FACULTY OF RESOURCE SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY

STK 2103 – POLYMER CHEMISTRY

ASSIGNMENT 1 : TO INVESTIGATE THE TOPIC “POLYMERS”

FROM A CHEMICAL PERSPECTIVE

DATE OF SUBMIT : 26th OCTOBER 2018

ASSIGNMENT

NAME & MATRIC : SHARIFAH ZULAIKHA BINTI SYED SAHIMI

NO (64138)

LECTURER NAME : PROFESOR DR. FASIHUDDIN BIN BADRUDDIN

AHMAD
QUESTION 1
Determine and demonstrate an understanding of the following key terms: monomer, polymer,
copolymer, elastomer, addition polymerisation, condensation polymerisation, thermoplastic,
thermosetting, catalyst, cross-linking.

1) Monomer
A monomer is a small molecule that reacts with a similar molecule to form a larger
molecule, which they joined together in a repeating fashion to form more complex molecules
called polymers.

The word monomer derives from the Greek prefix monos – which
means “single” or “only”.

In IUPAC definition, a monomer is a molecule which can

undergo polymerization, thereby contributing constitutional units to
the essential structure of a macromolecule.

Monomers are the building blocks for biological macromolecules such

as DNA, RNA, proteins and carbohydrates. Monomers are important
in the synthesis of many materials in the industrial world.
Monomer may bind to other monomers to form a repeating
chain molecule through a process called polymerization. Monomers
may be either natural or synthetic in origin.

Monomers are not just building blocks of polymers, but are important molecules in their own
right, which do not necessarily form polymers unless the conditions are right.
Examples of Monomers

 vinyl chloride (polymerizes into polyvinyl chloride or PVC)

 glucose (polymerize into starch cellulose, laminarin and glucans)
 amino acids (which polymerize into peptides, polypeptides and proteins)
2) Polymer
The word polymer comes from poly- (many) and –mer (part). A polymer may be a
natural or synthetic macromolecule compromised of repeating units of a smaller molecule
(monomers). Polymer also been called plastic interchangeably, because they are much larger
class of molecules which includes plastics, plus many other materials, such as cellulose, amber
and natural rubber.

In IUPAC definition, a polymer is a molecule of high relative molecule mass. The structure of
which essentially comprises the multiple repetition of units derived, actually or conceptually,
from molecules of low relative molecular mass.
Examples of polymers

 polyethylene
 silicons such as silly putty
 biopolymers such as cellulose and DNA
 natural polymer such as rubber and shellac
 other important macromolecules
Polymerization is the process of covalently
bonding the smaller monomers into the polymer.
During polymerization, chemical groups are lost
from the monomers so that they may join together.
In the case of biopolymers of carbohydrates, this is
a dehydration reaction in which water is formed.

Many common classes of polymers are composed of hydrocarbons, compounds of carbon

and hydrogen. These polymers are specifically made of carbon atoms bonded together, one to
the next, into long chains that are called the backbone of the polymer. Because of the nature of
carbon, one or more other atoms can be attached to each carbon atom in the backbone. There
are polymers that contain only carbon and hydrogen atoms.

Linear polymer can be arranged if they lack specific order or are amorphous. Controlling
the polymerization process and quenching molten polymers can result in amorphous
organization. An amorphous arrangement of molecule has no long-range order or form in
which the polymer chains arrange themselves. Amorphous polymers are generally transparent.
This is an important characteristic for many applications such as food wrap, plastic windows,
headlight lenses and contact lenses. Not all polymers are transparent.
3) Copolymer
When a polymer is made by linking only one type of small monomer, together it will
be homopolymer. When two different types of monomers are joined in the same polymer chain,
this called copolymer.

Synthetic copolymers are rarely complicated, but there are still possibilities for a simpler
systems. There are so many ways such as two polymers can be sequenced along the backbone.
There are some limiting case such as:

Copolymers are further classified as alternating copolymers or statically regular (where both
different repeating monomeric units are joined side by side) and random copolymers or
statically irregular (where there is no regularity in the joining of units of two different
monomers.
4) Elastomer
Elastomer is a polymer with the physical property of elasticity. Elastomer is a term
derived from elastic polymer, which is often used interchangeably with the term rubber. Each
of the monomers which link to from the polymer is usually made of carbon, hydrogen, oxygen
or silicon. Elastomer are usually thermosets requiring a curing process of rubber involving heat
and the addition of sulfur or other equivalent curatives. Elastomers might also be thermoplastic.

