Chem111

Polymers
Polymers are substances composed of macromolecules, very large molecules with
molecular weights ranging from a few thousand to as high as millions of grams/mole.
The IUPAC Gold Book definition of a macromolecule is: “A molecule of high relative
molecular mass, the structure of which essentially comprises the multiple repetition of
units derived, actually or conceptually, from molecules of low relative molecular mass.”
https://iupac.org/polymer-edu/what-a/re-polymers

Polymers may be naturally found in plants and animals (natural polymers) or may be
man-made (synthetic polymers)

Polymers are all created by the process of polymerization wherein their constituent
elements called monomers, are reacted together to form polymer chains i.e 3-
dimensional networks forming the polymer bonds.
The type of polymerization mechanism used depends on the type of functional
groups attached to the reactants. In biological contexts, almost all macromolecules are
either completely polymeric or are made up of large polymeric chains.

Classification of Polymers based on the Source of Availability

Natural Polymers:
They occur naturally and are found in plants and animals. For example proteins, starch,
cellulose, and rubber. To add up, we also have biodegradable polymers which are
called biopolymers.
Semi-synthetic Polymers:
They are derived from naturally occurring polymers and undergo further chemical
modification. For example, cellulose nitrate, cellulose acetate.
Synthetic Polymers:
These are man-made polymers. Plastic is the most common and widely used synthetic
polymer. It is used in industries and various dairy products. For example, nylon-6, 6,
polyether’s etc.

Classification of Polymers based on the Structure of the Monomer Chain

Linear Polymers
The structure of polymers containing long and straight chains fall into this category.
PVC, i.e. poly-vinyl chloride is largely used for making pipes and electric cables is an
example of a linear polymer.
Branched-chain Polymers
When linear chains of a polymer form branches, then, such polymers are categorized as
branched chain polymers. For example, Low-density polythene.
Cross-linked Polymers
They are composed of bifunctional and trifunctional monomers. They have a
stronger covalent bond in comparison to other linear polymers. Bakelite and melamine
are examples in this category.

Classification Based on Polymerization

• Addition Polymerization: Example, poly ethane, Teflon, Polyvinyl chloride

(PVC)
• Condensation Polymerization: Example, Nylon -6, 6, perylene, polyesters.
Classification Based on Monomers

• Homomer: In this type, a single type of monomer unit is present. For example,
Polyethene

• Heteropolymer or co-polymer: It consists of different type of monomer units.

For example, nylon -6, 6
Classification Based on Molecular Forces

• Elastomers: These are rubber-like solids weak interaction forces are present.
For example, Rubber.

• Fibres: Strong, tough, high tensile strength and strong forces of interaction are
present. For example, nylon -6, 6.
• Thermoplastics: These have intermediate forces of attraction. For example,
polyvinyl chloride.
• Thermosetting polymers: These polymers greatly improve the material’s
mechanical properties. It provides enhanced chemical and heat resistance. For
example, phenolics, epoxies, and silicones.

Structure of Polymers
Most of the polymers around us are made up of a hydrocarbon backbone.
A Hydrocarbon backbone being a long chain of linked carbon and hydrogen atoms,
possible due to the tetravalent nature of carbon.
A few examples of a hydrocarbon backbone polymer are polypropylene, polybutylene,
polystyrene. Also, there are polymers which instead of carbon have other elements in its
backbone. For example, Nylon, which contains nitrogen atoms in the repeated unit
backbone.

Types of Polymers
On the basis of the type of the backbone chain, polymers can be divided into:

• Organic Polymers: Carbon backbone.

• Inorganic Polymers: Backbone constituted by elements other than carbon.

Types of Polymers

On the basis of their synthesis:

• Natural Polymers
• Synthetic Polymers

Biodegradable Polymers
The polymers which are degraded and decayed by microorganisms like bacteria are
known as biodegradable polymers. These types of polymers are used in surgical
bandages, capsule coatings and in surgery. For example, Poly hydroxybutyrate co vel
[PHBV]

High-Temperature Polymers
These polymers are stable at high temperatures. Due to their high molecular weight,
these are not destroyed even at very high temperatures. They are extensively used in
the healthcare industries, for making sterilization equipment and in the manufacturing of
heat and shock-resistant objects.
Few of the important polymers are:
Polypropylene: It is a type of polymer that softens beyond a specific temperature
allowing it to be moulded and on cooling it solidifies. Due to its ability to be easily
moulded into various shapes, it has a lot of applications.
A few of which are in stationary equipment’s, automotive components, reusable
containers speakers and much more. Due to its relatively low energy surface, the
polymer is fused with the welding process and not using glue.
Polyethene: It is the most common type of plastic found around us. Mostly used in
packaging from plastic bags to plastic bottles. There are different types of polyethene
but their common formula being (C2H4)n.

Properties of Polymers

Physical Properties

• As chain length and cross-linking increases the tensile strength of the polymer
increases.
• Polymers do not melt, they change state from crystalline to semi-crystalline.

