Polymer

INTRODCTION

The word ‘polymer’ is made from two Greek words poly means many and mer means
small unit or part.

The polymer is defined as very large molecules having high molecular mass. These are
also known as macromolecules, which are formed by joining of repeating small structural units
on a large scale.

The repeating structural units are derived from some simple and reactive molecules
known as monomers and are linked to each other by covalent bonds. This process of formation
of polymers from respective monomers is called polymerisation.

Example: The transformation of ethene to polythene and interaction of hexamethylene diamine

and adipic acid leading to the formation of Nylon- 6, 6 are examples of two different types of
polymerisation reactions.

The degree of polymerization, or DP, is the number of monomeric units in a macromolecule

or polymer or oligomer molecule.
 Where n is the degree of polymerization, it can be 104 or more.

Functionality: The number of bonding sites in a monomer.

Classification of Polymers:

Polymer can have different chemical structures, physical properties, mechanical behaviour,
thermal characteristics etc. and can be classified in different ways.

Natural and synthetic polymer.

Organic and inorganic polymer.
Thermoplastic and thermosetting polymers.
Classification Based on the structure of the [Link] and condensation polymers.
Homopolymers and copolymers.
Fibres, plastics and elastomers.
Linear branched and cross-linked polymers.
(I) Based on the Origin:

Natural and Synthetic Polymer:

Those polymers which are isolated from natural materials are called natural polymer.
e.g. Cotton, silk, wool, rubber, starch, cellulose, proteins, nucleic acid etc.

Those polymers which are synthesized from low molecular weight compounds are called
synthetic polymer. e.g. polyethylene, PVC, nylon, Teflon, bakelite, terylene etc.

(II) Based on the carbon backbone

Organic and Inorganic Polymer:

A polymer whose backbone chain is made up of carbon atom is known as organic polymer.

A polymer whose backbone chain is made up of only inorganic molecules and not of carbon
atom is known as inorganic polymers. E.g. Glass, silicone, etc.

(III) Based on the behavior when heated to processing temperature

Thermoplastic and Thermosetting Polymer:

Thermoplastic: Those polymers which soften on heating and moulded to required shapes are
known as thermoplastic polymer which are used for the manufacturing of a wide range of
articles. E.g. Polyethylene, polypropelene, P.V.C, polystyrene, etc.

The process of heating, reshaping and retaining the same on cooling can be repeated several
times.

Thermosetting Polymers: A sample of such material is gigantic molecule and heating does not
soften it, since softening would require breaking of covalent bond. Indeed, heating may causes
formation of additional cross-links and make the material harder, for this reason space network
polymer are called thermosetting polymer. Such polymers, upon heating sets into an infusible
mass and once sets cannot be reshaped. E.g. Phenol-formaldehyde (Bakelite), Urea-
formaldehyde (polyurethane), epoxy etc.

(IV) Classification Based on the structure of the polymers

1. Linear polymers

These polymers consist of long and straight chains. The examples of Polymers are high density
polythene, polyvinyl chloride, etc. These are represented as:

2. Branched chain polymers

These polymers contain linear chains having some branches, e.g., low density polythene, starch
etc. These are depicted as follows:

3. 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. phenol-formaldehyde, melamine, etc.
These polymers are depicted as follows:
(V) classification on the basis of modes of synthesis:

(A) Addition polymers

(B) Condensation polymers

(A) Addition polymers: An addition polymer is a polymer that forms by simple linking of
monomers without the generation of other products.

(B) Condensation polymers: Condensation polymers are any kind of polymers formed through
a condensation reaction where molecules join together losing small molecules as byproducts
such as water, ammonia, HCl or methanol.
(VI) Classification based on monomer

Homopolymers ( same kind of monomer is used) e.g.: Polythene, PVC etc and;

copolymers (more than one type of monomer is used) e.g.: nylon 6,6 etc.

