Introduction to Polymer Chemistry

Presented By: Adedotun I. S.

 Polymer Introduction
• Polymers are widely used advanced materials, which are found almost in
every material used in our daily life. The very existence of life is
virtually the formation, transformation and decomposition of the
polymers. This includes carbohydrates, proteins and nucleic acid in our
bodies.
• Fibers in clothing; soil where food is grown; protein and starch we eat;
elastomers in automobile tyres, paints, plastic wall, floor coverings, foam
insulation, dishes, furniture, pipes etc are also polymeric. In-spite of the
many varieties like fibers, elastomers and plastic, they all have a similar
structure and are governed by same theories.
 DNA Rubber Cellulose Nylon

Polyester Wool Teflon Epoxy

Polymeric Materials
 Polymer
• The word polymer is derived from the Greek words “poly” and “meros”
meaning many and parts respectively. Thus polymers or macromolecules
are giant molecules made up of multiple repeating units which are joined
together by covalent bonds. They have molecular weights at least 100
times greater than those of smaller molecules such as water or methanol.

• Examples:
PVC(polyvinylChloride), Poly(methylmethacrylate), Nylon -6, Nylon -6,6,
Polyurethanes, Polyoxyethylene, Natural rubber, Orlon – PAN, Dacron –
PET, etc.
 Monomer
• Monomer is the basic building unit which repeats
itself to form a polymer.
Cl
• Examples: Chloroprene
Ethylene, vinylchloride, styrene, isoprene, chloroprene
(2-chlorobuta-1,3-diene),tetrafluoroethylene,
acrylonitrile, etc.
Isoprene

F F
Cl N C H2C CH2
F F
vinyl chloride Acrylonitrile Tetrafluoroethylene Styrene Ethylene
 Degree of polymerization

• Degree of polymerization is defined as the number of repeating

monomeric units in a polymer.
• Degree of polymerization of:
CH2 CH2
(i) 1000 = 1000
CH2 CH2 CH2
(ii) 50000 = 50000

(If DP = 1 then it is monomer; DP=2 dimer; DP = 3 trimer; DP = 4

tetramer).
 Oligo polymers
• Polymers with low degree of polymerization are known as oligo polymers
and their molecular weight ranges from 500 - 5000.
• Many oils are oligomeric, such as liquid paraffin. Plasticizers are
oligomeric esters widely used to soften thermoplastics such as PVC.
Polybutene is an oligomeric oil used to make putty.

High Polymers
• Polymers with high degree of polymerization are known as high polymers
and their molecular weight ranges from 10,000 - 2, 00,000.
 Nomenclature
Little rhyme or reason is associated with the common names of
polymers.

• Some names are derived from the origin of the material (Example :
Hevea brasilliensis (natural rubber) – meaning rubber plant from Brazil).
• Some named after the discoverer (Example : bakelite – discoverer Leo
Baekeland).
• Some named according to the number of carbons used in their
synthesis (Examples : nylon group – Nylon 6, 10; Nylon -6,6; Nylon -6).
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• Some names are source based i.e they are based on the common name of
the reactant monomer, preceded by the prefix “POLY”.
(Examples:Poly(methylmethacrylate);Polystyrenepolypropylene;poly-
acrylonitrile;polyvinylchloride; polytetrafluoroethylene).
• Some names are structure based (employed for simple polymers and
the IUPAC system is used). (Example: Poly(1 chloroethylene)).
• Many polymer families are referred to by the name of the particular
linkage that connects the polymers. (Examples : Polyamide;
Polyurethanes).
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• Trade names and abbreviations are also used to describe the materials.
(Examples : Orlon –PAN; Dacron – PET).

Functionality
Functionality is the number of reactive sites or number of bonding sites.
So a monomer should at least be bi-functional to undergo polymerization.
Significance: Depending on the functionality of the monomer used, linear,
branched or three dimensional cross linked polymers are obtained.

