ENGINEERING CHEMISTRY (BAS102/BAS202)

POLYMERS

Unit – 5 (11 Lectures)

Materials Chemistry:
Polymers; Classification, Polymerization processes, Thermosetting and Thermoplastic Polymers,
Polymer Blends and Composites, Conducting and Biodegradable polymers, Preparation, properties,
industrial applications of Teflon, Lucite, Bakelite, Kelvar, Dacron, Thiokol, Nylon, Buna-N and Buna-
S and their environmental impact on society, Specialty polymers.
Organometallic Compounds: General methods of preparation and applications of Organometallic
compounds (RMgX and LiAlH4).

(Lecture – 1)
POLYMER: (poly = many; meros = parts).
Polymers are macromolecules made of repeating units called monomers.
Example: Polythene, PVC, nylon-6,6.
n (CH2=CH2) - (CH2CH2CH2CH2CH2CH2)n
Ethene Polythene (polymer)

MONOMERS: are small repeating units of polymers. For example, ethene (CH2=CH2), act as monomer in
polythene.
n (CH2=CH2) (CH2CH2CH2CH2CH2CH2)n
Ethene (monomer) Polythene (polymer)

POLYMERISATION: is the process where monomers join by strong covalent bonds to form polymers.
n (CH2=CH2) polymerisation (CH2CH2CH2CH2CH2CH2)n
Ethene Polythene (polymer)

FUNCTIONALITY: (UPTU2001, 2004, 2011) Number of binding sites in a monomer is called its functionality.
For example, the functionality of ethene and propene is 2, as it can form two new bonds.
*Condition for a molecule to act as monomer: A molecule can act as a monomer only if it is at-least
bifunctional in nature.

DEGREE OF POLYMERISATION (DP): The number of repeating units (n) in a polymer chain is known as
degree of polymerisation.
Degree of Polymerization (DP) = M/m; Where, M= Mass of Polymer; m = mass of monomeric unit.
For example: 3(CH2 =CH2) (CH2 CH2) 3
In above case the degree of polymerization (DP) = 3, as three monomers have joined to form the polymer.

CHARECTERISTICS OF POLYMERS: (UPTU 2003, 2004, 2005, 2008)

• All the polymers are macromolecules, but all the macromolecules are not polymers.
• Polymers are semi crystalline material.
• Low tensile strength, low density.
• Easy to work with.
• High resistance to corrosion.
• Generally insulators, few are conductors.
• Have average molecular weight.
• Properties of polymers depend on their molecular weight, type of bonds between various chains.
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• Primary bonds (backbone) in polymers are covalent bonds whereas the secondary bonds (between
chains) can be van’der Waals forces, dipole-dipole interaction or hydrogen bond.

Why do polymers have average molecular weight?

Polymers are Polydisperse in nature that means polymers are not made of same molecules. In polymers all
the chains have different molecular weight. Because of this, polymer molecular weights are usually given as
averages.

Questions:-
Q1 What do you understand by the term functionality of a polymer? [2011-12(I)]
Q2. Why all simple organic compounds cannot act as monomer during polymerization process? (UPTU
2001)

(Lecture – 2)

CLASSIFICATION OF POLYMERS: Polymers can be classified into several ways as described below:
• Based on number of Monomers
• Based on action of heat (UPTU 2008, 2009, 2010, 2011, 2012)
• Based on Mode of Formation (polymerisation)
• Based on Structure
• Based on Tacticity ( or configuration) (UPTU 2006)
• By Application & Physical Properties
1. On the basis of monomers:

HOMOPOLYMERS COPOLYMERS

Polymers made up of same monomer units. Polymers made up of two or more than two
different monomer units.

Example: Polythene, PVC Example: Buna-N, Buna-S, Nylon-6,6.

Copolymers are further divided into:

Questions:-
Q1 . Differentiate between homopolymers and copolymers.

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2. On the basis of action of heat: [2022-23(II), 2022-23(I), 2012, 2011, 2010, 2009, 2008)]

Thermoplastic resins (or) Polymers Thermosetting resins

(1) Formed by addition polymerization Formed by condensation polymerization.
(2) Chains are linked by weak Vander Waal’s forces. Have three dimensional network structures.
(3) On heating they soften and on cooling become On heating become stiff & hard.
hard.
(4) It can be remoulded. It cannot be remoulded.
(5) It can be reused. It cannot be reused.
(6) Soft, weak and less brittle. Hard, strong tough & more brittle.
(7) Soluble in organic substances. Insoluble in organic solvents.
(8) Long chain polymer with no cross linkage. They have 3D network structure.
(9) Ex- PVC (Poly Vinyl Chloride) Ex- Bakelite, Melamine

3. On the basis of structure:

• Linear polymers: Long straight chains without any side chains. Ex - HDPE
• Branched polymers: Long chains with different side chains. Ex – LDPE
• Cross linked polymers:Monomeric units link together into 3 dimensional network structures. Ex –
Bakelite.

