LECTURE NOTE ON POLYMER SCIENCE AND TECHNOLOGY (CHE 310)

MODULE ONE

1.0 CLASSES OF POLYMERS AND THEIR RAW MATERIAL SOURCES

1.1 Introduction

What are polymers? Polymers are long-chain compounds composed of smaller molecular units
joined together by covalent bonds. Due to the large number of these smaller building blocks or
“units” which can be accommodated in these long chain molecules and consequently their high
molecular weight, they are sometimes called “giant molecules” or macromolecules. The term
macromolecules distinguish these complex compounds from simple compounds (such as ethanol,
CH3CH2OH, and carbondioxide, CO2) which can be described as monomolecular compounds.
Taking a simple compound such as cyanoethene (CH 2=CHCN) its polymer can be represented
thus

nCH2=CHCN [-CH2-CHCN-]n 1.1

cyanoethene poly(cyanoethene)

Where n is the number of repeat units contained in the polymer molecules. n is sometimes
described as the degree of polymerization (Dp). It is usually used to specify the length of the
polymer chain. The group -CH2-CHCN- is sometimes described as the repeat unit or the
monomer residue.

The molecular weight of the polymer (MWp) is the product of the repeat unit (MWr) and the
degree of polymerization (Dp), MWr.Dp

Using poly (vinylchloride) as an example, CH 2CHCl, MWr = 63, if the polymer has a Dp of
1000, thus its molecular weight = 63x1000 = 63000g/gmol.

Other examples of common polymers are shown in table 1.1.

 Table 1.1: Some common polymers and their repeat units.
Polymer Repeat unit

Polystyrene[PS] -CH2 - CH-

n

Polyethylene[ PE]

-CH2-CH2 -

Polyvinylchloride[PVC]

-CH2-CHCl- n

Polypropylene[PP]

-CH2-CH-
n
CH3

Polymethylmethacrylate [PMMA]
CH3

-CH2‒CCOOCH3 -

Polyisoprene[Natural rubber]

-CH2CH=C-CH2 -

CH3 n
1.2 Classification of polymers

The Classification of polymers is a very difficult business indeed. This is due mainly to the
diversity in the chemical structure and consequently the diverse properties and end-uses of
polymers. The difficulty arises from whether to classify polymers according to chemical
structure alone, or classify them on the basis of properties and outlet of utilization.

For example, polymers can be divided into two groups as follows

(a) Biological polymers

(b) Non Biological polymers

Biological polymers, besides providing much of our food, form the very basis of human life and
intelligence. In this scheme of classification, non- biological polymers will include most natural
and synthetic materials used for fibers, plastics and elastomers. Sometimes a simpler mode of
classification can be adopted. In this instance, polymers can be classified into natural and
synthetic materials. The natural polymers will include gums, resins, polysaccharides and
polynucleotides whereas the synthetic polymers will include the thermosetting and thermoplastic
materials and the synthetic elastomers.

The mode of classification used in this course is based on the origin of the polymer, polymer
structure, polymerization mechanism, preparative techniques, thermal behavior or end use.

1.2.1 The origin of the Polymer [Natural and synthetic]

Polymer may either be naturally occurring or purely synthetic.

Naturally occurring polymers are those derived from plants or animals and has been used for
many centuries; these materials include wood, natural rubber, cotton, wool, leather and silk.
Other natural polymers such as proteins, enzymes, starches, and cellulose are important in
biological and physiological processes in plants and animals. The synthetic (man-made)
polymers consisting of various families: plastics, fibers, synthetic rubber (elastomers), adhesive,
vanishes. Glass and porcelain are also to large extent polymeric substances. s
Today these substances (polymers) are truly indispensable to mankind, being essential to
clothing, shelter, transportation and communication as well as to the conveniences of modern
living.

1.2.2 Structure of Polymers

Based on the structure, polymers can be subdivided into four structural groups namely: linear,
branched, and cross-linked or network; Amorphous or crystalline; Homopolymer or copolymer;
fibers, plastics and elastomers.
1.2.2.1 Linear, branched, cross-linked or network
For a polymer to form linear, branched or cross-linked depend on the functionality. 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 maybe
classified as monofunctional, bifunctional or polyfunctional depending on whether it has one,
two or greater than two sites available for linking with other molecules. Before a polymer can be
formed the functionality must be at least two (2). Simple examples of bifunctional monomers
include:
Ethylene glycol, HO(CH2)2OH monomer for polyester (Terylene)
Terephthalic acid HOOC COOH monomer for polyester
Adipic acid HOOC(CH2)4COOH, monomer for nylon
(i) Reaction between two monofunctional groups
Reaction between two monofunctional groups results in compounds which has zero functionality
and thus give only low molecular weight products.
(ii) Reaction between two bifunctional groups results in linear polymers.
- Linear polymers are those in which the repeating units are joined together end to end in
single chain. These chains are flexible and may be thought of as mass of spaghetti as
shown below.
The molecules in linear polymers consist of long chains of monomers joined by bonds
that are rigid to a certain degree—the monomers cannot rotate freely with respect to each
other. Typical examples are polyethylene, polyvinyl alcohol, and polyvinyl chloride
(PVC).
(iii) Reaction between polyfunctional groups give branched and cross linked (three
dimensional) polymer.
 - Branched polymers are those in which side-branched chains are connected to the main
ones. Branched polymers have side chains that are attached to the chain molecule itself.
Branching can be caused by impurities or by the presence of monomers that have several
reactive groups. Chain polymers composed of monomers with side groups that are part of
the monomers, such as polystyrene or polypropylene, are not considered branched
polymers.
The branches, considered to be part of the main- chain molecule, result from side
reaction that occur during the synthesis of the polymer. Some of the polymers that may
form branched are polyethylene, polyvinylchloride, polystyrene, poly
methylmethacrylate, nylon. These polymers will also form linear structure.
- Cross-linked polymers are those polymers in which adjacent linear chains are joined to
another at various positions by covalent bonds, as represented below. The process of
cross linking is achieved either during synthesis or a non reversible chemical reaction that
is usually carried out at an elevated temperature. In cross-linked polymers, two or more
chains are joined together by side chains. With a small degree of cross-linking, a loose
network is obtained that is essentially two dimensional. High degrees of cross-linking
result in a tight three-dimensional structure. Cross-linking is usually caused by chemical
reactions. An example of a two-dimensional cross-linked structure is vulcanized rubber,
in which cross-links are formed by sulfur atoms. Thermosetting plastics are examples of
highly cross-linked polymers; their structure is so rigid that when heated they decompose
or burn rather than melt.
Many of the rubber elastic materials are cross linked.

A polymer that is highly cross linked may be classified as a network polymer.

1.2.2.2 Amorphous or crystalline
Structurally, polymer 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. Examples of crystalline polymers include
polyethylene, polyacrylonitrile, polyethylene terephthalate and polytetrafluoroethylene.
In contrast to crystalline polymers, amorphous polymers possess chains that are incapable of
ordered arrangement. They are characterized in the solid state 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. Polymethylmethacrylate and polycarbonate are
typical examples. In general, crystalline polymers are characterized by a long-range order of
molecular chains and a short-range order of repeating units.
1.2.2.3 Homopolymer or copolymer
When only one monomer specie is used as building block in a macromolecular substance, the
product is called a homopolymer. When the molecular chains are composed of two different
monomeric repeat units, the product is known as a copolymer.
An example is the copolymer formed when styrene and acrylonitrile are polymerized in the same
reactor