Elastomers are also cross-linked, but have a low cross-link density. The polymer chains
still have some freedom to move, but are prevented from permanently moving relative to each
other by the cross-links.

The main characteristic of elastomer materials is the high elongation and flexibility or elasticity
of these materials against its breaking or cracking.

Elastomeric materials can be classified into:

1) Thermoset Elastomer = the elastomer materials that not melt when heated
2) Thermoplastic Elastomer = the elastomer that melt when heated

The other properties of elastomer materials are swell in the presence of certain solvents. They
also generally insoluble, flexible, elastic and lower creep resistance than the thermoplastic
materials.
As for example, a rubber band or natural rubber and synthetic rubber.
5) Polymerization
Polymerization is a process where monomer are joined together to form long chain of
polymer. There are two types of polymerization take place which is Condensation
Polymerization and Additional Polymerization.

Chain-reaction polymerization sometimes called addition polymerization. It requires an

initiator to start growth of the reaction. While a step-reaction polymerization reaction,
sometimes called condensation polymerization. It grow by reactions that occur between two
molecular species.
The comparison for both polymerization are below:

Additional Polymerization Condensation Polymerization

 Formed when unsaturated organic
molecules joined together using 𝜋-
electrons to form covalent bond of ling
polymeric chain
 No side product is formed
 Empirical formula of the monomer is the
same as the empirical formula of
polymer formed
 Formed when two molecules, each
with two same functioning group at the
end of the molecule, joined up via
condensation reaction
 Small molecule is form as side product
(H2O, HCl)
 Empirical formula of the monomer is
different from the empirical formula of
polymer formed
6) Thermoplastic and Thermosetting
Most linear polymers take on new shapes by the application of heat and pressure. They
are thus called Thermoplastics whereas the cross-linked polymers cannot be made to flow or
melt irreversibly and are said to be Thermosetting resins. The difference between these two
types are listed in the table. A polymer may contain monomers of identical or different chemical
structure.

THERMOPLASTICS
 They are often formed by addition
polymerization leading to long linear
chain polymers with no cross-links.
 They soften readily on heating because
secondary forces between the individual
chains can break easily by heat or
pressure.
 They can be reshaped and reused.
 They are usually soft, weak and less
brittle.
 These can be reclaimed from wastes.
 They are usually soluble in suitable
solvents.
THERMOSETTS
 They are often formed by condensation
polymerization and three dimensional
network structures are formed.
 They do not soften on heating. On
prolonged heating, however charring of
polymers is caused.
 They cannot be reshaped and reused.
 They are usually hard, strong and more
brittle.
 They cannot be reclaimed from wasted.
 Due to strong bonds and intra- and
interchain cross-links, they are insoluble
in almost all organic solvents.
7) Catalyst
Ziegler-Natta catalyst is any of mixtures chemical compounds because they effect the
polymerization of hydrocarbons containing a double carbon-carbon bond or called olefins to
polymers of high molecular weights and highly ordered structures.

These catalysts were originated in the 1950s by the German chemist Karl Ziegler and Giulio
Natta for the polymerization of ethylene at atmospheric pressure. A typical Ziegler-Natta
catalyst system usually contains two parts:

 A transition metal (Group IV metals, like Ti, Zr Hf) compound

 An organoaluminum compound (co-catalyst).

