Unit-1

INTRODUCTION TO POLYMERS

Monomers, Oligomers, Polymers and their characteristics. Classification of polymers: Natural,

synthetic, linear, cross linked and network, Plastics, elastomers, fibers, Homopolymers and Co-
polymers. Bonding in polymers: Primary and secondary bond forces in polymers, cohesive energy.
Determination of Molecular mass of polymers: Number Average molecular mass (Mn) and weight
average molecular mass (Mw) of polymers.

Introduction
1. What are polymers?

Polymers are high molecular weight compounds whose structures are made up of a large number of simple
repeating units. The interlinking of many units has given the polymer its name‘Poly’ means many,mers means
units=polymers. Small molecules are combined to form a big molecule i.e., polymers.it Can be formed from one
or more chemical compounds.

Eg: Butadiene (CH2=CH-CH=CH2)

butadiene+butadiene+…. +→polybutadiene (m.w-54)(4000 times)

1.1 DEGREE OF POLYMERISATION:

The number of repeating units in a polymer is known as degree of polymerization.

• If n =low, Mol.Wt = 500 – 5000 Dalton units, it is Oligo polymer.

• If n = High, Mol.Wt = 10,000 – 2,00,000 Dalton units, it is High polymer.

1.2 Monomer:
The repeating units are usually obtained from low molecular weight simple compounds referred to as
monomers.The reaction by which monomers are converted into polymers is known as polymerization.The
formation of polyethylene from ethylene is an example of polymerization reaction.

Fig1.2 Example of ethylene monomer

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1.2.1Requirements of monomer

• It should possess at least

a) two bonding sites (multiple bonds) or b) reactive functional groups.

1.3 Oligomers:Oligomers are low molecular weight polymers comprising a small number of repeating units.This
process of formation is called as oligomerization. Oligomers are significantly dependent on the length of the chain.It
is the intermediate of the polymerization reaction.

• Types of oligomers:

• 1.Homo oligomers (multiple copies of same subunits)

• 2.Hetero oligomers (different protein chains).

1.4Characteristics of polymers:

Polymers are having Low density,Economical,Good mould ability,Corrosion resistance,Poor tensile strength,
Poor temperature strength, Non-toxic in nature, Low cost.

1.5Types of polymerization

The reaction in which monomers combine to give polymers is known as polymerization. It can be broadly classified
into three categories as

• addition polymerization:Monomers having multiple bonds (double or triple bond) undergo addition
polymerization. Monomers combine to give polymer through addition reaction without elimination of any
smaller molecules. Therefore, the molecular weight of the resulting polymer will be an integral multiple of
the molecular weight of monomers.Eg:Ethylene to polyethylene.

•
• condensation polymerization:Monomers having same or different types of functional groups undergo
condensation polymerization. The polymerization proceeds by step wise reaction between reactive functional
groups and small molecules are eliminated. Eg: polymerization reaction of nylon66.

•
Copolymerization:. It is a special kind of polymerization, otherwise known as “Joint polymerization”.
The product is known as ‘Co-polymers’. This is superior to other polymerization because it is used to alter the hardness,
strength, rigidity and crystallinity of the monomers.

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 • The differences between two major polymerization methods are tabulated as follows:

S. No Addition Polymerization Condensation Polymerization

1 Eg. PVC Eg. Nylon 6,6
2 Otherwise known as “Chain growth Otherwise known as “Step wise
Polymerization”. Polymerization”.
3 Monomers are adding together to form polymers. Monomers are condensed to form polymer.
4 No elimination of other molecules. Elimination of smaller molecules occur.
5 At least one multiple bond presence is essential Monomers must have two or more functional
condition. groups.
6 Homo polymers are formed. Hetero polymers are formed.
7 Thermoplastics are formed. Thermo set plastics are formed.
8 Molecular weight of the polymer is the integral Need not be so.
multiple of monomers.
9 Monomers disappear slow and steadily. Monomers disappear at the initial stage of the
reaction.
10 Longer processing time is needed to increase Longer time is essential for increasing
yield. molecular weight.

1.2Classification of polymers:

Based on origin of source:

Natural polymers:Depending on their origin, polymer can be grouped into natural or synthetic.Those isolated from
natural materials are called natural polymers.Example: cotton, wool, silk and rubber. It is also non-toxic.

Advantages:Readily and abundantly available,Comparatively inexpensive,Nontoxic products,Biodegradable.

Synthetic polymers:Polymers synthesized from low molecular weight compounds are called synthetic polymers.
Example : polyethylene ,nylon, PVC and terylene

Based on the structure:

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 Linear polymer:In these polymers’ monomers are linked with each other and form a long straight chain. These
polymer chains do not consist any side chains. A linear polymer can be schematically represented by a single
line. Example: polyethylene

-A-A-A-A-A-A-A-A-A-A- a polymer made of A atoms.

nCH2=CH2 →-CH2-CH2-→-(CH2-CH2-)n

Cross linked polymer:They have long straight chain with different branched side chains.Molecules are irregularly
packed. Example:polyethyleneHDPE-High Density polymer LDPE-Low Density polymer

Network polymers:Network polymers have trifunctional monomeric units that are formed by many
interconnected polymer chains.They are giant molecules in which movement of individual monomeric unit
is prevented by strong cross links.It is having three active covalent bonds. It should be in three-dimensional
network.Eg: Bakelite, urea formaldehyde, melamine formaldehyde,etc.