Chemical Properties

• Compared to conventional molecules with different side molecules, the polymer

is enabled with hydrogen bonding and ionic bonding resulting in better cross-
linking strength.
• Dipole-dipole bonding side chains enable the polymer for high flexibility.
• Polymers with Van der Waals forces linking chains are known to be weak, but
give the polymer a low melting point.
Optical Properties

• Due to their ability to change their refractive index with temperature as in the
case of PMMA and HEMA: MMA, they are used in lasers for applications in
spectroscopy and analytical applications.

Some Polymers and their Monomers

• Polypropene, also known as polypropylene, is made up of monomer propene.

• Polystyrene is an aromatic polymer, naturally transparent, made up of monomer
styrene.
• Polyvinyl chloride (PVC) is a plastic polymer made of monomer vinyl chloride.
• The urea-formaldehyde resin is a non-transparent plastic obtained by heating
formaldehyde and urea.
• Glyptal is made up of monomers ethylene glycol and phthalic acid.
• Bakelite or polyoxybenzylmethylenglycolanhydride is a plastic which is made up
of monomers phenol and aldehyde.

Types of Polymerization Reactions

Addition Polymerization
This is also called as chain growth polymerization. In this, small monomer units joined to
form a giant polymer. In each step length of chain increases. For example,
Polymerization of ethane in the presence of Peroxides

Condensation Polymerization
In this type small molecules like H2O, CO, NH3 are eliminated during polymerization
(step growth polymerization). Generally, organic compounds containing bifunctional
groups such as idols, -dials, diamines, dicarboxylic acids undergo this type of
polymerization reaction. For example, Preparation of nylon -6, 6.

What is Copolymerization?
In this process, two different monomers joined to form a polymer. Synthetic rubbers are
prepared by this polymerization. For example, BUNA – S.

Uses of Polymers
Here we will list some of the important uses of polymers in our everyday life.

• Polypropene finds usage in a broad range of industries such as textiles,

packaging, stationery, plastics, aircraft, construction, rope, toys, etc.
• Polystyrene is one of the most common plastic, actively used in the packaging
industry. Bottles, toys, containers, trays, disposable glasses and plates, tv
 cabinets and lids are some of the daily-used products made up of polystyrene. It
is also used as an insulator.
• The most important use of polyvinyl chloride is the manufacture of sewage pipes.
It is also used as an insulator in the electric cables.
• Polyvinyl chloride is used in clothing and furniture and has recently become
popular for the construction of doors and windows as well. It is also used in vinyl
flooring.
• Urea-formaldehyde resins are used for making adhesives, moulds, laminated
sheets, unbreakable containers, etc.
• Glyptal is used for making paints, coatings, and lacquers.
• Bakelite is used for making electrical switches, kitchen products, toys, jewellery,
firearms, insulators, computer discs, etc.

Commercial Uses of Polymers

Uses of
Polymer Monomer
Polymer

Isoprene (1, 2-methyl 1 Making tyres,

Rubber
– 1, 3-butadiene) elastic materials

(a) 1, 3-butadiene (b)

BUNA – S Synthetic rubber
Styrene

(a) 1, 3-butadiene (b)

BUNA – N Synthetic rubber
Vinyl Cyanide

Non-stick
Teflon Tetra Flouro Ethane cookware –
plastics

(a) Ethylene glycol (b)

Terylene Fabric
Terephthalic acid

(a) Ethylene glycol (b)

Glyptal Fabric
Phthalic acid

(a) Phenol (b) Plastic switches,

Bakelite
Formaldehyde Mugs, buckets

PVC Vinyl Cyanide Tubes, Pipes

 Melamine
(a) Melamine (b) Ceramic plastic
Formaldehyde
Formaldehyde material
Resin

Nylon-6 Caprolactum Fabric

https://byjus.com/jee/polymers/

Processing plastics
Processing converts plastics into useful articles. Processing methods are given in
Table 6
Process Application
Compression moulding Usually for thermosets - powder moulded under heat and
pressure.
Injection moulding Usually for thermoplastics - molten plastics injected into a
mould under pressure. The mould surface detail can be
accurately reproduced. Very widely used.
Rotational moulding Usually for thermoplastics. The powder is heated in a
closed mould which is rotated, fairly slowly, simultaneously
about two axes. Surface detail is poor but this method can
be used to make large hollow articles.
Reaction injection Usually for thermosets, polymerization takes place in the
moulding mould thereby producing the finished article directly from a
resin.
Extrusion Usually for thermoplastics - the molten plastics are fed by
a screw through a die, which for sheet or film, for instance,
is a slit. Various extensions to the process are possible -
e.g. a tube may be inflated by air whilst still hot to produce
a tubular film (for bags, etc.), or short lengths of hot
extruded tube can be inflated in moulds to form bottles.
Calendering Usually for thermoplastics - molten plastics squeezed
between hot rollers to form foil and sheet.
Thermoforming Heat-softened thermoplastic sheet is drawn into or over a
mould. If a vacuum is used to 'suck' the sheet into a
mould, the process is known as vacuum forming. This
process is used for a variety of articles, ranging from
chocolate box liners to acrylic baths.
Methods of processing plastics.
https://www.essentialchemicalindustry.org/polymers/polymers-