nCH2=CH + nCH2=CHCN [-CH2-CH]n-[CH2-CHCN]n

Copolymers are classified according to the disposition of the co-monomers to each other
and their arrangement in the polymer chain. There are in essential four main classes of
copolymers based on the simplest case that is copolymerization involving only two monomer
type. These classes are described briefly below.
1.2.2.3.1 Random copolymers
When the two monomeric units are arranged in a random manner in the polymer chain as shown
below
-ABBABAABAAAB-
This is termed a random copolymer. Random copolymers are thought to arise from irregular
propagation during the polymerization process.
1.2.2.3.2 Alternating copolymers
Alternatively, when the co-monomers are arranged in a regular alternating manner in the
polymer chain, this is described as an alternating copolymer.
-ABABAB-
1.2.2.3.3 Block copolymer
Block copolymers are similar in a way to the alternating copolymer except that instead of being
composed of short unit of comonomers, the copolymer contains long sequences or blocks of one
co-monomer joined to another long sequences (blocks) of the other comonomer, giving a linear
copolymer of this type
AAA-BBB-AAA-BBB-
1.2.2.3.4 Graft copolymers
As the name implies, when chains of one monomer are grafted onto the main chain or back bone
of another homopolymer, the polymer obtained is a graft copolymer. This is shown by the
following arrangements.
BBB-BBB-BBB-BBB-BBB
A A
A A
A A
1.2.2.4 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.
Chemical bonds may be classified as primary (ionic, covalent, metallic) or secondary (dipole,
hydrogen, induction, Vander waals) depending on the extent of electron involvement. Valence
electrons are involved in the formation of primary bonds- leading to quite strong bonds. On the
other hands valence electrons are not involved in the formation of secondary bonds- leading to
weak 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. The molecules with regular structure can
align themselves very closely for effective utilization of secondary intermolecular bonding force.
The result is the formation of a fiber. Fibers are linear polymers with high symmetry and high
intermolecular force that result usually from the presence of polar group. They are characterized
by high modulus, high tensile strength and moderate extensibilities (usually less than 70 %). 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. Elastomers exhibit high extensibility (up to 100 %), low modulus and tension.
Plastics fall between the structural extreme represented by fibers and elastomers.
1.2.3 Polymerization Mechanism
Polymer may be classified broadly as addition (chain-reaction) and condensation (step-
growth) polymers depending on the type of polymerization reaction involved in their
formation. Polymerization is the (chemical) process by which (one or more) monomer(s)
becomes a polymer. Polymerization process joins together the monomer molecules into large
molecule using heat, catalysts, light, and initiators. The polymerization rate and the molecule
weight of the polymer depend on temperature, pressure, catalyst activity, e.t.c.
Polymerization mechanism is divided into two groups known as condensation and addition
polymerization or, in more precise terminology, step-reaction and chain-reaction polymerization.
1.2.3.1 Condensation (or step reaction) polymerization
Is the formation of polymers by stepwise intermolecular chemical reactions that normally
involve more than one monomer specie, there is usually a small molecular weight by-product
such as water, which is eliminated. The reaction continues until almost all of one reagent is used
up, equilibrium is established that can be shifted at will at high temperatures by controlling the
amounts of reactants and products. The condensation usually takes place between two
polyfunctional molecules to produce one larger polyfunctional molecules.
1.2.3.2 Addition (or chain-reaction) polymerization
Addition polymerization is a reaction in which a single type of monomer gives rise to a single
polymer, with no other reaction products. It involves chain reactions in which the chain carrier
may be an ion or a reactive substance with one unpaired electron called a free radical. A free
radical is usually formed by the decomposition of a relative unstable material called an initiator.
The free radical is capable of reacting to open the double bond of a vinyl monomer and add to it,
with an electron remaining unpaired. In a very short time (usually a few seconds or less) many
more monomers add successfully to the growing chain. Finally two free radicals react to
annihilate each other’s growth activity and form one or more polymer molecules.
With some exception, polymers made in chain reactions often contain only carbon atoms in the
main chain (homo chain polymers), where as polymer made in step reactions may have other
atoms, originating in the monomer functional groups, as part of the chain (hetero chain
polymers).
1.2.4 Thermal Behaviour
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 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.
A thermoset is a polymer that, when heated, undergoes a chemical change to produce a cross-
linked solid polymer. Thermoset usually exist initially as liquid called prepolymer, they can be
shaped into desired forms by the application of heat and pressure, but are incapable of
undergoing repeated cycle of softening and hardening.
1.2.5 Preparative Techniques
Based on the preparative techniques, we have:
1. Bulk
2. Solution
3. Suspension
4. Emulsion
1.3 Raw Materials for the Polymer Industry
A finished polymer article may be made entirely from the neat or pure resin. More often,
it is necessary to compound the resin with additives to improve its processing behavior and/or
enhance product quality and service performance.
In this section we examine the various feed-stocks for polymer industry. The raw
materials can be divided essentially into the “base polymers” and the various additives.
1.3.1 Base Polymers
The petrochemical industry, that branch of the chemical industry which is based on the
exploitation of the crude-oil distillation products, has turned out to be the leading industry in
chemistry, where in most monomers and polymers are produced. It was preceded by the coal
industry, by the decomposition of coal at high temperature (an anaerobic process called cracking)
products like acetylene, methanol, or phenol are derived. These chemicals serve as the primary
source for an extended array of polymers.
The petrochemical industry (based on crude oil and partly on natural gas) essentially has
replaced the coal industry as the major source of monomer because petroleum as a raw material
for organic chemicals (petrochemicals) is relatively cheap, readily available in large tonnages,
and more easily processed than coal.
There are two stages involved in the production of petrochemicals from petroleum. The
first stage is the separation of petroleum, which is a mixture of hydrocarbons, into various
fractions (mainly liquid fuels) by a process called fractional distillation.
 The second stage is the further refining of certain fractions from the distillation process to
form petrochemicals. Most petrochemicals are derived from three sources:
1. Various mixtures of carbon monoxide and hydrogen, known as synthesis gas obtained
from steam reforming of natural gas (methane) or, in a few cases, steam reforming of naphtha
(light fraction with a boiling point between gasoline and kerosene).
2. Olefins and diolefins obtained by steam cracking (pyrolysis) of various feed stocks
include ethene, propene, butene (LPG), distillate (naphtha, gas oil) and even crude oil.
3. Aromatics; benzene, toluene and xylene (BTX), obtained from catalytic reforming.
These routes are the sources of the eight building blocks – ammonia, methanol, ethene, propene,
butadiene, benzene, toluene and xylene – from which virtually all large tonnage petrochemicals
are derived.
Below are some of the reactions for the production of some monomers from petrochemicals.
1. Monomers derived from Ethylene.
(a) Vinyl acetate may be synthesized by reacting ethylene with acetic acid.
H2C = CH2 + CH3COOH →CH2 = CH - O – C – CH3
O
Vinyl acetate
(b) Styrene can be synthesized by reacting benzene with ethylene
2CH2=CH2 + 2C6H6 → C6H5 – C2H5 + CH2 = CH
C6H5
2. Monomers derived from propylene
(a) Acrylonitrile is obtained by reacting propylene with ammonia.
CH2 = CH + NH3 + 3/2O2 → H2C = CH + 3H2O
CH3 CN
(b) Mehtylmethacrylate (acrylic) is also obtained by reacting propylene with carbon monoxide,
oxygen and methanol. CH3
H2C = CH + CO + 1/2O2 + CH3OH → H2C = C + H2O
CH3 COOCH3
Methyl methacrylate
3. Others are:
(a) Urea which is obtained by reaction between ammonia and carbon dioxide.
2NH3 + CO2 → H2N - C - NH2 + H2O
O
Urea
(b) Melamine may also be derived by thermal decomposition of urea.
6H2N – C – NH2 → C3N6H6 + 6NH3 + 3CO2
Melamine
The petrochemical industry currently supplies most monomers, while the coal-cracking industry

remains an alternative option.