Functionality of molecule = No of reactive sites

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• Bi-functional – Two reactive sites.
If the monomers are bifunctional then linear polymers are obtained.
Thus they are generally of thermoplastic in nature and usually obtained
by addition polymerization.
Examples: Ethylene, Acrylonitrile,propene , vinylchloride (reaction at
double bond), etc.

n H2C CH2 polymerization H2C CH2

n Functionality=2
Ethene polyethylene

CH3
CH3 H2
polymerization C C
n HC CH2 H n Functionality=2
propene polypropylene
 Cl Cl
H2
n HC CH2 polymerization C
H
C
Functionality=2
vinylchloride n
polyvinylchloride

• Trifunctional – Three reactive sites.

If the monomer is trifunctional then cross linked polymers are obtained. They
are thermosets and usually obtained by condensation polymerization.
Examples : Phenol (substitution reaction due to replaceable hydrogen at three
sites), glycerol, etc.
Each chain is held together by covalent bonds. So the movement of chain is
restricted. This type of polymers is hard and brittle,and possesses high
strength, high heat resistance. They are insoluble in solvents.
 polymerization

cross linked structure

• In a mixture of bifunctional and trifunctional, the ratio decides whether
the polymer shall be branched or cross linked.
• When bifunctional molecule is greater than trifunctional molecules,
branched polymer is obtained (n>>b).

polymerization

n b

Branched polymeric structure

• When trifunctional molecule is greater than bifunctional molecules
cross linked polymer is obtained (n>>b).

b n

Three dimensional network structure

• Tetrafunctional – Four reactive sites.

Examples : Acetylene (reaction at triple bond), divinylbenzene, etc.
 H H
HC CH polymerization C C
n Functionality=4
Acetylene Polyacetylene

Functionality Imparted by the presence of easily replaceable hydrogen atoms

OR O
OH

+ RCOCl + HCl Monofunctional

OH OH

Br Br
+ 3HBr
+ 3Br2 Trifunctional

Br
 Classification of polymers
Based on Classification
Origin or Source Natural or Synthetic polymers
Physical State Amorphous, Crystalline Polymers
Backbone Inorganic and Organic Polymers
Homopolymers, Heteropolymers and Copolymers
Structure Linear Polymers,Branched Polymers,Crossed linked Polymers,Graft
Polymers,Blocked Polymers
Tacticity Isotactic,Syndiotactic. Atactic polymers
Thermal characteristics Thermoplastic, Thermosets
Types of Polymerization Addition Polymerization
Copolymerisation
Condensation Polymerization
Applications Fiber,Elastomers, Plastics,Resins
 Classification of polymers
• Classification Based on Source: Natural, Synthetic
 Natural polymers: Synthesized in nature (OR) Isolated from natural
materials.
Examples: Cotton, Silk, Wool, starch, protein, glycogen, rubber, etc.
 Synthetic polymers: Man made (OR) Synthesized from low molecular
weight compounds.
Examples: Nylon, Ethylene, etc.
• Classification Based on Physical state: Amorphous, Crystalline
 Amorphous polymers: A polymer with less ordered arrangement of
chains and weak inter molecular forces.
 Example: Vinyl polymers etc.
 Crystalline polymers: A polymer with ordered structure that has been
allowed to disentangle and form crystals. The intermolecular forces are
high. So greater strength and higher density.
Example: Cellulose etc.
• Classification Based on Back bone: Inorganic, Organic polymer
 Inorganic polymers: A polymer with a skeletal structure that does not
include carbon atoms in the backbone.
Example: Sculpture nitride, Silicon carbide, Glass Silica, etc.
 Organic polymers: Contains organic frame work.
Example: Polyethylene, polystyrene, Polyethylene, etc.
• Classification Based on Structure: Linear, Branched polymers, Cross
linked polymers, Graft copolymers, Block copolymers,Alternate
copolymers and Random copolymers
 Linear polymers: Contains linear chain. Example: HDPE (High
density polyethylene).
 Branched polymers: Contains branches or extension attached to the
polymer chain. H2
C
H2
C
CH2

Example: LDPE(low density polyethylene).