8) Cross-linking
In IUPAC definition, cross-linking is a small region in a macromolecule from four
chains emanate and formed by reactions involving sites or groups on existing. The formation
of covalent bonds which hold portions of several polymer chains together is called cross-
linking. Extensive cross-linking produces a substance which has more rigidity, hardness and a
higher melting point than the equivalent polymer without cross-linking. Almost all the hard
and rigid plastics we used are cross-linked.
QUESTION 2

a) List five (5) products made from polymers and identify the polymers each contains.
1. Soft drink Bottle from Polyethylene Terephthalate (PET/PETE)
2. Trash Plastic from High Density Polyethylene (HDPE)
3. Yogurt Package from Polypropylene (PP)
4. Food Wraps/Plastics from Polyvinyl Chloride (PVC)
5. Take-out Containers from Polystyrene (PS)

Soft drink Bottle from Polyethylene Terephthalate (PET/PETE)

PET is produced by the polymerization of ethylene glycol and terephthalic acid.

Ethylene glycol is a colourless liquid obtained from ethylene, and terephthalic acid is
a crystalline solid obtained from xylene. When heated together under the influence of
chemical catalysts, ethylene glycol and terephthalic acid produce PET in the form of a molten,
viscous mass that can be spun directly to fibres or solidified for later processing as a plastic.
Under the influence of heat and catalysts, the hydroxyl and carboxyl groups react to
form ester (CO-O) groups, which serve as the chemical links joining multiple PET units
together into long-chain polymers. Water is also produced as a by-product. The overall reaction
can be represented as follows:
 The presence of the large benzene rings in the repeating units gives the polymer notable
stiffness and strength. PET is the most important of the man-made fibres in weight produced
and in value. At a slightly higher molecular weight, PET is made into a high-
strength plastic that can be shaped by all the common methods employed with other
thermoplastics.

Trash Plastic from High Density Polyethylene (HDPE)

HDPE is a hydrocarbon polymer prepared from ethylene/petroleum by a catalytic

process. It is a kind of thermoplastic which is famous for its tensile strength. Its unique
properties can stand high temperatures. HDPE is the most versatile of plastics and widely
recycled, in both its rigid form and flexible form.

Produced in fits and starts in the 1930s in the United

Kingdom. It’s made by stringing together ethylene
molecules, which are derived predominately from natural
gas resources in the U.S. HDPE is manufactured at low
temperatures and pressures, using Ziegler-Natta and metallocene catalysts or
activated chromium oxide or Phillips catalyst. The lack of branches in its structure allows the
polymer chains to pack closely together, resulting in a dense, highly crystalline material of high
strength and moderate stiffness. HDPE’s temperature is more than 20 °C (36 °F) higher than
LDPE, it can withstand repeated exposure to 120 °C (250 °F) so that it can be sterilized.
Products include blow-moulded bottles for milk and household cleaners, caps, appliance
housings, and toys. The plastic recycling code number of HDPE is #2.
Yogurt Package from Polypropylene (PP)

Polypropylene was discovered in

1954 and has the lowest density among
commodity plastics. PP has an excellent
chemical resistance and can be processed
through many converting methods such as
injection moulding and extrusion.

Polypropylene is a polymer prepared

catalytically from propylene. It is major advantage is related to the high temperature resistance
which makes PP particularly suitable for items such as trays, funnels, pails, bottles, carboys
and instrument jars that have to be sterilized (cleaned) frequently for use in a clinical
environment. Polypropylene is a free-colour material with excellent mechanical properties and
it is better than polyethylene for the previous reasons. Polypropylene is a downstream
petrochemical product that is derived from the olefin monomer propylene.

Polypropylene properties vary according to process conditions, copolymer components,

molecular weight and molecular weight distribution. Polypropylene is a vinyl polymer in which
every carbon atom is attached to a methyl group and can be expressed. Polypropylene chemical
resistance is excellent resistance to dilute and concentrated acids, alcohols and bases, good
resistance to aldehydes, esters, aliphatic hydrocarbons, ketones and limited resistance to
aromatic and halogenated hydrocarbons and oxidizing agents. Polypropylene has a crystalline
structure with a high level of stiffness and a high melting point compared to other commercial
thermoplastics.

