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
Consist of only one type of
Statistical/ ABAABABBBAABAABB
constitutional two or more different repeating unit
repeating unit (A) Random are distributed randomly
AAAAAAAAAAAAAAA
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. are the usual examples of this sub
category.
➢ 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.
➢ 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 joined 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.
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 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,
➢ Because radicals are tolerant of many functional groups and solvents (including water),
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, which is 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 with organometallic reagents such as alkyl aluminum, lithium
and zinc reagents.
➢ The catalyst formed by reaction of triethylaluminum with titanium tetrachloride
has been widely studied, but other metals (e.g. V & Zr) have also proven
effective.
➢ Polymerization of propylene through action of the titanium catalyst gives an
isotactic product; whereas, a vanadium based catalyst gives a syndiotactic
product.

Mechanism of Ziegler-Natta catalysis

 Molecular Weights of Polymers
1. Number average molecular weight (Mn)
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. In polymer science, it is called the number average
molecular weight (Mn). The total weight of the molecules present divided by the
total number of molecules.

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)

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 monodisperse
Polymer sample consisting of molecules all of which have the sam
chain length
Mw/ Mn > 1 polydisperse
Polymer consisting of molecules with the variety of chain length
Molecular weight: characterization techniques
Mn
➢ techniques related to colligative properties (dependence on the
number of molecules)
▪ membrane osmometry (> 25 000 g/mol)
▪ vapor pressure osmometry (< 25 000 g/mol)
➢ mass spectrometry
▪ electrospray ionization mass spectrometry (ESI-MS)
▪ matrix-assisted laser desorption/ionization (MALDI)
➢ size exclusion chromatography
Mw
➢ static laser light scattering
➢ analytical ultracentrifuge
➢ size exclusion chromatography
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.
 POLYMERIZATION TECHNIQUES
1. Bulk polymerization
▪ Mass or block polymerization: Polymerization of the undiluted
monomer carried out by adding a soluble initiator to pure monomer
(in liquid state).
▪ The mixture is constantly agitated & heated to polymerization
temperature.
▪ Once the reaction starts, heating is stopped as the reaction is
exothermic.
▪ The heat generated is dissipated by circulating water jacket.
▪ Viscosity increases dramatically during conversion.
▪ The method is used for the polymerization of liquid state monomers.
▪ It is usually adopted to produce polystyrene, polyvinyl chloride,
polymethyl methacrylate and low density polyethylene.
Advantages
✓ The system is simple and requires thermal insulation.
✓ The polymer obtained is pure.
✓ Large castings may be prepared directly.
✓ Molecular weight distribution can be easily changed with the use of a
chain transfer agent.

Disadvantages
❖ Heat transfer and mixing become difficult as the viscosity of
reaction mass increases.
❖ Highly exothermic.
❖ The polymerization is obtained with a broad molecular weight
distribution due to the high viscosity and lack of good heat transfer.
❖ Very low molecular weightsare obtained.
2. Solution polymerization
▪ Some disadvantages of bulk polymerization are eliminated in solution
polymerization.
▪ Monomer along with initiator dissolved in solvent, formed polymer stays
dissolved.
▪ The mixture is kept at polymerizaion temperature & constantly agitated.
▪ Depending on concentration of monomer the viscosity of solution does not
increase.
▪ After the reaction is over, the polymer is used as such in the form of
polymer solution or the polymer is isolated by evaporating the solvent.
▪ Polymer so formed can be used for surface coating.
▪ It is used for the production of Polyacrylonitrile, PVC,Polyacrylic acid,
Polyacrylamide, Polyvinyl alcohol, PMMA, Polybutadiene, etc
Advantages
✓ The solvent acts as a diluent & helps in facilitating continuous transfer of heat of
polymerization. Therefore temperature control is easy.
✓ The solvent allows easy stirring as it decreases the viscosity of reaction mixture.
✓ Solvent also facilitates the ease of removal of polymer from the reactor.
✓ Viscosity build up is negligible.