4. On the basis of synthesis: [2022-23(I)]

Addition polymerisation Condensation polymerisation
(1) Also known as chain growth polymerization (1) Also known as step growth polymerisation
(2) It requires the presence of double bond (or (2) It requires two reactive functional groups to be
multiple bonds) in the monomer. present at both ends of the monomer.
(3) No By-product is formed, i.e. No elimination. (3) By-product is formed and elimination of simple
molecule like H2O, NH3, HCl etc. takes place.
(4) Monomers are same. (4) Monomers are different.
(5) Reaction is fast and polymer is formed at once. (5) The polymer is formed in steps
(6) Very little change in the molecular mass during the (6) The molecular mass of increases throughout the
reaction. reaction.
Examples of Addition Polymerisation: Examples of Condensation Polymerisation:
Polymerisation of Ethylene to form Polyethylene (PE) Condensation polymerization of Hexamethylene
diamine and adipic acid to form Nylon-66
Polymerisation of Vinyl chloride to form Polyvinyl Condensation polymerization of Caprolactum to form
chloride (PVC) Nylon-6
Polymerisation of Styrene to form Polystyrene (PS) Condensation polymerization of Terephthalic acid and
Ethylene glycol to form Polyethylene terephthalate
(PET)

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7. On the basis of tacticity:
Tacticity: It is orientation or arrangement of side chains/groups on both the sides of main polymeric chain.
On the basis of tacticity there are three types of polymers:

i) Isotactic: Functional groups on the same side of the main carbon skeleton e.g. Natural rubber
ii) Syndiotactic: Functional groups arranged in the alternate fashion of the main carbon skeleton e.g. Gutta
percha
iii) Atactic: Functional groups arranged in a random manner around the main carbon skeleton e.g. all vinyl
polymers.

Questions:-
Q1. Differentiate between condensation polymerization and addition polymerization
Q2. Classify the polymers on the basis of tacticity?

(Lecture – 3)
Polymerisation: [2022-23(I)]
 It is the process by which simple (monomer) molecules join together to form very large molecules
(polymer).
 Hence the synthesis of large molecular weight polymers is termed as Polymerization.
 The polymerization reactions can be broadly classified into Addition and Condensation
polymerization.

1. Addition Polymerisation (UPTU 2002, 2007, 2010)

Polymer synthesized by addition polymerization has the same empirical formula as that of monomer. No
molecule is evolved during polymerisation and the polymer is an exact multiple of the original monomeric
molecule. For example:

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2. Condensation Polymerisation (UPTU 2002, 2007, 2010, 2011)

It takes place by the condensation of two different bi- or poly functional monomers having functional
groups which have affinity for each other.
For example: –COOH and –OH or –COOH and –NH2 carrying monomers undergo condensation
polymerization.
It always accompanies with the elimination of small molecules like H2O and HCl.
For example:
For example: Necessary condition for condensation polymerization
• Presence of at least two
reactive functional groups in
monomers.
• Two or more different
monomers
• Reactions in steps.

Example of condensation polymerization: Preparation

of Nylon-6,6

(iii) Coordination Addition Polymerisation:

These polymerization reactions are catalysed by Zeiglar Natta catalysts formed between triethyl aluminium
Al(C2H5)3 and Titanium halide (TiCl3). A coordination complex is formed between these two, in which ethyl
group is coordinated to titanium. This is an active catalyst and its structure is shown below:
Ziegler-Natta catalyst: Made of transition metal halides with organometallic reagent- TiCl3 + Al(C2H5)3

Mechanism of Zeigler Natta Catalyst:

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 ENGINEERING CHEMISTRY (BAS102/BAS202)
(Lecture – 4)
PREPARATION, PROPERTIES AND USES OF SOME IMPORTANT POLYMERS

a) Nylon-6: Monomer: Caprolactum

Preparation:

Properties: Tough, High tensile strength, Elastic in nature, Have shine.