Catalyst Polyethylene

Chlorine vinylchloride polyvinylchloride

Benzene styrene polystyrene

Ethylene Butadiene styrene-butadiene rubber

Oxygen ethylene glycol polyethylene

+
Water terephthalic acid terephthalate

Acetic acid vinyl acetate polyvinyl acetate

Fig. 1.3.1: Simplified flow diagrams for the production of some polymers from ethylene.
 Ethylene

Propylene

Natural gas butadiene

methanol

Olefin plant ammonia

Petroleum gas

naphtha

gas oil

crude oil benzene

toluene

reformate aromatic plant

xylene

Fig 1.3.2: simplified flow diagram for the production of petrochemicals from petroleum and

natural gas.
 MODULE TWO
2.0 CHEMISTRY OF POLYMERIZATION PROCESSES
2.1 Radical Chain (Addition) Polymerization
Chain polymerization is characterized by active centre which is responsible for the growth of the
chain, associated with a single polymer molecule through the addition of many monomer units.
Thus polymer molecules are formed from the beginning and almost no species intermediate
between monomer and high-molecular weight polymer are formed.
Three types of active center have been formed viz: cation, anion and free radical. Free radical
polymerization will be discussed.
Like all chain reactions, chain polymerization is characterized by three fundamental steps:
initiation, propagation and termination.
The carbon-carbon double bond is, because of its relatively low stability, susceptible to attack by
a free radical. The reaction of the double bond with a radical proceeds well for compound of the
type CH2=CHX and CH2=CHY called vinyl monomers (monomers in which fluorine is
substituted for hydrogen may be included).
2.1.1 Generation of free radicals
Free radicals can be generated in a number of ways, including thermal decomposition of
organic peroxides or hydroperoxides or azo or diazo compounds.
Two reactions commonly used to produce radicals for polymerization are thermal or
photochemical decomposition of benzoyl peroxide,
(C6H5COO)2 2C6H5COO* 2C6H5* + 2CO2
and of azobiisobutylonitrile,
(CH3)2CN=NC(CH3)2 2(CH3)2C* + N2

CN CN CN
To be useful in initiating polymerization, a compound undergoing thermal decomposition to free

radical should have a first-order decomposition rate constant of 10 -5 to 10-6 sec-1 at the desired

polymerization temperature, usually 50-150oC.

Photochemical initiator such as benzoin which is decomposed into free radicals by ultraviolet
light in the 3600-Å region, where direct initiation through decomposition of monomer do not
occur.
Other sources of free radicals generation are:
High-energy radiation from a wide variety of sources including electrons, gamma rays, X-rays
and slow neutrons is effective in producing free radicals that can initiate polymerization.
Radicals can also be generated as a result of oxidation-reduction reaction (redox initiation).
Appropriate to an aqueous medium, redox initiation is often used with emulsion polymerization.
Another source is electro-chemical initiation results from the generation of free radicals by
electrode reactions.
In all of these methods it is only the means of generating the free radicals that varies; the
remaining steps in the polymerization process are unchanged.
2.1.2 Mechanism of chain polymerization
Initiation: when free radicals are generated in the presence of a vinyl monomer, its radical adds
to the double bond with the regeneration of another radical. If the radical formed by the
decomposition of the initiator I is designated by R*
I 2R*
R* + M RM*
Where I = Initiator (concentration)
R* = Free radical (concentration)
M = Monomer (concentration)
RM* = growing chain radical
In essence, polymerization will ensue if a polymerizable monomer (M) is treated with a
suitable initiating agent, I which can yield an initiator R▪

Propagation: The chain radical formed in the initiation step is capable of adding successive
monomers to propagate the chain. The monomer reaches (by diffusion) the chain radical and is
attached to the growing chain. All this may happen during fraction of a second and lead to a
giant chain, with a free radical at the end. Propagation continues until the growing chain is
deactivated by chain termination or transfer. The growing chain which are either radicals or ions
themselves, constitute one type of reagent, and the monomer is the other. Propagation step
determines both the rate of the polymerization process and the chain length.
RCH2CHX* + CH2=CHX R-CH2CHX-CH2CHX*
Propagation continues until the growing chain is deactivated by chain termination or transfer.
In propagation head-tail step is found to be predominant however, other two steps are equally
possible.
RCH2CHX* + CH2=CHX R-CH2CHX-CHXCH2* Head-head.
Other possibility
RCH2CHX* + CH2=CHX R-CHXCH2-CH2CHX* Tail-tail
Note: The substituted carbon atom is regarded as the head and the unsubstituted carbon atom the
tail of vinyl monomer.
Termination: In termination, the growth activity of a polymer chain radical is destroyed by
reaction with another radical in the system to produce polymer molecule(s). Termination can also
occur by the reaction of the polymer radical with initiator radicals. This type of termination is
unproductive and can be controlled by maintaining a low rate for initiation.

R‒CH2‒CHX* +R* R‒CH2‒CHX‒R

The termination reactions that are more important in polymer production are combination
(or coupling) and disproportionation.

Termination by combination or coupling.

R‒CH2‒CHX* +R‒CH2‒CHX* R‒CH2‒CHX‒CH2‒CHX‒R

Produce a single polymer at low temperature.

And disproportionation.

R‒CH2‒CHX* +R‒CH2‒CHX* R‒CH2‒CH2X+R‒CH=CHX

In disproportionation in which hydrogen transfer results in the formation of two

molecules with one saturated and one unsaturated end group pronounces at high temperature.

Chain Transfer: - Ideally, free radical polymerization involves three (3) basic steps; Initiation,
propagation, and termination. However, a fourth step called chain transfer is usually involved. In
chain-transfer reactions, a growing polymer chain is terminated by transferring its growth
activity to a previously inactive species as shown below;

R‒CH2‒CHX* +TA R‒CH2‒CHX‒T + A*

The species, TA could be a monomer, polymer, initiator, impurity, solvent molecule or

other molecule deliberately or inadvertently introduced into the reaction mixture.

The new radical, A* may be a retarder or inhibitor. A retarder is defined as a substance

that can react with a radical to form products that slow down the reactivity of the radical. If the
retarder is very effective, no polymer may be formed; this condition is sometimes called
inhibition and the substance an inhibitor. Transfer reaction leads to the shortening of the chain
length or to the formation of side branches. In both cases many physical properties will be
affected. A retarder is defined as a substance that can react with a chain radical to form non
radical products or radical with low reactivity incapable of adding to monomer. Inhibitors are
substances added to a polymerizing system to stop the reaction spontaneously.

Transfer reactions do not result in the creation or destruction of radicals at any instant, the
overall number of growing radicals remains unchanged. However, the occurrence of transfer
reactions results in the reduction of the average polymer chain length and in the case of transfer
to a polymer it may result in branching.

2.1.3 Kinetics of Vinyl Polymerization

Conversion of monomer to polymer: The overall mechanism for the conversion of a monomer
to a polymer via free-radical initiation may be described by rate equation according to the
following scheme.

Initiation

This is a two step process involving

1. The decomposition of the initiator into primary radicals

kd
I 2R*
 2. The addition of a monomer to the primary free radical
kG
R*+ M RM*1

The overall rate of initiation depends on the concentrations of the monomer and initiator and also
on the rate constant of the two reactions i.e. k d and ki. Since the initiator dissociation is much
slower than monomer addition thus the first step of the initiation step is the rate-limiting step.
The constant kd is frequently the lower of the two, and thus controls the rate of the whole
initiation reaction. Therefore, the rate expression for initiation may be written as

d[ M]
Ri = = 2fkd[I]
dt

Where [I] = initiator concentration

f = efficiency factor (which estimate initiator decomposition with the number of polymer
chain formed).

Propagation

The successive addition of monomers during propagation may be represented as follows:

RM*1 + M kp RM*2
RM*2 + M kp RM*3
RM*X + M kp RM*X+1

If it is assumed that the rate of polymerization equals essentially the rate of consumption of
monomers in the propagation step. The rate expression for polymerization rate can there be
written thus

−d [ M ]
Rp = = kp[M*] [M]
dt

Where [M*] = ΣRM*X i.e the sum of the concentration of all chain radicals of type RM* X (it is
assumed that the concentration of the radical RM* is the same as that of M* because the
influence of radicals are not felt much).

Termination
Chain growth may be terminated at any point during polymerization by either or both of two
mechanisms.

Combination/coupling

M*X + M*y ktc Mx+y

M*X +M*y ktd Mx+My

If there is no need to distinguish between the two types termination which in any case are
kinetically equivalent, then termination may be represented as

M*X +M*y kt P

Where kt = ktc + ktd and

ktc and ktd = rate constants for overall termination process.

