Polymers

What is Polymers ?

• A polymer is a large molecule or a macromolecule which essentially is a combination of many

subunits. The term polymer in Greek means ‘many parts’.

• Polymers may be naturally found in plants and animals (natural polymers) or may be man-made
(synthetic polymers). Different polymers have a number of unique physical and chemical
properties due to which they find usage in everyday life.

• 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.

History of Polymers

With an increase in understanding in the structure of these materials there was rapid development in
the technology of polymers. Their historical development generally follows five stages:

1. from earliest time to 1900: the realization of a new material group

2. 1900 -1930 The birth of a plastic technology,

3. 1930 -1950 Plastics as substitute materials

4. 1950 -1970 The "Plastics" age

5. 1970 - now Engineering Plastics.

Hermann Staudinger

German organic chemist who demonstrated the existence of

macromolecules

John Wesley Hyatt

an American inventor. He is mainly known for simplifying the

production of celluloid
Structure of Polymers

Polymers consist of long chains, which are composed of simple structural units (mers) joined together.

Classification of Polymers

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.

Synthetic Polymers:

These are man-made polymers. It is used in industries and various dairy products. For example, nylon 6-
6, polyether’s etc.

Semi-synthetic Polymers:

They are derived from naturally occurring polymers and undergo further chemical modification. For
example, cellulose nitrate, cellulose acetate and Vulcanized rubber

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.. poly-vinyl chloride(PVC) 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.

Other Ways to Classify Polymers

• Classification Based on Polymerization

• Classification Based on Monomers

• Classification Based on Molecular Forces

Advantages of Polymer

• Many uses because of their different properties.

• Provide jobs in firms which make the polymer and the product.

• Some polymers can be recycled, melted down and made into something else which saves
valuable natural resources .If polymers are used instead of wood, fewer trees will have to be cut
down.

Disadvantages of Polymer

• The area nearby the polymer-producing industrial works area is dangerous on health.

• Its made from oil, a non-renewable resource.

• Most plastics are not biodegradable so there is a big problem of how to get rid of them and
accumulate easily in landfills.

• Give off toxic fumes when they burn.

• Sorting types of polymers for recycling can be expensive.

Types of Polymers

On the basis of the type of the backbone chain:

Organic Polymers - a Polymer whose backbone chain is essentially made of carbon

atoms. Ex. cellulose, proteins, polyethylene, nylons.

Inorganic polymer - a Polymer which does not have carbon atom in their chain.

Ex. Glass and silicone rubber.

On the basis of their synthesis:

Natural polymers - a polymers which are isolated from natural materials. Ex. Cotton, silk, wool, rubber.

Synthetic polymers - a polymers synthesized from low molecular weight compounds. Ex. polyethylene,
nylon, terylene.

Biodegradable polymers - a polymers which are degraded and decayed by microorganisms like bacteria.
These types of polymers are used in surgical bandages, capsule coatings. Ex. Poly(β-hydroxy butyrate-co-
β-hydroxy valerate)[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.

Ex. Polysulfone, Polyphenylene sulfide

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.

Optical Properties

Due to their ability to change their refractive index with temperature as in the case of PMMA (Poly-
methyl methacrylate) and HEMA (Hydroxyethylmethacrylate), they are used in lasers for
applications in spectroscopy and analytical applications.

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 is a plastic which is made up of monomers phenol and aldehyde

How polymer is manufactured

Polymerization, any process in which relatively small molecules, called monomers, combine
chemically to produce a very large chain like or network molecule, called a polymer.

POLYMERIZATION REACTION

Polymers are high-molecular-weight compounds, fashioned by the aggregation of many smaller

molecules called monomers. The plastics that have so changed society and the natural and synthetic
fibers used in clothing are polymers.

There are two general types of polymerization reactions:

Chain reaction / Addition polymerization, and

Step-reaction / Condensation polymerization.

