake tubing, electrical cable antitermite
sheathing, flexible oil and gas pipes, control fluid umbilicals, sports shoes, electronic
device components, and catheters.
Bioderived Polyethylene. The basic building block (monomer) of polyethylene is
ethylene. Ethylene is chemically similar to, and can be derived from ethanol, which
can be produced by fermentation of agricultural feedstocks such as sugar cane or
corn. Bio-derived polyethylene is chemically and physically identical to traditional
polyethylene it does not biodegrade but can be recycled. Bio derivation of
polyethylene can also reduce greenhouse gas emissions considerably.
Genetically Modified Bioplastics. Genetic modification (GM) is also a challenge
for the bioplastics industry. None of the currently available bioplastics which can
be considered first generation products require the use of GM crops, although GM
corn is the standard feedstock. Looking further ahead, some of the second
generation bioplastics manufacturing technologies under development employ the
"plant factory" model, using genetically modified crops or genetically modified
bacteria to optimise efficiency.
With the pioneering advancements being made plastic manufacturing in this
industry, the world is increasingly becoming aware of the environmental effects of
these materials. Greener, more environmentally friendly plastics are increasingly in
demand. Eco-friendly bioplastics, which are based on polymer resins from plants,
find a wide array of applications in electronics, telecommunications, aerospace,
automotive and other markets. Plastics that decompose with the help of bacteria
have also been developed.
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SMART POLYMERS
Smart polymers or stimuli-responsive polymers are high-performance
polymers that change according to the environment they are in. Such materials can
be sensitive to a number of factors, such as temperature, humidity, pH, the
wavelength or intensity of light or an electrical or magnetic field and can respond in
various ways, like altering colour or transparency, becoming conductive or
permeable to water or changing shape (shape memory polymers). Usually, slight
changes in the environment are sufficient to induce large changes in the polymers
properties.
Smart polymers appear in highly specialised applications and everyday
products alike. They are used for the production of hydrogels, biodegradable
packaging, and to a great extent in biomedical engineering. One example is a
polymer that undergoes conformational change in response to pH change, which
can be used in drug delivery.
Smart polymers are not just for drug delivery. Their properties make them
especially suited for bioseparations. Microscopic changes in the polymer structure
are manifested as precipitate formation, which may be used to aid separation of
trapped proteins from solution. These systems work when a protein or other
molecule that is to be separated from a mix, forms a bioconjugate with the polymer,
and precipitates with the polymer when its environment undergoes a change.
Removal of this component from the conjugate depends on recovery of the polymer
and a return to its original state, thus hydrogels are very useful for such processes.
Another approach to controlling biological reactions using smart polymers is
to prepare recombinant proteins with built-in polymer binding sites close to ligand
or cell binding sites. This technique has been used to control ligand and cell binding
activity, based on a variety of triggers including temperature and light.
It has been suggested that polymers might be developed that can learn and
self-correct behavior over time. One of these is the idea of smart toilettes that
analyze urine and help identify health problems. In environmental biotechnology,
smart irrigation systems have been also been proposed. It would be incredibly
useful to have a system that turns on and off, and controls fertilizer concentrations,
based on soil moisture, pH and nutrient levels. Many creative approaches to
targeted drug delivery systems that self-regulate based on their unique cellular
surroundings, are also under investigation.
There are obvious possible problems associated with the use of smart
polymers in biomedicine. The most worrisome is the possibility of toxicity or
incompatibility of artificial substances in the body, including degradation products
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and byproducts. However, smart polymers have enormous potential

biotechnology and biomedical applications if these obstacles can be overcome.

in

NANOCOMPOSITES
Nanocomposite is a multiphase solid material where one of the phases has
one, two or three dimensions of less than 100 nanometers (nm), or structures
having nano-scale repeat distances between the different phases that make up the
material. In the broadest sense this definition can include porous media, colloids,
gels and copolymers, but is more usually taken to mean the solid combination of a
bulk matrix and nano-dimensional phase(s) differing in properties due to
dissimilarities in structure and chemistry. The mechanical, electrical, thermal,
optical, electrochemical, catalytic properties of the nanocomposite will differ
markedly from that of the component materials.
In the simplest case, appropriately adding nanoparticulates to a polymer
matrix can enhance its performance, often dramatically, by simply capitalizing on
the nature and properties of the nanoscale filler (these materials are better
described by the term nanofilled polymer composites). This strategy is particularly
effective in yielding high performance composites, when good dispersion of the filler
is achieved and the properties of the nanoscale filler are substantially different or
better than those of the matrix.
Nanoparticles such as graphene, carbon nanotubes, molybdenum disulfide
and tungsten disulfide are being used as reinforcing agents to fabricate
mechanically strong biodegradable polymeric nanocomposites for bone tissue
engineering applications. The addition of these nanoparticles in the polymer matrix
at low concentrations (~0.2 weight %) cause significant improvements in the
compressive and flexural mechanical properties of polymeric nanocomposites.
Potentially, these nanocomposites may be used as a novel, mechanically strong,
light weight composite as bone implants. The results suggest that mechanical
reinforcement is dependent on the nanostructure morphology, defects, dispersion of
nanomaterials in the polymer matrix, and the cross-linking density of the polymer.
In general, two-dimensional nanostructures can reinforce the polymer better than
one-dimensional nanostructures, and inorganic nanomaterials are better reinforcing
agents than carbon based nanomaterials. In addition to mechanical properties,
polymer nanocomposites based on carbon nanotubes or graphene have been used
to enhance a wide range of properties, giving rise to functional materials for a wide
range of high added value applications in fields such as energy conversion and
storage, sensing and biomedical tissue engineering. For example, multi-walled
carbon nanotubes based polymer nanocomposites have been used for the
enhancement of the electrical conductivity.
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Nanoscale dispersion of filler or controlled nanostructures in the composite

can introduce new physical properties and novel behaviors that are absent in the
unfilled matrices. This effectively changes the nature of the original matrix (such
composite materials can be better described by the term genuine nanocomposites
or hybrids). Some examples of such new properties are fire resistance or flame
retardancy, and accelerated biodegradability.
A range of polymeric nanocomposites are used for biomedical applications
such as tissue engineering, drug delivery, cellular therapies. Due to unique
interactions between polymer and nanoparticles, a range of property combinations
can be engineered to mimic native tissue structure and properties.
A range of natural and synthetic polymers are used to design polymeric
nanocomposites for biomedical applications including starch, cellulose, alginate,
chitosan, collagen, gelatin, and fibrin, poly(vinyl alcohol) (PVA), poly(ethylene
glycol) (PEG), poly(caprolactone) (PCL), poly(lactic-co-glycolic acid) (PLGA), and
poly(glycerol sebacate) (PGS). A range of nanoparticles including ceramic,
polymeric, metal oxide and carbon-based nanomaterials are incorporated within
polymeric network to obtain desired property combinations.

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REFERENCES
Painter, PC and Coleman, MM (2009). Essentials of Polymer Science and
Engineering, (3rd Ed). DEStech Publications, Inc.
Morris, PJT (1989). Polymer Pioneers: A Popular History of the Science and
Technology of Large Molecules. University of Pennsylvania Press.

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