(VII) Classification Based on Molecular Forces

A large number of polymer applications in different fields depend on their unique mechanical
properties like tensile strength, elasticity, toughness, etc. These mechanical properties are
governed by intermolecular forces, e.g., van der Waals forces and hydrogen bonds, present in the
polymer. These forces also bind the polymer chains. Under this category, the polymers are
classified into the following four sub groups on the basis of magnitude of intermolecular forces
present in them.

1. Elastomers

These are rubber – like solids with elastic properties. In these elastomeric polymers, the
polymer chains are held together by the weakest intermolecular forces. These weak binding
forces permit the polymer to be stretched. A few ‘crosslinks’ are introduced in between the
chains, which help the polymer to retract to its original position after the force is released as in
vulcanised rubber. The examples are buna-S, buna-N, neoprene, etc.

2. Fibres

Fibres are the thread forming solids which possess high tensile strength. These characteristics
can be attributed to the strong intermolecular forces like hydrogen bonding. These strong forces
also lead to close packing of chains and thus impart crystalline nature. The examples are
polyamides (nylon 6, 6), polyesters (terylene), polyacrylonitrile etc.

3. Thermoplastic polymers

These are the linear or slightly branched long chain molecules capable of repeatedly softening on
heating and hardening on cooling. These polymers possess intermolecular forces of attraction
intermediate between elastomers and fibres. Some common thermoplastics are polythene,
polystyrene, polyvinyls, etc.

4 Thermosetting polymers

These polymers are cross linked or heavily branched molecules, which on heating undergo
extensive cross linking in moulds and again become infusible. These cannot be reused. Some
common examples are bakelite, urea-formaldelyde resins, etc.

(VIII) Based on the Tacticity (or Configuration)

Isotactic polymers

Isotactic polymers are composed of isotactic macromolecules. In isotactic macromolecules all

the substituents are located on the same side of the macromolecular backbone.

Eg. Polypropylene formed by Ziegler–Natta catalysis is an isotactic polymer. Isotactic polymers

are usually semicrystalline and often form a helix configuration.
Syndiotactic polymers

In syndiotactic or syntactic macromolecules the substituents have alternate positions along the
chain. Syndiotactic polystyrene, made by metallocene catalysis polymerization, is crystalline
with a melting point of 161 °C. Gutta percha is also an example for Syndiotactic polymer.

Atactic polymers

In atactic macromolecules the substituents are placed randomly along the chain.

Polymers that are formed by free-radical mechanisms such as polyvinyl chloride are usually
atactic. Due to their random nature atactic polymers are usually amorphous. In hemi isotactic
macromolecules every other repeat unit has a random substituent.
Polymers of Commercial Importance

Besides, the polymers already discussed, some other commercially important polymers along
with their structures and uses are given below in Table

Application of polymers:
 The common use of polymers in the manufacture of plastic buckets, cups and saucers,
children’s toys, packaging bags, synthetic clothing materials, automobile tyres, gears, electrical
components, contact lenses, adhesives, medical supplies (i.e. bone cement and blood begs) and
seals, electrical insulating materials and machine parts has completely revolutionised the daily
life as well as the industrial scenario. Indeed, the polymers are the backbone of four major
industries viz. plastics, elastomers, fibres and paints and varnishes.
POLYMERIZATION:

It is the process by which simple (monomer) molecules join together to form very large
(polymer) molecule. Hence, the synthesis of large molecular weight polymers is termed as
polymerization.
 Addition and Condensation polymerization
Difference between Addition and Condensation polymerization
 Step and chain growth polymerization
Step-growth polymerization refers to a type of polymerization mechanism in
which bi-functional or multifunctional monomers react to form first dimers, then trimers,
longer oligomers and eventually long chain polymers.

Example:

Chain-growth polymerization is a process in which the high molecular

weight polymer is formed early in the polymerization process and the polymer yield
(the percentage conversion of the monomer into the polymer) gradually increases with
time.
  Mechanism of addition (Chain-growth) polymerization:

It takes place with compounds having the multiple bonds such as vinyl monomer.