The termination rate is given by

−d [ M ]
Rt = = 2kt[M*]2
dt

The factor of 2 arises from the fact that at each incidence of termination reaction, two radicals
disappear. At steady state (Ri = Rt) i.e. the rate of radicals production equal to the rate of radical
destroyed. Since Ri = Rt

Thus [M*] = (fkd /kt )1/2 [I]1/2

Since the overall polymerization rate is essentially the rate of monomer consumption during
propagation,

For Rp = kp[M*] [M]

Substituting for [M*] we have

Rp = kp(fkd /kt )1/2 [I]1/2[M] (**)

Note that the equation (**) above predicts that the rate of polymer formation in free-radical
polymerization is first order in monomer concentration and half order in initiator concentration.
2.2 Mechanism of Condensation Polymerization

Condensation polymerization is the formation of polymers by stepwise intermolecular chemical

reactions that normally involve more than one monomer species; there is usually a small
molecular weight by-product such as water, which is eliminated. The intermolecular reaction
occurs by addition-elimination “mechanism”.

For example, consider the formation of polyester from the reaction between ethylene glycol
and adipic acid. The intermolecular reaction is as follows:

HO-CH2-CH2-OH + HOOC-CH2-CH2-CH2-CH2-COOH

HO-CH2-CH2-O-CO-CH2-CH2-CH2-CH2-COOH + H2O

This stepwise process is successively repeated every time a repeat unit is formed.

Condensation reactions often produce trifunctional monomers capable of forming crosslinked

and network polymers.

The thermosetting polyester and phenol-formaldehyde, the nylons and the polycarbonates are
produced by condensation polymerization.

2.2.1 Kinetics of stepwise polymerization

Consider the formation of polyester from a glycol and a dibasic acid.

nHOOC-(CH2)4-COOH + nHO-CH2-CH2-O-CH2-CH2-OH

Adipic acid diethylene glycol

[-OC-(CH2)4-CO-O-CH2-CH2-O-CH2-CH2-O]n + 2n H2O
polyester
It is well known that this reaction is catalyzed by acids.
Case 1: In the absence of added strong acid, a second molecule of the acid being esterified act as
a catalyst. The reaction is followed by measuring the rate of disappearance of carboxyl groups.
 −d [COOH ]
= k[COOH]2[OH] (2.1)
dt
If the concentrations of carboxyl and hydroxyl groups are equal, (2.1) may be written as
−dC
=kC3 (2.2)
dt
and on integration thus yield
2kt = 1/C2 – constant (2.3)
Now let us introduce the extent of reaction p, defined as the fraction of the functional group that
has reacted at time t. that is
(C o−C )
P= (2.4)
Co
Where Co = Initial concentration
C = Final concentration
Equation (2.4) can be written as,
C = Co(1-P) (2.5)
Hence, on substitution equation (2.3) becomes
2 Co2kt = 1/(1-P)2 + constant (2.6)
Case 2: with added strong acid. In this case the concentration of the catalyst may be included in
the rate constant.
−d [COOH ]
= k’[COOH][OH]
dt
With equimolar concentration of carboxyl and hydroxyl group, keeping catalyst concentration
constant,
−dC
= k’C2 (2.7)
dt
Integrating yield,
1
k’t = – constant
C
In terms of extent of reaction p
1
Cok’t = + constant (2.8)
(1− p)
The number-average degree of polymerization is given as:
 Co Co 1
Xn = = = (2.9)
C C o (1− p) (1− p)

From the definition of Xn it follows that the number-average molecular weight will be given by
the expression
Mo
Mn = XnMo = (2.10)
(1− p)
Where Mo = average molecular weight of the repeat unit.
Impurities (excess of a functional group) within reaction
For number- average degree of polymerization
1+r
Xn = (2.11)
2r (1− p)+(1−r)
Co
Where r = the fraction of non-impurity present =
Co+ Excess
When r = 1 (no impurity and equimolar)
1
Xn =
(1− p)
For maximum extent of reaction i.e. degree of polymerization is maximum C = 0
p = Co/Co = 1
1+r
Xn = (2.12)
1−r
Probability of finding X-mer
The total probability that a given polymer contains X units is
Px = Px-1(1-p) (2.13)
(C o−C )
Where P = and x = dimmers, trimers, tetramers etc.
Co
Weight fraction of X-mer
The weight fraction Wx of x-mers is given as
xC x
Wx =
Co
But C = Co(1-p)
Cx
and Px = Px-1(1-p) =
C
thus Cx = PxC = PxCo(1-p)
therefore Wx = xPx-1(1-p)2 (2.14)
Weight-average degree of polymerization
The weight-average degree of polymerization is defined by
1+ p
Xw =
1− p
and Mw = Mo Xw
Xw
The ratio = 1+p is a measure of polydispersity or the spread of molecular weight.
Xn
2.3 Molecular Size and Weight
In simple monomolecular compounds, the molecular weight is the sum of the atomic weights of
all the elements in the compound, and the molecules are all of exactly the same weight and size.
But the molecules of a polymer do vary considerably in both size and weight. Some molecules
will be very much longer than others. The major reason for this variation is the fact that in
addition and condensation polymerization reactions, the length of the polymer chain is
determined by purely random events. In both cases therefore the polymer contains molecules
having many different chain lengths. Because a distribution of molecular weights exists in any
polymer sample, any experimental measurement of molecular weight can only give an average
value.
Two main types of averages are important. They are the number-average molecular weight (M n)
and the weight-average molecular weight (Mw).
The number-average molecular weight is obtained by dividing the chains into a series of size
ranges and then determining the number fraction of chains with each size range. This number-
average molecular weight is expressed as
ΣW i
Mn = ΣxiMi = Wi (2.31)
Σ( )
Mi
Where Mi = mean (middle) molecular weight of size range i
xi = the fraction of the total number of chains within the corresponding size range
Wi = the weight (g) of total number of chains within the corresponding size range
Ni
But xi =
Σ∋¿ ¿
Where, Σ∋¿ = N is the total number or moles or molecules of chains
Ni is the number or moles or molecules of chains with molecular mass Mi
Therefore
N 1 M 1+ N 2 M 2+ …+ NnMn Σ N iMi
Mn = = (2.32)
N 1+ N 2+…+ Nn ΣNi
W 1+ W 2+ W 3+…+Wn ΣW i
Mn = W 1
M1 ( )( )( ) ( )
+
W2
M2
+
W3
M3
+ …+
Wn
Mn
= Wi
Σ( )
Mi
(2.33)

The weight-average molecular weight (Mw) is based on the weight fraction of molecules within
the various size ranges. It is calculated according to

W 1 M 1+ W 2 M 2+…+WnMn
Mw = = ΣyiMi = y1M1+y2M2+y3M3+…+ynMn (2.34)
W 1+W 2+ …+Wn
Where Mi = mean (middle) molecular weight of size range i
yi = weight fraction of molecules within the same size interval
Wi Wi
but yi = =
Σ Wi W
The relationship between weight (Wi) and number (N) of the chains is simply expressed by
Wi = NiMi. Therefore
Σ N iMi 2
Mw = (2.35)
Σ N iMi

The ratio Mw/Mn is the polydispersity index (PDI) and indicates how uniform or otherwise the
molecular weight distribution is. In general, a narrow molecular weight distribution leads to
more uniform property values, a narrower softening/melting temperature range, a lower stress
cracking sensitivity and better chemical resistance. A broad molecular weight distribution has
advantages for processing because the low molecular weight fractions behave like lubricants.
The polymer is less brittle because the low molecular weight fractions can act as plasticizers.
2.4 Difference between the kinetics of Addition and condensation polymerization.

2.4.1 Addition polymerization

1. Long chains appear at the early stage

2. Monomers are added to long chains, and steadily disappear during the process
3. There is no elimination of small molecules
4. Quite high molecular weights maybe obtained (105 to 2x106)
2.4.2 Condensation polymerization

1. At the early stages dimers, trimers, and tetramers are formed by reacting pairs of opposing
functional groups, so that the growth develops in stages.
2. Monomers disappear at the early stage.
3. There is (usually) an elimination of a small molecule.
4. Molecular weights are low to medium (below 50,000 normally).

