UNIT III

MACROMOLECULES FOR ENGINEERING APPLICATIONS

Introduction:

A Polymer is a macromolecule formed by the repeated union of several simple molecules

called monomers. The repeating units in a polymer chain are linked through covalent bonds. E.g.
Polyethylene, Teflon, Polystyrene, PVC, Plexiglas etc.

A Monomers is a simple molecule having two or more bonding sites through which each
can link to the other monomers to form a polymer chain. Monomers are called as building blocks
of a polymer chain.
Ex: Vinyl chloride, styrene, adipic acid, hexamethylendiamine etc.

The chemical process by which low molecular weight monomers are converted into high
molecular weight polymer is called Polymerization.

Degree of polymerization:

The total number of monomers used in polymerization process is called degree of polymerization

Where n is degree of polymerization

Polymers are broadly classified based on their origin as

 Natural polymer – Are those obtain naturally, for example cellulose, silk and proteins.
 Synthetic polymer- Are those obtained from man-made process example polyethylene,
polystyrene etc.

Polymers based on their monomer linkage they are classified as

 Linear polymer – monomeric units combine with each other in for of straight chain to form
a polymer.
 Branched polymer- if linear polymer branches out than its called branched polymer.
 Crosslinked polymer- cross linked polymer are obtained by joining separate linear or
branched polymer by cross links.

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 In polymerization process if only one type of monomer is used the polymer formed contains
same repeating units such polymers are called homopolymer

In polymerization process if polymer is formed by different monomer than the polymer formed
is called co-polymer.

Types of polymerization
There are 2 types:
1. Addition polymerization
2. condensation polymerization
1. Addition polymerization: A polymerization reaction in which addition of several bifunctional
or unsaturated monomers to each other takes place by chain reaction in the presence of catalyst,
without elimination of byproducts is called addition or chain polymerization.

2. Condensation polymerization: A polymerization reaction in which a bi or poly functional

monomers undergo intermolecular condensation with elimination of byproducts like H2O, HCl,
NH3 etc is called condensation or step polymerization.

Free radical mechanism of addition polymerization taking vinyl chloride as

example:

The polymerization of vinyl chloride in presence of initiator such as dibenzyl peroxide gives
polythene. Addition polymerization is a chain reaction which proceeds through free radical
mechanism involving three steps

i.e. 1) Initiation 2) Propagation 3) Termination.

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1. Initiation: The addition polymerization is initiated by initiator free radical which is produced
by the thermal decomposition of organic peroxide. Dibenzyl peroxide on heating undergoes
hemolytic fission to give a pair of free radical which are highly reactive and contain an odd
electron. It adds to vinyl chloride to produce new free radical.

2. Propagation: In this step new free radical attacks another monomer to form yet another free
radical. This process continues to give long polymer chain until termination occurs.

3. Termination: In this step the growing chain of the polymer stops growing and terminates.
Termination may takes place by

a. Coupling of 2 growing chains-

Dead Polymer

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 b. Disproportionation: The hydrogen atom of one growing chain is transferred to another
growing chain which results in the formation of one saturated and the other unsaturated
polymer.

Saturated Polymer Unsaturated Polymer

GLASS TRANSITION TEMPERATURE (Tg)

“Glass transition temperature is the temperature at which a polymer abruptly

transforms from the glossy hard state to the rubbery soft state” denoted as Tg.

Factors Affecting Tg :

.1. Flexibility: Linear polymers have lower Tg due to free molecular rotation. Presence of bulky
substitute groups in a polymer decreases flexibility and increases Tg. This is because it requires
more energy for molecular rotation.

2. Molecular mass: Higher the molecular mass higher is the restriction in molecular rotation
and hence Tg increases.

3. Intermolecular forces: Presence of a large number of polar groups in the polymer chain leads
to strong intermolecular forces between polymer chains, which restrict the molecular mobility.
This leads to an increase in Tg.

4. Branching and cross linking: The branched chain polymers with less branching and high
density will have high Tg due to restriction in free molecular rotation. The branched chain
polymers with more branching and low density will have relatively lower Tg due to less
restriction in free molecular rotation. Cross- linked polymers have higher Tg due to higher
restriction in molecular rotation.