Disadvantages
❖ To get pure polymer, evaporation of solvent is required additional technology, so
it is essential to separate & recover the solvent.
❖ The method is costly since it uses costly solvents.
❖ Polymers of high molecular weight polymers cannot be formed as the solvent
molecules may act as chain terminators.
❖ The technique gives a smaller yield of polymer per reactor volume, as the solvent
waste the reactor space.
❖ The purity of product is also not as high as that of bulk polymerization. Removal
of last traces of solvent is difficult.
3. Suspension Polymerization
▪ Liquid or dissolved monomer suspended in liquid phase like water.
▪ Initiators used are monomer soluble e.g. dibenzoyl peroxide.
▪ Polymer is produced in heterogeneous medium.
▪ The size of monomer droplets is 50-200 μm in diameter.
▪ The dispersion is maintained by continuous agitation and the droplets are
prevented to coalesce (unite or merge) by adding small quantity of stabilizers.
▪ The stabilizers used are PVA, gelatin, cellulose are used along with inorganic
stabilizers such as kaolin, magnesium silicate, aluminum
hydroxide,calcium/magnesium phosphate, etc if necessary.
▪ As it concerns with droplets, each droplet is tiny bulk reactor. The polymerization
takes place inside the droplet & product formed being insoluble in water.
▪ The product separated out in the form of spherical pearls or beads of polymer.
▪ Hence the technique is also known as Pearl polymerization/Granular
polymerization/Bead polymerization.
▪ This technique is used to form PVC, Polyvinyl acetate, Polystyrene, Styrene-divinyl
benzene copolymer beads (used for ion exchange) etc.
Advantages
✓ The process is comparatively cheap as it involves only water instead of solvents.
✓ Viscosity increase is negligible.
✓ Agitation & temperature control is easy.
✓ Product isolation is easy since the product is insoluble in water.

Disadvantages
❖ The method can be adopted only for water insoluble monomers.
❖ It is difficult to control polymer size.
❖ Polymer purity is low due to the presence of suspending & stabilizing additives that
are difficult to remove completely.
❖ Suspension polymerization reaction is highly agitation sensitive.
❖ Larger volume of reactor is taken up by water.
❖ The method cannot be used for tacky polymers such as elastomers because of the
tendency for agglomeration of polymer particles.
 4. Emulsion Polymerization
▪ The technique is used for the production of large number of commercial plastics &
elastomers.
▪ The system consists of water insoluble monomer, dispersion medium & emulsifying
agents or surfactants (soaps and detergents) and a water soluble initiator (potassium
persulphate / H2O2, etc).
▪ The monomer is dispersed in the aqueous phase, not as a discrete droplets, but as a
uniform emulsion.
▪ The size of monomer droplet is around 0.5 to 10 μm in diameter depending upon
the polymerization temperature & rate of agitation.
▪ The emulsion of monomer in water is stabilized by a surfactant.
▪ A surfactant has a hydrophilic and hydrophobic end in its structure.
▪ When it is put into a water, the surfactant molecules gather together into aggregates
called micelles.
▪ The hydrocarbon tails (hydrophobic) orient inwards & heads (hydrophilic) orient
outwards into water.
▪ The monomer molecules diffuse from monomer droplets to water & from water to
the hydrocarbon centre of micelles.
Advantages
✓ High molecular weight polymers
✓ fast polymerization rates.
✓ allows removal of heat from the system.
✓ viscosity remains close to that of water and is not dependent on molecular
✓ weight.
✓ The final product can be used as such ,does not need to bealtered or
processed
Disadvantages
❖ Surfactants and polymerization adjuvants -difficult to remove
❖ For dry (isolated) polymers, water removal is an energy intensive
process
❖ Designed to operate at high conversion of monomer to polymer. This
can result in significant chain transfer topolymer.
❖ Can not be used forcondensation, ionic or Ziegler-Natta polymerization.