Polymers & Plastics

 Polymers (derived from the Greek words, poly or many and mer
means units or parts) are macro molecules formed by the
combination of a large number of small molecules known as
monomers.
 Polymers are high molecular weight compounds whose structures
are composed of a large number of simple repeating units. The
repeating units are usually obtained from low molecular weight
simple compounds referred to as monomers.
 The properties of polymer depend on their molecular
configuration, the degree of polymerization, branching and cross
linking.
 Monomer is a micromolecule (smaller molecule) which combines
with each other to form a polymer. Eg. Ethylene, vinyl chloride,
styrene, butadiene, acrylonitrile etc.,
Polymerization: Polymerization is a process in which large number of
small molecules (called monomers) combine to form a big molecule
(called a polymer) with or without elimination of small molecules like
H2O, CH3OH etc.,
Degree of Polymerization (DP): It refers to the number of repeating
units in the polymer molecule. The degree of
polymerization of polyacrylonitrile is y. The definition given here is
evidently useful only for polymers which have regular identifiable
repeating units.
 Strength of the polymer can be increased by increasing its DP
–High DP==== hard and heat resistant
–Low DP===== soft, gummy
 AAAAAAAAABBBBBBBBB
long sequences of a monomer are
Consists of two or more followed by long sequences of another
constitutional
Block monomer
repeating units (A.B )

AAAAAAAAAAAAAAAAAA
Copolymer
Graft B B B
B B B
Classification
by monomer Alternating ABABABABABABABAB
composition are made of alternating sequences
of the different monomers
Homopolymer

Statistical/ ABAABABBBAABAABB
Consist of only one type of two or more different repeating unit
constitutional repeating unit (A) Random are distributed randomly
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Based on Source
 Natural polymers: These polymers are found in plants and animals.
e.g. proteins, cellulose, starch, resins and rubber.
 Semi-synthetic polymers: Cellulose derivatives as cellulose acetate
(rayon) and cellulose nitrate, etc.
 Synthetic polymers: A variety of synthetic polymers as plastic
(polythene), synthetic fibres (nylon 6,6) and synthetic rubbers (Buna
- S) are examples of manmade polymers extensively used in daily life
as well as in industry
Based on Structure
 Linear polymers: These polymers consist of
long and straight chains. e.g. high density
polythene, polyvinyl chloride, etc.
 Branched chain polymers: These polymers
contain linear chains having some branches,
e.g., low density polythene
 Cross linked or Network polymers: These
are usually formed from bi-functional and
tri-functional monomers and contain strong
covalent bonds between various linear
polymer chains, e.g. bakelite, melamine, etc.
Based on Molecular Forces
 Elastomers: These are rubber-like solids weak interaction forces are
present. e.g. Rubber.

 Fibres: Strong, tough, high tensile strength and strong forces of

interaction are present. e.g. nylon 6-6, nylon6.

 Thermoplastics: These have intermediate forces of attraction. e.g.

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.
Tacticity
Orientation of monomeric units in polymer takes place in
orderly/disorderly fashion w.r.t. main chain. The difference in
configuration affects their physical properties

1. Isotactic: Head-to-tail configuration Functional

groups (Y) are all on the same side of the
main chain.
2. Syndiotactic: Functional groups occupy
alternating position

3. Atactic: Functional groups arranged in

random manner
Based on mode of polymerization
1. Addition Polymerization: This is also called as chain growth
polymerization. In this, small monomer units join to form a giant
polymer. In each step length of chain increases.

For example, Polymerization of ethane in the presence of Peroxides.