5. Plasticizers: Addition of plasticizers increases flexibility and decreases Tg, since plasticizers
enhance free molecular rotation.

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Significance of Tg:

 The Tg value is a measure of flexibility of a polymer.

 The use of any polymer at any temperature is decided by its Tg value.
 The polymers above their Tg value are soft and flexible while below Tg they are hard and
brittle.

COMPOUNDING OF RESINS INTO PLASTICS

Resins are basic binding materials which hold different constituents together. Conversion
of a resin in to plastic is called compounding of resin. This can be done by mixing the resin with
ingredients like filler, plasticizer, colorant and other ingredients. The functions of additives are,

 To introduce new properties in fabricated articles

 To assist polymer processing etc.

a. Fillers are used to increase the bulk of the plastic without altering its salient features. Fillers
improve the thermal stability, strength, non-combustibility, water resistance, electrical
insulating properties and external appearance. ex., wood, mica, clay, cotton and fabric scrap
etc.

b. Plasticizers increase the plasticity of the material and reduce cracking on the surface. Ex. Esters
of fatty acids, phthalates etc.

c. Accelerators give the necessary rate of solidification at lower temperatures. Ex. Hydrogen
peroxide, Benzoyl peroxide etc.

d. Hardeners change resin to solid state by forming a polymer with three dimensional structure.

Ex. Polyamide.

e. Colorants impart desired color to the plastic.

ex: TiO2, ZnCr2O4, Azo dyes etc

f. Stabilizers retain the properties of plastics for a long time and decrease the degradation due to
UV, heat, air etc.
Ex., Alkyl phenols, phenyl salicylate etc.

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Molecular weight – Number average and weight average
The molecular weight of a synthetic polymer does not have a single value, since different chains
will have different lengths and different numbers of side branches. So it is common to calculate
the average molecular weight of the polymer.
There are several different ways to define the average molecular weight, the two most common
being
 the number average molecular weight
 the weight average molecular weight. .

Number average molecular weight defined as the sum of molar masses od individual
molecules to the total number of molecules in the mixture. It gives the average of the molecular
masses of the individual macromolecules.
n1M1 + n2M2 + −−−−−−−− + niMi
Mn =
n1 + n2 + −−−−−−−−−−−−−−−ni
∑ niMi
Mn =
∑ni
Where n and M represent the number and the molecular mass of each species present in the
polymer.
The number average molecular weight can be determined using gel permeation chromatography,
viscometry and colligative methods such as vapour pressure osmometry.

Weight average molecular weight is determined by sum of the weights of all the chains and
then dividing by the total number of chains. The weight average molecular weight depends not
only on the number of molecules present, but also on the weight of each molecule. Weight average
molecular weight is the weight fraction of molecules in a polymer sample.
w1M1 + w2M2 + −−−−−−−− + wiMi
Mw =
w1 + w2 + −−−−−−−−−−−−−−−wi
Where W and M represent the weight and molecular mass of each species
Since W = n M
We can write the above equation as
𝑛1 𝑀12 +𝑛2 𝑀22 + −−−−−−−−−−−−−−− + 𝑛𝑖 𝑀𝑖2
Mw =
𝑛1 𝑀1 + 𝑛2 𝑀2 + −−−−−−−−−−+𝑛𝑖 𝑀𝑖

∑ 𝑛𝑖 𝑀𝑖2
Mw =
∑𝑛𝑖 𝑀𝑖

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The weight average molecular weight can be determined using static light scattering, small angle
neutron scattering, X-ray scattering, and sedimentation velocity.

Polydispersion index and its significance

 The polydispersity index (PI) is a measure of the heterogeneity of a sample based on size.
 Polydispersity can occur due to size distribution in a sample or agglomeration or aggregation
of the sample during isolation or analysis.
 The polydispersity index is defined as the ratio of the weight average molecular weight to the
number average molecular weight, and it gives a measure of the distribution of the molecular
weight within a sample.
 Usually Mw is greater than Mn Therefore Mw/Mn is greater than or equal to one. This ratio
is called distribution ratio.
𝑀𝑤
 If = 1 the polymer is homogeneous and contains polymer of same chain length.
𝑀𝑛
𝑀𝑤
 If the > 1 than the polymer has high degree of heterogeneity.
𝑀𝑛

𝑀𝑤
Polydispersity index = 𝑀𝑛

Mw is the weight average and Mn is the number average molecular weight

Significance: PI is employed to measure the breadth of the molecular weight distribution (MWD)
of the polymer.