Applications
• Gears, fittings, and bearings
• In toothbrushes.
• In guitars, sitars, violins etc.
• Making threads, ropes, nets.
b) Nylon-6,6:Monomers: Adipic acid and Hexamethylene diamine

c) Preparation:

Properties: Light weight, water resistant, high melting point.

Applications: Used in parachutes
• To make swimwear
• Used to make machine parts.
• To make airbags, socks, carpets, ropes, tyres etc.

d) Dacron or Polyester (or) Terylene (or) Polyethylene Phthalate:-Monomers:

Ethylene glycol and terephthalic acid.

Properties:
• Crease resistant, weightless; Resistant to mineral & organic acids; Hydrophobic in nature; high melting
point.
Applications:
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• Ropes • Raincoats
• Nets • Clothing
• Thread

2. RUBBERS
a) Buna-S or SBR: (Elastomer):
Monomers: Butadiene (about 75% by weight) and styrene (25% by weight)Preparation:

Properties:
High load bearing capacity; gets oxidized in the presence of ozone; Swells in oils and solvents.

Applications:
• Used in shoe soles, gaskets • Car, motor cycle, scooter & cycle tyres
• Chewing gum • Electrical insulation
• As a sealing and binding agent

b) NBR or Buna-N or nitrile rubber (Elastomer):

Monomers: Butadiene (about 75% by weight) and Acrylonitrile (25% by weight).
Preparation:

Properties: Highly polar, oil resistant.

Applications:
• Conveyor belts • Aeronautical application
• Seals, gaskets • Tank lining
• Protective gloves in the nuclear industry • Adhesives
Neoprene (Elastomer): Monomer: Chloroprene Preparation:

Properties: Inert to chemicals, Fire resistant, corrosion resistant, water resistant.

Applications:
1. Corrosion-resistant coatings 4. Used for Halloween masks
2. Used in power transformers. 5. Masks used for face protection
3. Used in wet-suits and diving-suits
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PMMA (Poly Methyl Methacrylate) OR Lucite OR Prespex OR Plexiglass
Monomer: Methyl meth acrylate [CH2 = C(CH3). COOCH3]
Preparation:
Properties:
1. It is hard, amorphous, colourless and transparent
thermoplastic material.
2. It has high optical clarity
3. Capable of acquiring different colours and tints.
Applications:
1. It is used for making lenses, transparent objects,
domes and skylights.
2. For making wind screen, aircraft windows
3. Light fitting, ceiling lighting etc.
4. Protective coatings etc.

PTFE OR Poly Tetra Fluoro Ethylene OR Teflon

Monomer: Tetra Fluoro Ethylene (CF2 = CF2)
Preparation:
Properties:
1. High density
2. Chemically inert
3. Electrically insulated
4. Non – adhesive and heat resistant
Applications:
1. Used for Wire and cable insulation
2. Coating of frying pan
3. Variety of seals, gaskets and packing valves

KEVLAR
Monomer: Terephthaloyl Chloride (Terephthalic acid dichloride) and 1,4-diamino benzene

Preparation:

Properties:

1. It is exceptionally strong (5 times stronger than steel)

2. It has high heat stability and flexibility.

Application:
1. Aerospace and aircraft industries.
2. Tyres, Brakes and Clutches lining etc.
3. Bullet proof vests and motorcycle helmet
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Thiokols (or Polysulphide Rubber) or GR-P:
It is prepared by the reaction between Sodium polysulphide (Na2Sx) and Ethlene dichloride (CH2Cl – CH2Cl).
Cl – CH2 – CH2 – Cl + Na2Sx + Cl – CH2 – CH2 – Cl →  CH2 – CH2 – S – S –CH2 – CH2 
Ethylene dichloride Sodium Poly Sulphide Ethylene dichloride  
S S
Thiokol Rubber
Properties of Thiokol:

 Highly resistant to oxygen, ozone and sunlight.

 Highly resistant to swelling by mineral oil, lubricants and organic solvents.
 Temperature range for working is 45C to 105C.
 Thiokol films are impermeable to gases.

Applications of Thiokol:

 Used in oil resistant and weather resistant seals.