C
H2C H2
H2C
C
H2
CH2
H2
H2C H2 C
CH2 H2
C
C C
H2C H2 CH2
C H2C
H2 C
H2
H2C
H2 CH2
C
CH2 H2 H2
H2C C C CH2
H2C C C
C H2 H2
H2

HDPE
 CH3

 Cross linked polymers: Contains cross links CH2

that are covalent bonds, between two or more CH2

linear polymeric chains. H2 H2

CH2

H2 H2 H H2 H2

Examples: Bakelite, any thermosets, etc.

C C C C C C C C
H

CH2

 Graft copolymers: A branched copolymer in CH3

which the backbone and the branches LDPE

consists of different monomers. OH OH OH

Examples: Vinyl chloride – acrylonitrile H2

C
H2
C

copolymer, etc. H 2C H 2C CH2

 Block copolymers: A copolymer with a long

sequence of one monomer followed H2
C
H2
C

by long sequence of another monomer.

(M1) m X (M2) n. OH OH OH

Bakelite
 A A B B A A
A A A A A A

B B B B

Graft copolymer Block copolymer

• Classification Based on Tacticity:Isotactic , Atactic and Syndiotactic

polymers
• Tacticity is the arrangement of pendant groups in space. This orientation
of groups results in three types of stereo – regular polymers. (Note:
Pendant groups are groups attached to the main polymer chain or
backbone like methyl groups in polypropylene).
Isotactic polymers: Pendant groups are all on the same side of the
polymer backbone.
Examples: isotactic PP, Isotactic Polystyrene, etc.
 CH2 CH CH2 CH CH2 CH CH2

Isotactic polystyrene
 Atactic polymers: Pendant groups are arranged randomly on each
side of the polymer backbone.
Examples: atactic PP, Atactic Polystyrene, etc.

H2 H H2 H2 H H H2 H2
C C C C C C C C C C C
H H2 H

Atactic polystyrene
 Syndiotactic polymer: Pendant groups are arranged alternatively on
each side of the polymer backbone.
Example: syndiotactic PP, syndiotactic Polystyrene, etc.

H2 H2 H H2 H H H2
C C C C C C C C C
H H2

Syndiotactic polystyrene
• Classification Based on Thermal characteristics:
Sr.No Thermoplastic Thermosetting
1 Long straight chained carbon compounds Cross linked compounds
2 Formed by addition polymerization Formed by condensation(step growth)
polymerization
3 Low strength compared to thermosets More strength compared to thermoplastics
4 Can be processed again and again Cannot be processed again or recycled
5 Eg. Polyethylene Eg. Bakelite,Epoxy

• Classification Based on application or end use:

 Fibers
Plastics
Elastomers
Resins
 Fibers: The polymer drawn into long filament – like materials, whose
length is at least 100 times. its diameter is called Fiber. Fibers are linear
and drawn in one direction.
Examples: Cotton, Silk, Ethylene, Nylon, etc.
 Plastics: The word plastic originated from Greek, meaning a material
which can be molded or formed into any shape of one’s choice. The
polymer, shaped into hard and tough utility article by the application of
heat and pressure is called plastic.
Few Major types of plastics
Acrylic plastics: PMMA, PAN
Amino plastics: Urea –formaldehyde(UF), MF
Cellulosics: Cellulose nitrate, Cellulose acetate
Vinyl plastics: PVC, PVC-AC
Styrene plastics: PS, ABS
 Elastomers: The polymer with good strength and elongation when
vulcanized into rubbery products is called Elastomers.
Examples: Vinyl polymers, natural rubber, silicone rubber, etc.
 Resins Polymers used as adhesives, sealants, etc., in a liquid form is
called resins.
Examples: polysulphide sealants, epoxy adhesives, silicone resin, etc.
Thank you