SYNTHESIS AND APPLICATIONS :

PMMA (Polymethyl methacrylate) :

PMMA has the trade name as PLEXIGLASS. The monomer used in the manufacture of
PMMA is methyl methacrylate and it is obtained as follows. Acetone with hydrogen cyanide gives
acetone cyanohydrin which on hydrolysis with sulphuric acid yields methyl acrylic acid. This on
esterification with methyl alcohol gives methyl methacrylate.

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 PMMA is obtained by the bulk polymerization of methyl methacrylate using hydrogen
peroxide as indicator.

Properties:

 Plexiglas is a transparent thermoplastic.

 It has excellent optical clarity and is highly resistant to chemicals.

Applications:

It is used for making lenses, artificial eyes, light fixtures, aircraft windows, artificial teeth
(dentures), transparent moulds and tubes etc.

Application: they are used

 For tyre threads, industrial wheels, light weight garments, swimsuits etc.
 As floor coating for gymnasium and dance floors, furniture cushions etc.

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PHENOLFORMALDIHYDE RESIN:

It is prepared by the condensation of phenol and formaldehyde using acid or base as

catalyst. The nature of the product depends on the relative concentrations of phenol and
formaldehyde and on whether acid or base is used as catalyst. A large excess of phenol on heating
with an aqueous solution of formaldehyde in the presence of acid catalyst gives you polymer
called NOVOLAC resin. It is a liner polymer of low molecular weight.

On the other hand a large excess of an aqueous solution of formaldehyde on heating with
phenol in the presence of base as catalyst gives a polymer called resol which is cross linked
polymer of high molecular weight.

Further heating of novalac and resol causes excessive cross linking in the formation of
hard and rigid polymer called phenol-formaldehyde or Bakelite.

Properties: Phenolic resins are very good insulators, possess good thermal and abrasion resistance.

Uses: In making electrical fittings like switches and plugs, telephone and TV parts etc.,

ELASTOMERS:

Elastomers are high polymers which undergo very large elongation under stress but regain
original dimension on release of stress. This property of elastomers is called elasticity

Natural rubber is a high polymer of isoprene and hence it is called polyisoprene

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Deficiency of natural rubber

 Attacked by sunlight and air

 Less resistant to heat and cold
 Holds less air and water at high pressure
 Softens and swells on storing organic solvents
 Rubber properties is lost at extreme temperature
 Ages quickly and loosens surface luster

Vulcanization of rubber

Natural rubber is of little use because it has low tensile strength, poses elasticity over a
limited range of temperature, and becomes softer and sticky on heating, brittle on cooling. In order
to give more strength and elasticity natural rubber is heated with Sulphur at 150o C for few hrs.
Sulphur combines with double bonds of different rubber strings and a crossed linked network is
formed. This process is called vulcanization and it was invented by chales Goodyear in 1839.
Vulcanization of rubber has good tensile strength good resistance to organic solvents and working
temperature of vulcanization rubber is enhanced up to 100 oc where as raw rubber is 10-60o C.

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NEOPRENE RUBBER:
Neoprene is an addition polymer of chloroprene (2-chloro-1, 3-buradine), Acetylene
linkage presence of catalyst cupric chloride gives vinyl acetylene. Addition of hydrogen chloride
to vinyl acetylene in the presence of cupric chloride gives chloroprene.

Properties:
 It has high tensile strength
 resistant to oxidative degradation and aging
 Good ozone ad chemical resistance.

Uses : It is used for making hoses, tubes for carrying oils and chemicals, gloves, coated fabrics,
cable and wire coatings, belts, shoe heels, solid tires etc.

BUTYL RUBBER:
It is a copolymer. It is manufactured by mixing isobutylene with 1.5 to 4.5% of isoprene.
The monomers are polymerized in presence of CH 3Cl and anhydrous AlCl3 as catalyst at -95oC

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Properties:
 Butyl rubber has good chemical inertness, low gas permeability, better ozone and solvent
resistance.
Uses:It is used for making inner tubes for tyres, conveyer belts, for insulation of high voltage
wires and cables.