1.1. Common addition polymers
2. 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, nylon6.

2.1. Common condensation polymers
3. Copolymerization: Copolymerization is defined as the process of
combining two polymers that are different

COPOLYMERS:Polymers which are formed by combining two different

monomers in alternating fashion are called copolymers.

butadiene

Styrene
Styrene-butadiene rubber (SBR)
 Mechanism of Addition Polymerization
 Radical Polymerization: The initiator is a radical, and the propagating
site of reactivity is a carbon radical.
 Cationic Polymerization: The initiator is an acid, and the propagating
site of reactivity is a carbocation.
 Anionic Polymerization: The initiator is a nucleophile, and the
propagating site of reactivity is a carbanion.
 Coordination Catalytic Polymerization: The initiator is a transition
metal complex, and the propagating site of reactivity is a terminal
catalytic complex.
Radical Polymerization
When radical polymerization is desired, it must be started by using a
radical initiator, such as a peroxide or certain azo compounds.
 By using small amounts of initiators, a wide variety of monomers can be polymerized.
e.g. conversion of styrene to polystyrene,
 radical polymerizations are widely used in the chemical industry.
Chain Termination: The most common termination processes are
Radical Combination and Disproportionation
Chain Transfer reactions: Another reaction that diverts radical chain-growth
polymerizations from producing linear macromolecules is called chain transfer.

Chain transfer reactions are especially prevalent in the high pressure radical
polymerization of ethylene, the method used to make LDPE (low density polyethylene).
Cationic Polymerization
Anionic Polymerization
Initiation

Propagation

Termination
 Ziegler-Natta Catalytic Polymerization
 An efficient and stereospecific catalytic polymerization procedure
developed by Karl Ziegler (Germany) and Giulio Natta (Italy) in the
1950’s.
 Their findings permitted, for the first time, the synthesis of unbranched,
high molecular weight polyethylene (HDPE), laboratory synthesis of
natural rubber from isoprene, and configurational control of polymers
from terminal alkenes like propene (e.g. pure isotactic and syndiotactic
polymers).
 For this important discovery these chemists received the 1963 Nobel
Prize in chemistry.
 Ziegler-Natta catalysts are prepared by reacting certain transition metal
halides (Group IVB or VB) with organometallic reagents such as alkyl
aluminum, lithium and zinc reagents.
 Polymers thus formed are linear and high in molecular weight. These catalyst an
polymerize various other olefins like propylene, butylene and higher-a-olefins.
 The titanium catalyst gives an isotactic product; whereas vanadium-based
catalyst gives a syndiotactic product.
Mechanism of Ziegler-Natta catalysis
 Molecular Weights of Polymers
1. Number average molecular weight (Mn)
It is defined as the sum of all the molecular weights of the individual molecules
present divided by their total number. The weight of polymer divided by the number of
polymer molecules. This average molecular weight follows the conventional definition for the
mean value of any statistical quantity.

Mi molecular weight of the ith polymer chain

Ni number of polymer chains with molecular weight Mi
wi weight fraction of polymer chains with molecular weight Mi
2. Weight average molecular weight (Mw): In this average each molecule
contributes according to the ratio of its particular weight to that of the total. The weight-
average molecular weight is larger than or equal to the number-average molecular weight.

A polymer consists of five molecules of molecular weights of 2,4,6,8, and 10. To

calculate the number average molecular weight all the weights of the individual
molecules are added. The sum is then divided by the total number of molecules in
the sample.

Mn = 2/5 + 4/5 + 6/5 + 8/5 + 10/5 = 6

To calculate the weight average molecular weight of the above sample, the squares
of each individual weight are divided by the total sum of their molecular weights
Mw = 22/30 + 42/30 + 62/30 + 82/30 + 102/30 = 7.33
3. Polydispersity Ratio or Index (PDI)
 A measure of the molecular-weight distribution is given by the ratios of molecular
-weight averages.
 For this purpose, the most commonly used ratio is Mw/Mn, which is called the
polydispersity index or PDI.

Mw/Mn = 1 then the sample is monodisperse

Polymer sample consisting of molecules all of which have the same chain length

Mw/ Mn > 1 then the sample is polydisperse

Polymer consisting of molecules with the variety of chain length
Question: A polymer has been found to possess the population of
various molecules as follows:
(i) 10 molecules of molecular mass each 35000.
(ii) 5 molecules of molecular mass each 20000.
(iii) 10 molecules of molecular mass each 45000.
(iv) 20 molecules of molecular mass each 62000.
(v) 15 molecules of molecular mass each 900000.
Calculate its Number Average Molecular weight, Weight Average
Molecular weight and P.D.I.