Types of addition (Chain-growth) polymerization

1. Free radical
2. Cationic
3. Anionic

Free radical polymerization:

It is a series of reactions. In which an initiator such as peroxide is added to monomer to

form a bigger free radical. This bigger radical adds to another monomer (alkene) to generate a
still larger radical and so on. And finally at the chain termination large molecule known as
polymer is produced.
e.g. Polymerization of vinyl compound it proceeds via three steps.

(i) Chain initiating step: Free radical generated from initiator, adds to the double bond of
monomer to form a new bigger free radical.

__
(a) Peroxide UV light______ Rad.

(b) Rad . + CH2=CH ___________ Rad-CH2-CH .

(ii) Chain propagation:

(c) Rad-CH2-CH . + CH2=CH _______________ Rad –CH2-CH-CH2-CH .

(d) Rad–CH2-CH-CH2-CH.+nCH2=CH__ Rad –CH2-CH-[CH2-CH]n__CH2-CH .

In the propagation step, radical combines with second monomer molecule. This forms a new
radical and then after many similar repetition produce large radical. Thus in each step
consumption of free radical is accompanied by the formation of new; bigger free radical.

(iii) Chain Termination:

Reaction chain is terminated by combination or disproportionation of two free radicals.

(a) Combination the two radical may pair their odd electrons to produce a polymer.
Rad _ CH2 _ CH _[_ CH2 _ CH_]_ n CH2 _ CH .+ .CH _ CH2_[_ CH _ CH2_]_ n CH _ CH2 _ Rad

Rad _ CH2 _ CH _[_ CH2 _ CH_]_ n CH2 _ CH . __.CH _ CH2_[_ CH _ CH2_]_ n CH _ CH2 _ Rad

(b) The active site of one radical may strike on the second carbon in the chain of other
radical. Here first one radical abstracts an H .from the other radical, which forms a

π-bond and produce a mixture of two polymers.

Rad _ CH2 _ CH _[_ CH2 _ CH_]_ n CH2 _ CH .+ .CH _ CH2_[_ CH _ CH2_]_ n CH _ CH2 _ Rad

Rad _ CH2 _ CH _[_ CH2 _ CH_]_ n CH2= CH + CH2 _ CH2_[_ CH _ CH2_]_ n CH _ CH2 _ Rad

Mechanism of Free radical Vinyl Polymerization.

The polymerization of ethylene and substituted ethylene (i.e. styrene, acrylonitrite, vinyl
chloride.)are carried out using free radicals; Which are generated in the presence of a small
amount of an initiator such as peroxide. Here the reaction occurs at the doubly bonded carbons
i.e. at the vinyl groups and hence is called vinyl polymerization. E.g.
Inhibitor:

When compound such as phenols, quinones and some amines are added during polymerization
process the growing free radical may react with such compound and therefore reaction chain is
terminated, but no new one begun. Such compound is known as inhibitor.

Cationic radical polymerization:

Anionic radical polymerization:

 Step growth Polymerization:

Step reaction polymerization proceeds through a series of reaction in which two monomers each
of which contains two functional groups are combined to produced high molecular weight
substance and a small molecule like H2O, HCl or CH3OH.

Synthesis of NYLON-- 6,6

It is an example of step reaction Polymerization. In which Carboxylic acid that contains more
than one __COOH group reacts with an amine that contains more than one __NH2 group then the
products are polyamides. Nylons are aliphatic polyamides. There are different types of nylons
and are indicated by numbering systems. This numbers gives the number of carbon atom present
in (first) the diamines and (second) in the dicarboxylic acid.

NYLON--6,6: It is prepared by the condensation between adipic acid and 1,6-hexanediamine.

It is used as plastic as well as fibres. As a plastic it is used in gears and bearings. As a fiber it is
used in tyres cord and rops.