ADHESIVES:
An adhesive is defined as polymeric substance used to bind together two or more similar
or dissimilar materials such as metals, glasses, plastics etc., by surface attachment.

Types of Adhesives :

1. Natural adhesive: ex. Gum, glue, starch etc.

2. Synthetic adhesives: ex. Epoxy resins

EPOXY RESINS (ARALDITE):

Epoxy resins are polymeric materials containing epoxy group

Epoxy resins are made by condensation polymerization of Epichlorohydrine and Bisphenol-A in

the presence of alkali catalyst at 600c.

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Properties:

 Epoxy resins have excellent adhesion quality for various surfaces.

 Good abrasion resistance.
 Excellent resistant to acid, alkali’s and corrosive chemicals.
 Good electrical insulating property.

Uses: Used as structural adhesives, laminating materials to impart crease and shrinkage resistance
to fabrics, in industrial flooring, highway surfacing etc.

Conducting polymers

Definition: “An organic polymer with highly delocalized pi-electron system having electrical
conductance of the order of a conductor is called conducting polymer”

Mechanism of conductance in polyacetylene

a. Reductive doping
 Poly acetylene is conjugated polymer consisting of alternate double and single c-c bonds. It has linear
structure. This is subjected to reductive doping.
 When a suitable reducing agent such as sodium naphthalide is added, it gives an electron to the pi-
backbone of the polyacetylene chain.
 It creates -ve charge on one of the carbons. The other electron resides on another carbon making it a
radical. So a delocalised radical ion called polaron is formed.
 A dipolaron is formed on second reduction.

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 Then these two radicals migrate and combine to establish back one double bond.
 As two electrons are added to the chain will have two -ve centres. The delocalized -ve charges on the
polymer chain are mobile, not dopent cations (Na+). Thus these delocalized -ve charges are current
carries for conduction. These charges must move from chain to chain as well as along the chain for
bulk conduction. Hence it behaves as n – type conductor.
 Conductivity of pure polyacetylene is about 4.4 X 10-5 S/cm. Upon doping with oxidizing
agent such as iodine, it increases to about 400S/cm.

b. Oxidative doping
 When a suitable oxidizing agent such as iodine vapour or iodine in CCl4 or perchloric acid is
added, it takes away an electron from the pi-backbone of the polyacetylene chain.
 It creates +ve charge on one of the carbons. The other electron resides on another carbon
making it a radical. So a delocalised radical ion called polaron is formed.

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 A dipolaron is formed on second oxidation.
 Then these two radicals migrate and combine to establish back one double bond.
 As two electrons are removed the chain will have two +ve centres. The delocalized +ve
charges on the polymer chain are mobile, not dopent anions (I 3¯ ). Thus these delocalized +ve
charges are current carries for conduction. These charges must move from chain to chain as
well as along the chain for bulk conduction. Hence it behaves as p – type conductor.
 Conductivity of pure polyacetylene is about 4.4 X 10-5 S/cm. Upon doping with oxidizing
agent such as iodine, it increases to about 400S/cm.

Biodegradable polymer
 Bio-degradable polymers are polymers which get decomposed under aerobic or anaerobic
conditions, as a result of the action of microorganism/enzymes.
Eg - Nylon 2–Nylon 6, Polyhydroxybutyrate (PHB).

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 “Biodegradable” refers to the ability of things to get decomposed by the action of micro-
organisms such as bacteria or fungi biological (with or without oxygen) while getting
assimilated into the natural environment. There's no ecological harm during the process.
 Natural biodegradable polymers are called biopolymers. Polysaccharides, as starch and
cellulose, represent the most characteristic family of these natural polymers. Other natural
polymers as proteins can be used to produce biodegradable materials.

Process of biodegradation: The process is carried out in 3 steps

 Biodeterioration, which is the mechanical weakening of its structure;
 Biofragmentation, which is the breakdown of materials by microorganisms;
 Assimilation, which is the incorporation of the old material into new cells.