Table 2.1: Examples of Addition Polymers

CH2 = CHX (vinyl monomer)

X Monomer Polymer

H Ethylene Polyethylene (PE)

CH3 Propylene Polypropylene (PP)

Cl Vinyl chloride Poly(vinyl chloride) (PVC)

CN Acrylonitrile Polyacrylonitrile (PAN)

Styrene Polystyrene (PS)

O Vinyl acetate Polyvinyl acetate (PVA)

C=O

CH3

Others are Monomer Polymer

CH3 Methyl methacrylate Polymethylmethacrylate

CH2=C (PMMA)

COOCH3

CH3 Isobutylene Polyisobutylene

C=CH2

CH3

Table 2.2: Examples of Condensation polymers

Polymer Monomers
1 PES: Polyester HOCH2 – CH2OH Ethylene glycol
PET: (Polyethylene terephthalate) HOOCC6H4COOH Terephthalic acid
Typical group -CO – O
2 PA: Polyamide H2N(CH2)6NH2 Hexamethylene diamine
(Nylon 6 – 6) HOOC(CH2)4COOH Adipic acid
Typical group - NH – CO -
3 MF: Melamine-formaldehyde C3N6H6 Melamine
HCHO formaldehyde
4 PF: Phenol-formaldehyde C6H5OH phenol
HCHO or CHOH formaldehyde
5 UF: Urea-formaldehyde H2N-CO-NH2 urea
HCHO formaldehyde

2.2.6 Copolymerization
 The polymerization of two or more different monomers by chain reaction mechanism. Polymers
obtained via condensation are not copolymers, as their repeat unit is identical. Copolymers are
widely used in elastomers and artificial textiles, as in many plastomers. The most common are;
1. SAN (Styrene-acrylonitrile)
2. SB (Styrene-butadiene)
3. EP (Ethylene-propylene)
4. ABS (a terpolymer comprised of acrylonitrile, butadiene, and styrene)
5. SBS (styrene-butadiene-styrene)
ACTIVITY
Read up mechanism and kinetics of copolymerization

MODULE THREE

3.0 PRINCIPLE OF POLYMER MANUFACTURE

3.1 Preparative Techniques

Polymerization of monomers on an industrial scale can be carried out in a number of

polymerizing systems which include bulk polymerization, solution polymerization, suspension
polymerization and emulsion polymerization. The bulk and solution methods are used for the
formation of both addition and condensation type polymers, whereas suspension and emulsion
techniques are used largely for addition polymerization.

3.1.1 Bulk polymerization: - 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. The bulk
polymerization system is used widely in the manufacture of condensation polymers (e.g. amino
acids and hydro acids) or radically initiated polymerization reaction involving only the monomer
and possibly initiator. For condensation polymers, the reactions are mildly exothermic and the
viscosity of the mixture is low during the reaction, thus facilitating good mixing and better heat
transfer. For vinyl monomers however, bulk polymerization is more difficult due to high
exothermicity of the reaction. Examples of common polymers manufacture using the bulk
polymerization system are polyethylene, polystyrene and polymethylmethacrylate.

Advantages

 Minimum contamination of the product

 Carried out to high conversion

Disadvantages

 Viscosity increases with conversion, making heat removal and processing more
difficult.
 Rt (rate of termination) decreases at high conversion, making the reaction hard to
control.

3.1.2 Solution polymerization: - This involves polymerization of a monomer in a solvent

(chemically inert medium) in which both the monomer (reactant) and polymer (product) are
soluble (homogeneous) and if polymer is insoluble (heterogeneous), it leads to precipitation.
Typical polymers synthesized using the solution polymerization techniques are polyacrylonitrile,
esters of acrylic acid and polyvinyl acetate.

Advantages

 Solvent acts as a diluents and aids in removal of heat of polymerization

 Solvent reduces viscosity, making processing easier
 Thermal control is easier than in bulk

Disadvantages

 Chain transfer to solvents occurs, leading to low molecular weights

 Environmental pollution due to solvent release
 Difficult to remove solvent from final form which cause impurity
  High polymers in the solution increase the viscosity of the solvent greatly and so a lot
of solvent is needed which is uneconomical.

3.1.3 Suspension polymerization: - Called pearl polymerization and is used only for catalyst-
initiated or free radical addition polymerizations. The monomer is mechanically dispersed in a
liquid, usually water, which is a non-solvent for the monomer as well as for all size of polymer
molecules form during the reaction. This technique is used to polymerize styrene,
methylmethacrylate, vinylchloride, vinylacetate.

The catalyst-initiator is dissolved in the monomer, and it is preferable that it does not
dissolve in the water so that it remains with the monomer. The monomer and polymer being
formed from it remains within the beads of organic material dispersed in the phase. Viscosity of
the complete suspension does not vary with polymerization and stabilizer is added to prevent
clumping together of the polymer formed. Suspension polymerization is essentially a finely
divided form of bulk polymerization.

Advantages

 The advantage over the bulk type is that it allows the operator to effectively cool
exothermic polymerization reactions and thus maintain closer control over the chain
building process.
 Also by controlling degree of agitation, monomer-to-water ratio and other variables, it is
possible to control the particle size of the finished polymer, thus eliminating the need for
re-forming the material into pellets from a melt, as is usually necessary with bulk
polymerization.
 The water-insoluble monomer is suspended as droplets in aqueous phase, as a result of
vigorous agitation of the system. This technique obviates the problems of heat and
viscosity build-up, as obtained in bulk polymerization.
 Easy heat removal due to high heat capacity of water.
 Polymerization yields finely divided, stable latexes and dispersions to be used directly in
coatings, paints and paints.
Disadvantages

 Cannot be used for polymers whose glass transition (Tg) temperature is less than the
polymerization temperature, or else aggregation will occur.
 Must separate and purify polymer, or accept contaminated product.

3.1.4 Emulsion polymerization: - Emulsion polymerization describes a polymerization

system containing the monomer, water-soluble initiator, emulsifier or surfactant (soap) and
water. This involves causing the reaction to take place within a small hollow sphere composed of
a film of soap molecules, called micelles. Monomer diffuses into these micelles’, and control of
the soap concentration, and overall reaction-mass recipe, and reaction conditions provides
additional controls over the reaction. The emulsion polymerization technique is used
commercially to prepare polyvinyl acetate, acrylic polymers, and many important copolymers.

Advantages

 It is much more rapid than bulk or solution polymerization at the same temperatures
 Produces polymer with molecular weights much greater than those obtained at the same
rate in bulk polymerization.
 The latex may be used directly without purification.
 Thermal and viscosity problems are minimized due to the high heat capacity and ease of
stirring of the continuous aqueous phase.

Disadvantages

 It blocks the emulsifiers used in the process.

 In addition, the process has poor capacity and low electrical resistance, which
sometimes create major problems.

The polymer particles are dispersed in the aqueous phase, similar to what is obtained in
the suspension polymerization system. There are however major differences between the
suspension and emulsion techniques.

 Whereas in suspension polymerization, the initiator is dissolved in the monomer phase,

in emulsion polymerization, the initiator is dissolved in the aqueous phase.
  The second major difference is the size of polymer particles. It has been found that the
polymer particle sizes obtained in suspension polymerization are of the order 0.001 –
1cm. Particle sizes in emulsion polymerization are much smaller, being in the range of
0.1mm in diameter.

3.2 Polymerization Reactors

The course of a polymerization reaction and hence the properties of the resultant polymer are
determined by the nature of the polymerization reaction and the characteristics of the reactor
employed in the reaction. In other words, the reactor is essentially the heart of any
polymerization process. The reactor affects the conversion of the monomer to the polymer. The
reactor also effectively establishes the ultimate properties of the polymer such as polymer
structure, molecular weight, molecular weight distribution, and copolymer composition. To
perform its function satisfactorily, the reactor must:

 Remove the heat of polymerization

 Provide the necessary residence time
 Provide good temperature control and reactant homogeneity
 Control the degree of back-mixing in a continuous polymerization
 Provide surface exposure.

In addition, the reactor must be applicable to mass production and economical to operate.
Therefore, the control of polymer properties requires a careful selection of a reactor appropriate
for the particular polymerization process.

Reactors may be divided into three simple, idealized model categories: batch reactor, tubular or
plug flow reactor and the continuous stirred tank reactor (CSTR).