Addition polymerization

(sometimes called chain reaction polymerization) is a process by which monomer units are attached
one at a time in chainlike fashion to form a linear macromolecule. The composition of the resultant
product molecule is an exact multiple of that of the original reactant monomer.

• Three distinct stages—initiation, propagation, and termination—are involved in addition

polymerization.
• Initiation step

During the initiation step, an active center capable of propagation is formed by a reaction
between an initiator (or catalyst) species and the monomer unit. This process has already
been demonstrated for polyethylene. which is repeated as follows.

Again, R represents the active initiator, and is an unpaired electron.

• Propagation Step

Propagation involves the linear growth of the polymer chain by the sequential addition of
monomer units to this active growing chain molecule. This may be represented, again for
polyethylene, as follows:

Chain

growth is relatively rapid; the period required to grow a molecule consisting of, say, 1000
repeat units is on the order of 10-2 to 10-3s.

• Termination Step

Propagation may end or terminate in different ways. First, the active ends of two
propagating chains may link together to form one molecule according to the following
reaction:

The other termination possibility involves two growing molecules that react to form two
“dead chains” as:

thus terminating the growth of each chain.

CONDENSATION POLYMERIZATION

Condensation polymerization (or step reaction polymerization) is the formation of polymers by

stepwise intermolecular chemical reactions that may involve more than one monomer species.

There is usually a small molecular weight by-product such as water that is eliminated (or
condensed). No reactant species has the chemical formula of the repeat unit, and the intermolecular
reaction occurs every time a repeat unit is formed. For example, consider the formation of the
polyester poly(ethylene terephthalate) (PET), from the reaction between ethylene glycol and
terephthalic acid; the intermolecular reaction is as follows:

This stepwise process is successively repeated, producing a linear molecule. The chemistry of the
specific reaction is not important, but the condensation polymerization mechanism is. Furthermore,
reaction times for condensation are generally longer than for addition polymerization.

MOLECULAR MASS OF POLYMERS

• Repetitive units make up a polymer.

• These repetitive units were originally the monomer molecules.

• When polymer chains form their lengths and thus their weights differ.

• It is important to be able to characterize the polymer structure.

• Molecular weight of a polymer is defined as sum of the atomic weight of each of the atoms in
the molecules, which is present in the polymer
 • Number average molecular weight The number average molecular weight is just the total
weight of all the polymer molecules in a sample, divided by the total number of polymer

molecules in a sample

where Ni the number of molecules having a molecular weight Mi, and wi is the weight
fraction of all molecules having a molecular weight Mi.

• Weight average molecular weight

Another way to express the average molecular weight is to calculate the weight average,
which is the sum of all molecular weights multiplied by their weight fractions:

where Ni the number of molecules having a molecular weight Mi, and wi is the weight
fraction of all molecules having a molecular weight Mi.

• Polydispersive index

It is the ratio of weight average molecular mass and number average molecular mass of
Polymers
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INNOVATION 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

lymer Monomer Uses of Polymer

Rubber Isoprene (1, 2-methyl 1 – 1, 3-butadiene) Making tyres, elastic materials

BUNA – S (a) 1, 3-butadiene (b) Styrene Synthetic rubber

BUNA – N (a) 1, 3-butadiene (b) Vinyl Cyanide Synthetic rubber

Teflon Tetra Flouro Ethane Non-stick cookware – plastics

Terylene (a) Ethylene glycol (b) Terephthalic acid Fabric

Glyptal (a) Ethylene glycol (b) Phthalic acid Fabric

Bakelite (a) Phenol (b) Formaldehyde Plastic switches, Mugs, buckets

PVC Vinyl Cyanide Tubes, Pipes

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

Formaldehyde
Resin
Nylon-6 Caprolactum Fabric
Reference:

• https://byjus.com/jee/polymers/

• https://www.essentialchemicalindustry.org/polymers/polyethene.html

• https://getrevising.co.uk/grids/polymers

• https://www.sciencehistory.org/the-history-and-future-of-plastics