 Used in gasoline hoses.
 Used for Barrage balloons, life rafts and life jackets which are inflated by CO 2.
 Also used for lining hoses for conveying gasoline and oil for printing rolls.
A barrage balloon is a type of airborne barrage, a large
uncrewed tethered balloon used to defend ground targets
against aircraft attack, by raising aloft steel cables which
pose a severe risk of collision to hostile aircraft, making
the attacker's approach difficult and hazardous. Early
barrage balloons were often spherical. Barrage balloons
are not practical against high-altitude aircraft—the long
cable required for a high-altitude balloon would be too
heavy.

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Speciality Polymers:
Dendrimers:

 It resembles to star polymers except that each leg of star exhibits repetitive branching in the
manner of a tree.
 The structure of dendrimers consist of three parts: (a) a central core (b) an interior dendritic
structure (c) an exterior surface
Applications:

 Viscosity modifier
 Molecular sensor
 Drug delivery systems
 Control release of agricultural chemicals
Phenolic Resins (Bakelite):
These are condensation product of phenol and formaldehyde. They are also known as phenoplasts
and PF resins.
(1) In the first stage, phenol and formaldehyde in 1:1 molar ratios react with each other in the presence of
acid or base:

(2) In the two stage process, phenol and formaldehyde are heated with an acid catalyst to form a linear
polymer known as NOVOLAC. On further heating , a three dimensional polymer called BAKELITE is formed.

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Properties:
1. PF resins have excellent heat resistance.
2. It has remarkable adhesive properties and bonding strength.
3. They are hard, rigid and scratch resistant.
Uses:
1. They are widely used in making telephone parts, cabinets for radio, television and automobile parts.
2. In producing brake linings, abrasive wheels and sand paper.
3. In making switches, plugs, switch boards, heater handles etc.
4. In varnishes, paints and protective coatings.

Questions:-
Q1. Give the preparation, properties and applications of Buna-N and Terylene.
Q2. Give preparation, properties and application of following polymer:-
a) Neoprene b) Terylene c) Nylon 6,6 d) PTFE [2022-23(I)]

(Lecture – 5)
CONDUCTING POLYMERS:
Q. Giving examples write a brief note on conducting polymers. [2022-23(I)]
Ans. Conducting polymers are organic polymers that conduct electricity, due to extensive conjugation in
their backbone.
Examples of conductive polymers: Polypyrole, Polyacetylene, Polythiophene.
CLASSIFICATION:

1. Intrinsically conducting polymers: They have pie-conjugation in the main chain and can conduct
electricity either normally or on doping. They can be further classified as:

a) Conjugated conducting polymers: They contain conjugated pie bonds in their backbone, which helps
them to form valence band and conduction band. So, there is movement of electrons. Example:
polypyrrole, polythiophene, polyacetylene, polyparaphenylene.

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a) Doped conducting polymers: These are the polymers which have gap between valance and
conduction band and cannot conduct electricity normally. They are doped with electron donor or electron
acceptors to make them conducting. Doping can be done by:

i) p-Doping: Formed by removal of electron from backbone. This is done by using Lewis acid as FeCl 3

(CH)x + A (oxidation) (CH)x + A- Acetylene

Lewis Acid
ii) n-Doping: Formed by addition of electron in backbone. This is done by adding Lewis base
e.g. Na, Li .

(CH)x + B (reduction) (CH)x- B+

Acetylene Lewis Base

2. Extrinsic polymers: They do not contain the factors responsible for conduction and are made conducting
by adding external factors in them.
a). Polymers with conducting element:
• Conductive elements such as C black, metal oxide are added to polymer
• Polymer acts as binder and hold these elements
b) Polymers with Conducting blend or Blended conducting polymer:
• Blending a conventional polymer with conducting polymer takes place
• Conventional polymer gains the conducting property
Questions:-
Q1. What are conducting polymer? Classify conducting polymer and mention their important
application. How can the conductivity of polymers be increased?
(Lecture – 6)
BIODEGRADABLE POLYMERS: The polymers which can degrade in nature by the action of enzymes and
microbes are known as biodegradable polymers.

Characteristics Of Biodegradable Polymers:

• Inert • Non- toxic • Controlled rate of
• Permeable • Bio-compatible degradation

FACTORS AFFECTING BIODEGRADATION:

• Size and shape: Polymers should not be very large and too branched.
• Crystallinity: Polymers should be semi-crystalline. The percentage of crystallinity should be less.
• Hydrophillicity: Polymers should be water soluble.
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• Presence of functional groups: Polymers should be having biodegradable functional groups.
• Presence of suitable microorganism.
• Presence of favourable conditions like suitable temperature, pressure, moisture, Oxygen, Light, type
and concentration of salts, pH etc.