3.2.1 Batch reactors: - In batch reactors, the reactants are charged into the reactor and mixed
properly for the duration of the reaction and then the product is discharged. The batch reactor has
essentially the following characteristics.

a) It is simple and does not need extensive supporting equipment.

b) It is ideal for small scale production (operations).

c) The operation is an unsteady-state operation, with composition varying with time.

Batch
reactor

Material balance for a reactor

[Rate of monomer flow into the reactor] = [Rate of monomer flow out of the reactor] + [Rate of
monomer loss due to reaction within the reactor] + [Rate of monomer accumulation within the
reactor]

For a batch reactor, the first two terms of the equation are equal to zero since by definition
nothing flows in or out of the reactor. Consequently, the equation reduces to;

Rate of monomer loss Rate of accumulation

due to reaction within the + of monomer within the =0
reactor reactor
3.2.2 Tubular (plug flow) reactor: - This is essentially a tube or unstirred vessel with very
high length/diameter (L/d) ratio. Fluid flow in the ideal plug flow reactor is orderly, with no
element of fluid overtaking any other element (i.e. no lateral or back-mixing). However, tubular
reactors have limited application in polymer production. This is so because, the high viscosities
characteristics of polymerization reactor media present temperature control problems. In
addition, the material temperature increases from the tube wall to its radius. This broad
temperature distribution leads to a broad molecular weight distribution – a situation that is
common with chain-growth polymerization by the decrease in initiator and monomer
concentrations with increasing conversions. Since the reactor walls are cooler than the centre of
the reactor, there is a tendency to form a slow-moving polymer layer on the walls. This reduces
the production capacity and aggravates the heat transfer problems.
 Qv
D

3.2.3 Continuous stirred tank reactor (CSTR):- The ideal continuous stirred tank reactor is a
reactor with well-stirred and back-mixed content. As a result, instant blending of the feed with
the reactor contents is assumed to occur. The composition of the contents of reactor is uniform
throughout the reactor.

During polymerization with a CSTR, the monomer and the other components of the
polymerization recipe are fed continuously into the reactor while the polymerization product
mixture is continually withdrawn from the reactor. The application of CSTR in suitable
polymerization process reduces, to some extent, the heat removal problems due to the cooling
effect from the addition of cold feed and the removal of heat of reaction with the effluent. Even
though the supporting equipment requirements may be relatively substantial, CSTR are
economically attractive for industrial production and consistent product quality. Characteristics
of CSTR are;

a) Steady flow process

b) Lower labor cost
c) Relatively easily automated.

Qv

CSTR
 Qv

Input = Output + Disappearance + Accumulation.

MODULE FOUR
4.0 POLYMER MATERIALS (NATURAL AND SYNTHETIC)
4.1 Natural resins (latex)
Resin is a term applied to a group of sticky, liquid, organic substances that usually harden upon
exposure to air, into brittle, amorphous, solid substances. Natural resins are secreted by many
plants, appearing on the external surface of a plant after a wound. The resins form protective
coatings over the plant wounds, preventing the entrance of pathogenic microorganisms and also
excessive loss of sap from the wound. In obtaining natural resins commercially, cuts are made in
the tree bark, and the globules of liquid resin that flow from the cut are directed by troughs into
collecting buckets.
4.1.1 Properties of natural resin
 They are yellow to brown in color.
 They burn with a smoky flame and exude an aromatic odour.
 Chemically, they differ from one another in detail, but they all contain carbon, hydrogen,
and oxygen.
  All resins are insoluble in water, as distinguished from the water-soluble gums. Resins
are also soluble in alcohol, ether and other organic solvents.
The natural resin known as lac is not a plant exudate but is formed by the tiny scale insect,
lacciferlacca, indigenous to south East Asia. Lac is deposited on trees and is harvested for the
production of shellac.
The many natural resins are classified according to hardness and chemical constitution into three
principal categories. Hard resins, oleoresins, and gum resins.
The hard resins, among which are amber, copals, mastics, and sandarac are hard, brittle,
odourless, and tasteless and exhibit a glass-like fracture. Hard resins are obtained either as fossils
or as distillation products of the oleoresins. The most important of the hard resins, and possibly
the most commercially important of all the resins, is rosin, which is used in sizing paper, in soap
making, as a constituent of varnishes and paints, and as a friction-producing coating for the bows
of stringed instruments. Rosin is obtained by distillation of the oleoresin turpentine.
The oleoresins are sticky, amorphous, semisolids that contain essential oils. Among the
oleoresins are the balsam, dragon’s blood, and copaiba, turpentine is possibly the most widely
used oleoresin. The essential oil of turpentine is used as a solvent for paints and varnishes and is
employed in the manufacture of shoe polish and scaling wax. During the era of sailing vessels,
the crude oleoresin turpentine was much used for caulking and waterproofing. Resins such as
frankincense, myrrh, benzoin, and asafetida contain gums and are called gum resins.
Latex: Is a milky fluid found in specialized cells, called lactiferous cells, of many higher plants.
Latex, a polymer dispersed in water, contains a complex emulsion composed of varying
proportions of gums, resins, tannins, alkaloids, proteins, starches, sugars and oils. It is usually
white, but in a few plants it may be yellow, orange, or red. Latex is found in most species of the
milkweed, dogbane, sapodilla, spurge, many commercial gums, including rubber, chicle, opium,
and chewing gum, are products made from refined latex. It is now also produced synthetically.
4.2 Synthetic Resins (Plastics)
Plastics, materials made up of large, organic (carbon-containing) molecules that can be formed
into a variety of products. The molecules that compose plastics are long carbon chains that give
plastics many of their useful properties. In general, materials that are made up of long, chainlike
molecules are called polymers. The word plastic is derived from the words plasticus (Latin for
“capable of molding”) and plastikos (greek for “to mold”, or “fit for molding”). Plastics can be
made as hard as stone, strong as steel, transparent as glass, light as wood, and elastic as rubber.
Plastics are also light weight, waterproof, chemical resistant, and produced in almost any colour.
More than 50 families of plastics have been produced, and new types are currently under
development.
Like metals, plastics come in a variety of grades. For instance, nylons are plastics that are
separated by different properties, costs, and the manufacturing processes used to produce them.
Also like metals some plastics can be alloyed, or blended, to combine the advantages possessed
by several different plastics. For example, some types of impact-resistant (shatterproof) plastics
and heat-resistance plastics are made by blending different plastics together.
Plastics are moldable, synthetic (chemically-fabricated) materials derived mostly from
fossil fuels, such as oil,coal, or natural gas. The raw forms of other materials, such as glass,
metals, and clay, are also moldable. The key difference between these materials and plastics is
that plastics consist of long molecules that give plastics many of their unique properties, while
glass, metals, and clay consist of short molecules.

4.2.1 Uses of Plastics

Plastics are indispensable to our modern way of life. Many people sleep on pillows and
mattresses filled with a type of plastic ‒ either cellular polyurethane or polyester. At night,
people sleep under blankets and bedspreads made of acrylic plastics, and in the morning, they
step out of bed onto polyester and nylon carpets. The cars we drive, the computers we use, the
utensils we cook with, the recreational equipment we play with, and the houses and buildings we
live and work in all include important plastic components. The average car contains almost
136kg (almost 300lb) of plastics ‒ nearly 12 percent of the vehicles overall weight. Telephones,
textiles, compact discs, paints, plumbing fixtures, boats and furniture are other domestic products
made of plastics. In1979 the volume of plastics produced in the United States surpassed the
volume of domestically produced steel.
Plastics are extensively used by many key industries, including the automobile, aerospace,
construction, packaging, and electrical industries. The aerospace industry uses plastics to make
strategic military parts for missiles, rockets, and aircraft. Plastics are also used in specialized
fields, such as the health industry, to make medical instruments, dental fillings, optical lenses,
and biocompatible joints.
4.2.2 General properties of Plastics
Plastics possess a wide variety of useful properties and are relatively inexpensive to produce.
They are lighter than many materials of comparable strength and unlike metals and wood,
plastics do not rust or rot. Most plastics can be produced in any color. They can also be
manufactured as clear as glass, translucent (transmitting small amounts of light), or opaque
(impenetrable to light).
Plastics have a lower density than that of metals, so plastics are lighter. Most plastics
vary in density from 0.9 to 2.2 g/cm 3 (0.45 to 1.5 0z/cu in), compared to steels density of
7.85g/cm3 (5.290z/cu in). Plastic can also be reinforced with glass and other fibers to form
incredibly strong materials. For example, nylon re-in forced with glass can have a tensile
strength (resistance of a material to being elongated or pulled apart) of up to 165MPa
(24,000psi).
4.2.3 Disadvantages of Plastics