POLYETHYLENE TEREPHTHALATE (PETP) (Terylene, Dacron):

When Carboxylic acid or it’s ester that contains more than one __COOH group or __COOR group
reacts with diol then the products are,

They are use as fiber. It is commonly known as terylene. PETP is also used in to films of
magnetic recording tapes. The material in sheet form also marketed as Malar.

If each monomer molecules contains just two functional groups, growth can occur in only two
direction and a linear polymer is obtained as in Dacron. But if reaction can occur at more than
two positions in a monomer, there is a formation of a highly cross linked space network polymer
as in glyptal, an alkyd resin.
Phenol - Formaldehyde (Bakelite) resins are formed by the poly condensation between phenol
and formaldehyde. It can be catalysed by either acids or base.

when phenol is treated with formaldehyde in presence of alkali or acid, there is obtained a high
molecular weight Phenol – formaldehyde resin, in which many phenol resin are held together by
-CH2 groups. The stages involve in the formation of polymer seem to be the following. First
phenol reacts with formaldehyde to form O- or P- hydroxylmethylphenol. Hydroxymethylphenol
then reacts with another molecule of phenol, with the loss of H2O, to form a compound in which
two rings are joined by a -CH2 link. This process is then continuous to yield a product of high
molecular weight. Since three position in each phenol molecule are susceptible to attack, the
final product contains many cross links and hence has a rigid three-dimensional structure. It is
thus a space network polymer.
COPOLYMERIZATION

A copolymer is a polymer derived from more than one species of monomer. The polymerization
of monomers into copolymers is called copolymerization. Copolymers obtained
by copolymerization of two monomer species are sometimes called biopolymers.
Methods of molecular weight determination of polymers

 Molecular Mass of Polymers

Polymer properties are closely related to their molecular mass, size and structure. The growth of
the polymer chain during their synthesis is dependent upon the availability of the monomers in
the reaction mixture. Thus, the polymer sample contains chains of varying lengths and hence its
molecular mass is always expressed as an average. The molecular mass of polymers can be
determined by chemical and physical methods.

1. Number Average Molecular Weight (Mn)

Consider a property which is only sensitive to the number of molecules present, a

property that is not influenced by the size of any particle in the mixture. The best example of
such properties is the colligative properties of the solutions such as boiling point elevation,
freezing point depression and osmotic pressure. For such properties, the most relevant average
molecular weight is the total 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.

Then the total weight of all polymers is

and the total number of polymer molecules is

As discussed above, the number average molecular weight is

Where, Ni is the number of molecules of molecular mass Mi

2. Weight Average Molecular Weight (Mw)

Consider of polymer property which depends not just on the number of polymer molecules but
on the size or weight of each polymer molecule. A classic example is light scattering. For such a
property we need a weight average molecular weight. To derive the weight average molecular
weight, replace the appearance of the number of polymers of molecular weight i or Ni in the
number average molecular weight formula with the weight of polymer having molecular weight i
or NiMi. The result is

Where, Ni is the number of molecules of molecular mass Mi

3. Z-Average Molecular Weight (Mz)

The average molecular weight measured by ultracentrifugation is named z-average molecular

weight.

Where, Ni is the number of molecules of molecular mass Mi

 4. Viscosity-average Molecular Weight (Mv)

The molecular weight of the polymer is measured by using viscometer and the molecular
weight obtained by this technique is called viscosity average molecular weight.
The molecular weight of the polymer solution is very high so the viscosity of polymer solution
is very high compared to that of pure solvent.

Where, Ni is the number of molecules of molecular mass Mi and a is the exponent in mark-
Howink-Sakurada equation.

Degree of polymerization

The degree of polymerization, or DP, is usually defined as the number of monomeric units in a
macromolecule or polymer or oligomer molecule.

For a homopolymer, there is only one type of monomeric unit and the number-average degree
of polymerization is given by,
Weight average degree of polymerization

Where, Mn is the number-average molecular weight, Mw is the weight-average molecular

weight and M0 is the molecular weight of the monomer unit.

Index of polydispersity or polydispersity index (PDI)