Cause for biodegradation of Biodegradable polymers is action of micro-organism on the

surface or inside the polymer.
Uses of Biodegradable polymers:
 Biodegradable polymers have diverse applications such as surgical sutures, wound dressings,
tissue regeneration, enzyme immobilization, controlled drug delivery and gene delivery, tissue
engineering scaffold, cryopreservation, nanotechnology, medical implants and devices.
 Biodegradable polymers are often used to reduce the volume of waste in packaging materials.
 There is also significant effort to replace materials derived from petr cochemicals with those
that can be made from biodegradable components.

Synthesis, Degradation and Uses of Polyglycolic acid (PGA)

Polyglycolic acid (PGA) is one of the most known synthetic biodegradable

polyester. Polyglycolic acid, is a biodegradable, thermoplastic polymer and the simplest
linear, aliphatic polyester. PGA has been known as a tough fiber-forming polymer.
Synthesis of Polyglycolic acid (PGA).
It can be prepared starting from glycolic acid by means of polycondensation or ring-opening
polymerization. Due to its hydrolytic instability, initially it has been for limited use. Currently
polyglycolide and its copolymers are widely used as a material for the synthesis of
absorbable sutures and are being evaluated in the biomedical field.
PGA is synthesized using Glycolic acid via 2 pathways:
1. polycondensation of glycolic acid;
2. ring-opening polymerization of glycolide;

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Polycondensation of glycolic acid(PGA):
This is the simplest process available to prepare PGA, but it is not the most efficient
because it yields a low molecular weight PGA.
In this method of synthesis, glycolic acid is heated at temperature of about 175-185 °C and
1 atmospheric pressure. Subsequently, pressure is reduced keeping the temperature unaltered for
about two hours and the low molecular weight PGA is obtained.
Ring-opening polymerization of glycolide: This is another method of synthesis where high
molecular weight PGA is obtained. In this method Glycolic acid is heated to get cyclic glycolide
which undergoes ring opening in presence of catalyst octanoate.

Polyglycolic acid (PGA) degradation

 PGA is highly susceptible to the action of water and can also be degraded by esterases.
 Degradation studies have shown that the polymer loses its strength due to hydrolysis in 1–2
months, and loses mass within 6–12 months.
 Polyglycolide is characterized by hydrolytic instability owing to the presence of
the ester linkage in its backbone.

The degradation process take place in two steps during which the polymer is converted back to its
monomer glycolic acid:
 In first step water diffuses into the amorphous (non-crystalline) regions of the polymer matrix,
cleaving the ester bonds;
 The second step starts after the amorphous regions have been eroded, leaving the crystalline
portion of the polymer susceptible to hydrolytic attack. Upon collapse of the crystalline
regions the polymer chain dissolves.

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Polyglycolic acid uses
 Screws and nails used in drug delivery, dental, and orthopedic applications are made up of
PGA due to their biocompatibility, biodegradability, non-toxicity and ease of fabrication.
 PGA suture is classified as a synthetic, absorbable which render the thread extremely
smooth, soft and safe for knotting. It has the advantages of high initial tensile strength,
smooth passage through tissue, easy handling, excellent knotting ability, and secure knot
tying. PGA suture are naturally degraded in the body by hydrolysis and is absorbed as
water-soluble monomers, completed between 60 and 90 days.

QUESTIONS:
1. What is polymerization? Describe addition and condensation polymerization with example.
2. Explain the free radical mechanism of addition polymerization taking vinyl chloride as an
example.
3. What is glass transition temperature (Tg) ? Explain factors that affect the glass transition
temperature of a polymer. Mention few of its significance.
4. Discuss compounding of resins into plastics.
5. Write a Note on
 Number average and weight average molar mass.
 Polydispersion Index
6. Give the synthesis and applications of PMMA.
7. Give the synthesis, properties and uses Phenol-formaldehyde resin.
8. What are elastomers? What are the deficiencies of natural rubber? Explain Vulcanization
with suitable reaction.
9. Give the synthesis and uses of
i) Neoprene rubber ii) Butyl rubber.
10. Give synthesis and applications of Epoxy resin.
11. What are conducting polymers? Explain the mechanism of conduction in polyacetylene
12. Write a short note on Biodegradable Polymers.
13. Give the synthesis, degradation and uses of polyglycolic acid(PGA).

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