Plastics have some disadvantages when burned, some plastics produce poisonous fumes.
Although certain plastics are specifically designed to withstand temperatures as high as 288 0C
(5500F), in general,plastics are not used when high heat resistance is needed.
Because of their molecular stability, plastics do not easily breakdown into simpler components.
As a result, disposal of plastics creates a solid waste problem.
4.3 Thermoplastic and Thermosetting Plastics
All plastics, whether made by addition or condensation polymerization, can be divided into two
groups’ thermoplastics and thermosetting plastics.
These terms refer to the different was these types of plastic respond to heat.
Thermoplastics can be repeatedly softened by heating and hardened by cooling. Thermosetting
plastics, on the other hand, harden permanently after being heated once.
The reason for the difference in response to heat between thermoplastics and thermosetting
plastics lies in the chemical structures of the plastics. Thermoplastic molecules, which are linear
or slightly branched, do not chemically bond with each other when heated. Instead, thermoplastic
chains are held together by weak van deer forces (weak attractions between the molecules) that
cause the long molecular chains to clump together like piles of entangled spaghetti.
Thermoplastics can be heated and cooled, and consequently soften and hardened, repeatedly, like
candle wax. For this reason, thermoplastics can be reheated and reused almost indefinitely.
Thermosetting plastics consist of chain molecules that chemically bond, or cross-link, with each
other when heated. When thermosetting plastics cross-link, the molecules create a permanent,
three-dimensional network that can be considered one giant molecule. Once cured, thermosetting
plastics cross-link, the molecules create a permanent, three-dimensional network that can
permanent, three-dimensional network that can be considered one giants molecule. Once cured
thermosetting plastics cannot be reheated, in the same way that cured concrete cannot be reset.
Consequently, thermosetting plastics are often used to make heat-resistant products, because
these plastics can be heated to temperatures of 2600C (5000F) without melting.
The different molecular structures of thermoplastics and thermosetting plastics allow
manufacturers to customize the properties of commercial plastics for specific applications.
Because thermoplastic materials consist of individual molecules, properties of thermoplastics are
largely influenced by molecular weight. For instance, increasing the molecular weight of a
thermoplastic material increases its tensile strength, impact strength, and fatigue strength (ability
of a material to withstand constant stress). Conversely, because thermosetting plastics consist of
a single molecular network, molecular weight does not significantly influence the properties of
these plastics. Instead, many properties of thermosetting plastics are determined by adding
different types and amounts of fillers and reinforcements, such as glass fibers.
4.3.1 Thermoplastics
Thermoplastic materials are in high demand because they can be repeatedly softened and
remolded. The most commonly manufactured thermoplastics are presented in this section in
order of decreasing volume of production.
4.3.1.1 Polyethylene: Polyethylene (PE) resins are milky white translucent substances derived
from ethylene (CH2=CH2). Polyethylene, with the chemical formula (-CH 2-CH2-)n (where n
denotes that the chemical formula inside the brackets repeats itself to form the plastic molecule)
is made in low-and high-density forms. Low-density polyethylene (LDPE) has a density ranging
from 0.91 to 0.93 g/cm3 (0.6 to 0.61 oz/cu in). The molecules of LDPE have a carbon backbone
with side groups of four to six carbon atoms attached randomly along the main backbone. LDPE
is the most widely used of all plastics, because it is inexpensive, flexible, extremely tough, and
chemical-resistant. LDPE is molded into bottles, garment bags, frozen food packages, and plastic
toys. High-density polyethylene (HDPE) has a density that ranges from 0.94 to 0.97 g/cm 3 (0.62
to 0.64 oz/cu in). Its molecules have an extremely long carbon backbone with no side groups. As
a result, these molecules align into more compact arrangements, accounting for the higher
density of HDPE. HDPE is stiffer, stronger, and less translucent than LDPE. HDPE is formed
into grocery bags, car fuel tanks, packaging, and piping.
4.3.1.2 Polyvinylchloride: Polyvinyl chloride (PVC) is prepared form the organic compound
vinyl chloride (CH2=CHCl). PVC is the most widely used of the amorphous plastics. PVC is
lightweight, durable, and water proof. Chlorine atoms bonded to the carbon backbone of its
molecules gives PVC it’s hard and flame – resistant properties.
In its rigid form, PVC is weather-resistant and is extruded into pipe, house siding, and gutters.
Rigid PVC is also blow molded into clear bottles and is used to form other consumer products,
including compact discs and computer casings. PVC can be softened with certain chemicals.
This softened form of PVC is used to make shrink-wrap, food packaging, rainwear, shoe soles,
shampoo containers, floor files, gloves, upholstery, and other products. Most softened PVC
plastic products are manufactured by extrusion, injection molding, or casting.
4.3.1.3 Polymethylmethacrylate (acrylics): Polymethylmethacrylate (PMMA), more
commonly known by the generic name acrylic, is polymerized from the hydrocarbon compound
methyl methacrylate (C5O2H8). PMMA is a hard material and is extremely clear because of the
amorphous arrangement of its molecules. As a result, this thermoplastic is used to make optical
lenses, watch crystals, aircraft windshield, skylights, and outdoor signs. These PMMA products
are marketed under familiar trade names, including Plexiglas, Lucite, and acrylite. Because
PMMA can be cast to resemble marble, it is also used to make sinks, countertops, and other
fixtures.
4.3.1.4 Polyamide (Nylons): Polyamides (PA), known by the trade name Nylon, consist of
highly ordered molecules, which give polyamides high tensile strength; some polyamides are
made by reacting dicarboxylic acid with diamine (carbon molecules with the ion-NH 2, on each
end), as in nylon-6,6, and nylon-6,10 (The two numbers in each type of nylon represent the
number of carbon atoms in the diamine and the dicarboxylic acid respectively). Other types of
nylon are synthesized by the condensation of amino acids.
 Polyamides have mechanical properties such as high abrasion resistance, low coefficients
of friction (meaning they are slippery), and tensile strengths comparable to the softer of the
aluminium alloys. Therefore, nylons are commonly used for mechanical applications, such as
gears, bearings, and bushings. Nylons are also extruded into millions of tons of synthetic fibers
every year. The most commonly used nylon fibers, polyhexamethylene adipamide or nylon-6, 6
and polycaproamide or nylon-6 (single number because this nylon forms by the self-
condensation of an amino acid) are made into the textiles, ropes, fishing lines, brushes, and other
items.
4.3.2 Thermosetting Materials
Because thermosetting plastics cure, or cross-link, after being heated, these plastics can be made
into durable and heat-resistant materials. The most commonly manufactured thermosetting
plastics are presented below in order of decreasing volume of production.
4.3.2.1 Phenolic: Phenolic (phenol-formaldehyde) resins, first commercially available in 1910,
were some of the first polymers made. Today phenolic are some of the most widely produced
thermosetting plastics. They are produced by reacting phenol (C 6H5OH) with formaldehyde
(HCOH). Phenolic plastics are hard, strong, inexpensive to produce, and they possess excellent
electrical resistance. Phenolic resins cure (cross-link) when heated and pressure is applied during
the molding process. Phenolic resin-impregnated paper or cloth can be laminated into numerous
products, such as electrical circuit boards. Phenolic resins are also compression molded into
electrical switches, pan and iron handles, radio and television casings, and toaster knobs and
bases.
4.3.2.2 Polyester: Polyester, form of plastic used in textiles and objects. Polyester fiber is
commonly used to make fabrics. It is formed by the interaction of dihydric alcohol with
terephthalic acid.
Different polyester fibers have slightly different characteristics, but they share similar properties.
They absorb little moisture and can be washed or dry-cleaned. Prolonged exposure to sunlight
reduces their strength. They melt at about 2600C (about 5000F).
Polyester is most familiar as a component of fabric. Clothes with high polyester content became