The Hardness resulted from the methyl groups in its molecular chain structure.
Polypropylene is a lightweight polymer with a density of 0.90 g/cm3 that makes it suitable in
many industrial applications. Still, polypropylene is not suitable to be used at temperatures
below 0°C. It is relatively stiff and has a high melting point, low density and relatively good
resistance to impacts.
Food Wraps/Plastics from Polyvinyl Chloride (PVC)

Polyvinyl Chloride (PVC) is a naturally white and very brittle (prior to the additions of
plasticizers) plastic. PVC has been around longer than most plastics having been first
synthesized in 1872 and commercially produced by B.F. Goodrich Company in the 1920s. By
comparison, many other common plastics were first synthesized and became commercially
viable only in the 1940s and 1950s. It is used most commonly in the construction industry but
is also used for signs, healthcare applications, and as a fibre for clothing.

PVC is produced in two general forms:

 rigid or unplasticized polymer (RPVC or uPVC)

 flexible plastic

PVC is low price, resistance to environmental degradation high hardness, and outstanding
tensile strength for a plastic as for rigid PVC. It is widely available, commonly used and easily
recyclable (categorized by resin identification code “3”).

Rigid PVC in particular has very high density for a plastic making it extremely hard
and generally very strong. It is also readily available and very economical which combined
with the long-lasting characteristics of most plastics make it an easy choice for many industrial
applications like construction.

Polyvinyl Chloride is made from one of three emulsion processes:

1. Suspension polymerization
2. Emulsion polymerization
3. Bulk polymerization
PVC can pose a health hazard when it is burned as it emits hydrogen chloride (HCl) fumes. In
applications where the likelihood of fire is high, PVC free electrical wire insulation is
sometimes preferred.

Take-out Containers from Polystyrene (PS)

Polystyrene (PS) plastic is a naturally transparent thermoplastic that is available as both

a typical solid plastic as well in the form of a rigid foam material. PS plastic is commonly used
in a variety of consumer product applications and is also particularly useful for commercial
packaging. The solid plastic form of polystyrene is commonly used in medical device
applications like test tubes or petri dishes, or in day-to-day items like the housing on smoke
detectors. The foam form of polystyrene is used most often as a packing material. Styrofoam
is also used for “to-go” containers and disposable tableware from many restaurants.

Three major types of polystyrene:

 polystyrene foam
 polystyrene plastic
 polystyrene film

Amongst the different types of foam are expanded polystyrene (EPS) and extruded
polystyrene (XPS). EPS includes the most well-known and common types of polystyrene to
include Styrofoam and packing peanuts. XPS is a higher density foam typically used in
applications like architectural building models. Some types of polystyrene plastic are
copolymers. Oftentimes homopolymer PS is fairly brittle and can be made more impact
resistant if combined with other materials. Polystyrene film can also be vacuum formed and
used in packaging applications.

Generally speaking polystyrene is non-toxic and odourless. It is a predominant plastic in the

food packaging industry. While that might lead you to believe it is entirely safe. Polystyrene is
flammable and similar to other organic compounds, it emits carbon dioxide and water when it
is burned.
b) Identify five (5) polymers as examples that allow you to explain and demonstrate; addition
polymerisation, condensation polymerization and cross-linking.
For each of the five polymers given as examples provide:
o the name of the monomer or copolymers
o the structure of the polymer
o the reaction(s) for producing the polymer
o the main properties and uses of the polymer
 Types of Types of Name of the Structure Reaction for Main properties
Polymers Polymerization monomer or of the producing the and uses of the
copolymer polymer polymer polymer
Polyethylene Condensation Ethylene Semi- Free radical High clarity and
Terephthalate Polymerization Terephthalate Crystalline polymerization good chemical
(PET/PETE) resistance solid.
Uses for
cosmetic and
baked goods
containers.
High Density High-pressure Ethylene and Linear Coordination Rigid and
Polyethylene polymerization LHDPE polymerization translucent solid.
(HDEPE) Uses for
electrical
insulation and
toys.
Polypropylene Addition Propylene Linear Addition Soft and elastic
(PP) Polymerization polymerization solid. Uses for
carpet and
upholstery.
Polyvinyl Suspension Vinyl Linear Free radical Strong and rigid
Chloride Polymerization chloride polymerization solid. Uses for
(PVC) pipes, siding and
flooring.
Polystyrene Free Radical Styrene Linear Addition Hard, rigid and
(PS) Vinyl polymerization clear solid. Uses
Polymerization for food
packaging.