1.3Plastics:The term plastic or plastic material, is given to “organic materials of high molecular weight, which
can be moulded into any desired form,when subjected to heat and pressure in the presence of a catalyst’.The term
plastics are differentiated from the resin.resins are the basic binding materials which form a major part of the
plastics,and which actually has undergone polymerization and condensation reactions,during this preparation.

1.3.1Thermoplastic polymers:

These polymers are linear,long chain polymers, which can be softened on heating and cooling reversibly.This is
called thermoplastics’.,their hardness is a temporary property, subject to change with rise or fall of
temperature.Eg:polythene,polypropylene (PP), polyvinylchloride (PVC), PTFE.,etc.

1.3.2Thermosetting polymers(thermosets):Thermosets are those polymers, which during moulding (by heating)get
hardened and once they have solidified i.e.they are permanent polymers.Such polymers during moulding acquire
three-dimensional cross-linked structure,with strong covalent bonds.

Thus,a thermosetting polymer once moulded cannot be reprocessed.

Eg: polystyrene (terylene), Bakelite, epoxy resin, melamine, urea formaldehyde etc.

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Differences between Thermoplastics and thermosetting plastics

S.No THERMOPLASTICS THERMOSETTING PLASTIC

1 Eg.PVC , Polyethylene Polyester, Bakelite
2 Plastics which are melted at high They cannot be remoulded after their first
temperature, solidified at low temperature usage.
They can be remelted and remoulded into
any desired shapes for any number of times.
3 Scrap can be used again. Scrap cannot be used again.
4 Formed by addition polymerization Formed by condensation polymerization
5 The bond strength is low The bond strength is high
6 Molecular weight is low Molecular weight is high
7 Soluble in organic solvents. Insoluble in organic solvents.
8 Prepared by Injection moulding Prepared by compression moulding.
9 They have linear structure They have complex 3D structure.

1.4 Elastomers:Elastomer are high polymers, which have elastic properties in excess of 300%.An
elastomer(rubber)is any vulcanisable man-made rubber-like polymer. when vulcanized into the rubbery products
exhibiting good strength and elongation, polymers used as elastomers. An elastomer molecule is not straight
chained eg: polyethene, nylon etc.,but in the case of coil,it can be stretched like a spring.Natural rubber consists
of basic material latex, which is a dispersion of isoprene.The isoprene molecules polymerize to form,long –coiled
chains of cis –polyisoprene.Structure of natural rubber:

1.4.1Fibres: are those polymers whose chains are held by strong intermolecular forces like hydrogen bonding.They
are crystalline in nature and of high tensile strength,due to strong intermolecular forces.

Eg: nylon,polyester

1.5Homopolymers:When all the repeating units in a particular polymer have the same structure,that polymer is called
a homopolymer.Eg: vinyl chloride

1.5.1Copolymers:When different repeating units make up the polymer chain ,the polymer is called a copolymer.A-
A-B-B-B-A-B-A-A-B—

Types of copolymer:

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 • Alternating copolymers(A-B-A-B-A-B-)

• Block copolymers (A-A-A-A-B-B-B-B)

• Random copolymers(A-B-B-B-A-A-B-B-)

• Eg:poly[vinyl chloride –vinyl acetate ]copolymers

1.5.6Bonding in polymers:A molecule is connected by covalent bonds.Chemical reactions are required to form
or break covalent bonds. Weaker attractions often form between molecules, encouraging them to stick together
in groups. The weaker attractions are called secondary bonds or intermolecular forces. These can be overcome
by adding heat or dissolving in a liquid. the functional groups on a polymer determine the type and strength of
its secondary bonds.

• Types of interactions present in bonding of polymers:

Polar interactions:The valence electrons moving around a molecule may not be symmetrically distributed. The
nonmetallic elements closest to the right top corner of the periodic table - nitrogen, oxygen, fluorine and chlorine
- tend to shift shared electrons away from carbon and hydrogen. When there is a functional group with one of
those elements, it has a slight negative charge and the rest of the molecule (carbon and hydrogen) is slightly
positive. The molecule is polarized. Its positive sections are attracted to negative sections of neighboring
polymers.eg: PET (Poly (ethylene terephthalate).it has oxygen containing functional groups make it
polar.Positive and negative charges can be localized on a covalent molecule since they have no path for
conduction of electrons. The carbon atoms in the backbone always follow the octet rule with four covalent bonds,
so can't pass extra electrons along the chain. If polymer fibers are rubbed together, they can build up a static
electricity charge.

• Hydrogen bonds:Molecules with either -N-H or -O-H groups will form strong secondary bonds. Eg:hydrogen
bonding in water.This phenomenon is responsible for the relative high boiling point of water, and for the fact
that its solid form (ice) is less dense than its liquid form. Polymers with hydrogen-bonding groups will soak up
water.

Non-polar interactions:As valence electrons move around the nuclei in a nonpolar polymer, like polyethylene or
polyfluoroethylene, they can become temporarily imbalanced. So,one part of a molecule would be negative, another
part positive; it is temporarily polar. These occasional imbalances are enough to allow nonpolar molecules to attract
each other, but the interaction is much weaker than that observed for polar or hydrogen bonding polymers.

eg: Polyfluoroethylene is nonpolar (not polar) because it is completely covered with fluorine atoms; there is no
exposed positive section to interact with a neighboring molecule's negative section.