popular in the 1970s. Partly because they lacked the texture and feel of natural fabrics such as
cotton and wool, their popularity decreased. However, polyester is still a component in many
fabrics used in clothing and other items.
A polyester fiber made from polyethylene terephthalate (PET) is used in a wide range of
products including tire cords, shrink wrap, and clothing. The fiber resists wrinkling, mildew, and
a variety of chemicals. PET is also used to make bottles as containers for soft drinks. The most
common use of polyester today is in textiles.
4.3.2.3 Epoxy: Epoxy (EP) resins are named for the epoxide groups (cycl-CH 2OCH, cycl or
cyclic refers to the triangle formed by this group) that terminate the molecules. The oxygen along
epoxy’s carbon chain and the epoxide groups at the ends of the carbon chain give epoxy resins
some useful properties. Epoxies are tough, extremely weather – resistant, and do not shrink as
they cure (dry).
Epoxies cross-link when a catalyzing agent (hardener) is added, forming a three-dimensional
molecular network. Because of their outstanding bonding strength, epoxy resins are used to make
coatings, adhesives, and composite laminates. Epoxy has important applications in the aerospace
industry. All composite aircraft are made of epoxy. Epoxy is used to make the wing skins for the
F-18 and F-22 fighters, as well as the horizontal stabilizer for the F-16 fighter and the B-1
bomber. Inaddition, almost 20% of the harrier Jet’s total weight is composed of reinforcements
bound with an epoxy matrix.
Because of epoxy’s chemical resistance and excellent electrical insulation properties, electrical
parts such as relays, coils and transformers are insulated with epoxy.
4.3.2.4 Reinforced Plastics: Reinforced plastics, called composites, are plastics strengthened
with fibers, strands, cloth, or other materials. Thermosetting epoxy and polyester resin are
commonly used as the polymer matrix (binding material) in reinforced plastics. Due to a
combination of strength and affordability, glass fibers, which are woven into the product, are the
most common reinforcing material. Organic synthetic fibers such as aramid (an aromatic
polyamide with the commercial name Kevlar) offer greater strength and stiffness than glass
fibers, but these synthetic fibers are considerably more expensive.
The boeing 777 aircraft makes extensive use of light weight reinforced plastics. Other products
made from reinforced plastics include boat hulls and automobile body panels, as well as
recreation equipment, such as tennis rackets, golf clubs, and jet skis.
4.4 Plastics and the Environment
Every year in the United States, consumers throw millions of tons of plastic away – of the
estimated 210 million metric tons of municipal waste produced annually in the United States,
10.7% are plastics. As municipal landfill reach capacity and additional space diminishes across
the United States, alternative methods for reducing and disposing of wastes – including plastics
are being explored. Some of these options include reducing consumption of plastics, using
biodegradable plastics, and incinerating or recycling plastic waste.
A. Source Reduction: Sources reduction is the practice of using less material to
manufacture a product. For example, the wall thickness of many plastic and metal
containers has been reduced in recent years, and some European countries have proposed
to eliminate packaging that cannot be easily recycled.
B. Biodegradable Plastics: Due to their molecular stability, plastics do not easily
breakdown into simplex components. Plastics are therefore not considered biodegradable.
However, researchers are working to develop biodegradable plastics that will disintegrate
due to bacterial action or exposure to sunlight. For example, scientists are incorporating
starch molecules into some plastic resins during the manufacturing process. When these
plastics are discarded, bacteria eat the starch molecules. This causes the polymer
molecules to break apart, allowing the plastic to decompose. Researchers are also
investigating ways to make plastics more biodegradable from exposure to sunlight.
Prolonged exposure to ultraviolet radiation from the sun causes many plastics molecules
to become brittle and slowly break apart. Researchers are working to create plastics that
will degrade faster in sunlight, but not so fast that the plastic begins to degrade while still
in use.
C. Incineration: Some wastes, such as paper, plastics, wood, and other flammable materials
can be burned in incinerators. The resulting ash requires much less space for disposal
than the original waste would. Because incineration of plastics can produce hazardous air
emissions and other pollutants, this process is strictly regulated.
D. Recycling Plastics: All plastics can be recycled; Thermoplastics can be melted and made
into new products. Thermosetting plastics can be ground, commingled (mixed), and then
used as filler in moldable thermoplastic materials. Highly filled and reinforced
thermosetting plastics can be pulverized and used in new composite formulations.
Chemical recycling is a depolymerization process that uses heat and chemicals to break
plastic molecules down into more basic components, which can then be reused. Another
 process, called pyrolysis, vaporizes and condenses both thermoplastics and thermosetting
plastics into hydrocarbon liquids.
If plastic types are not segregated, the recycled plastic cannot achieve high
remolding performance, which results in decreased market value of the recycled plastic.
Other factors can adversely affect the quality of recycled plastics. These factors include
the possible degradation of the plastic during its original life cycle and the possible
addition of foreign materials to the scrap recycled plastic during the recycling process.
For health reasons, recycled plastics are rarely made into food containers; instead, most
recycled plastics are typically made into items such as carpet fibers, motor oil bottles,
trash carts, soap packages, and textile fibers.
To promote the conservation and recycling of materials, the U.S federal government
passed the resource conservation and recovery Act (RCRA) in 1976. In 1988 the plastic
bottle institute of the society of the plastics industry established a system for identifying
plastic containers by plastic type. The purpose of the ‘chasing arrows’ symbols that
appears on the bottom of many plastic containers is to promote plastics recycling. The
chasing arrows enclose a number (such as 1 indicating PET,polyethylene terephthalate, 2
indicating HDPE, High density polyethylene, 3 indicating PVC, polyvinylchloride, 4
indicating LDPE, low density polyethylene, 5 indicating PP, polypropylene, 6 indicating
PS, polystyrene and 7 indicating others), which aids in the plastics sorting process.
Table 4.1: Type, Identification Code, Properties and Uses of Plastics.
Type of plastic Type of plastic Properties of plastic Uses of plastic
Identification
Polyethylene • Clear • Mineral water
terephthalate • Hard bottles
(PET/PETE) • Tough • 2 liter soda bottles
• Barrier to gas and • Cooking oil bottles
water • Powder detergent
• Resistance to heat jars
• Resistance to • Fibre for clothing
grease/oil • Fibre for carpets
• Strapping
• Peanut butter jars
High density • Chemical resistance • “Crinkly” shopping
polyethylene • Hard to semi- bags
(HDPE) flexible • Film
• Strong • Milk packaging
 • Soft waxy surface • Toys
• Low cost • Buckets
• Permeable to gas • Rigid pipes
• Natural milky white • Crates
colour • Bottle caps
Barrier to water Jerry cans

Polyvinyl chloride Transparent Pipes and fittings

(PVC) • Hard, rigid (flexible • Carpet backing
when • Window frames
plasticised) • Water, shampoo and
• Good chemical vegetable oil bottles
resistance • Credit cards
• Long term stability • Wire and cable
• Electrical insulation sheathing
• Low gas • Floor coverings
permeability • Shoe soles and
uppers
Low density •Tough •Agricultural films
polyethylene •Flexible •Refuse sacks
(LDPE) •Waxy surface •Packaging films
•Soft - scratches •Foams
easily •Bubble wrap
•Good transparency •Flexible bottles
•Low melting point •Wire and cable
•Stable electrical applications
properties
•Moisture barrier
propylene (PP) • Excellent chemical • Yoghurt containers
resistance • Potato crisp bags
• High melting point • Drinking straws
• Hard, but flexible • Medicine bottles
• Waxy surface • crates,
• Translucent • plant pots
• Strong • Car battery cases
• Heavy gauge woven
bags
Polystyrene (PS) • Clear to opaque • Packaging pellets
• Glassy surface • Yoghurt containers
• Rigid • Fast food trays
• Hard • disposable cutlery
• Brittle • Coat hangers
• High clarity
• Affected by fats and
solvents
Other plastics