BIODEGRADATION PROCESS:
STEP- 1:
Polymer Breaking or Biofragmentation:
The long polymer molecules are reduced to shorter and shorter lengths and Undergo oxidation. The
molecules become hydrophilic (water attracting) and small. Biodegradation occurs in the presence of
moisture and micro-organisms. The polymer is completely broken down in to the residual products.

STEP 2:
Bioassimilation or Mineralisation:
Micro- organisms consume the degraded plastic. Carbon dioxide, water and biomass are produced and
returned to nature by way of the bio cycle.

Importance of biodegradable polymers:

• 100% Biodegradable.
• Produced from renewable resources.
• Able to be recycled, burned without producing toxic products.
• In Localized drug delivery.
• Reduced side effects.
• Controllable degradation rate

Limitations of Biodegradable Polymers:

 Biodegradation and recycling are two major approaches to plastic waste management. However,
biodegradable polymers are not suitable in the recycling of committed plastics

Applications:
 Used for making films for packaging and other related applications.
 In making agricultural aids such as mulching films. (Mulch films are films that help in the covering of the
soil over which the plants are grown. These films are extremely useful in the effective growth of the plants
since they offer a lot of protection to the plants.)
 Used as a matrix for contolled release of plant growth regulators such as fertilizers, nutrients,
pesticides etc.
 In medical applications such as controlled drug release, bone plates and surgical sutures.

Questions:-
Q1. What are biodegradable polymers? Discuss their application.

(Lecture – 7)
Formation, properties and uses of some biodegradable polymers:

1. Poly(lactic acid): Monomer: lactic acid.

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Properties: PLA is compostable and biodegradable. It is resistant to grease and moisture.

Uses: It is used in food packaging.
Used for surgical sutures, implants.
Used in drug delivery systems.

2. Polyglycolic acid (PGA): It was the first synthetic absorbable suture. Monomer: Glycolic
acid

Properties: Highly crystalline, High melting point and low solubility in organic solvents.
Uses:
 in tissue engineering.
 in controlled drug delivery
 in biodegradable sutures.

3. Poly-ß-hydroxybutyrate-co- ß-hydroxyvalerate (PHBV) (BIOPOL) (BIOMER L)

Monomers: 3-Hydroxybutanoic acid and 3-Hydroxypentanoic acid

Properties: Thermoplastic polymer, brittle, biodegradable.

Applications: Used in controlled drug release.
Used in medical implants and repairs.
Manufacturing bottles.

Nylon-2-nylon-6: Monomers: Glycine and Amino caproic acid

Uses:
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Nylon is very strong fibre infact it is stronger than the steel wire so that is why it is used to make ropes and
parachutes and tooth brush bristles .nylon is also used as dressing material in shirts etc.

Questions:-
Q1. Give the preparation, properties and applications of Nylon -2-6 and PHBV.

(Lecture – 8)
POLYMER COMPOSITES:
Composite material is a combination of two or more materials that exhibit a significant proportion of the
properties of all the constituent material. It made up of two or more phases (matrix phase and dispersed
phase).
A composite material meets the following conditions:
 It is prepared artificially
 It consists of two or more physically or distinct phases separated by a distinct interface
 The polymer matrix composite aims to create a material that is stronger than pure polymer.

Matrix Phase Dispersed or Reinforcing Phase

It is primary phase It is secondary force
It is in continuous form It is in discontinuous form
It holds the dispersed phase and shares load with it. It is embedded in matrix
Weaker than dispersed phase. Stronger than matrix phase

Classification of composite materials:

There are two classification systems of composite materials:
1. Based on matrix phase.
2. Based on reinforcement phase.

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Classification based on Reinforcement
Composite

Advantages of composite materials:

• Light Weight
• Chemical resistance
• Corrosion resistant
• Good performance at high temperatures
• Durable
• Very good electrical insulation

Questions:-
Q1. Write a note on:- Polymer composite.
(Lecture – 9)
POLYMER BLENDS

“Polymer Blends are mixture of two or more same or different polymers, that are not linked by covalents
bonds and having physical properties different from the component polymers”.
 The components of polymer blend should be friendly with each other.
 Blending is done to improve the properties of components.

Example: Terrywool (mixture of wool and terylene)

Why Blends?
 In the developed countries, plastic has displaced conventional material for most applications.
 Todaay, the market demands the resin manufacturers to provide better, more economic
material with superior properties.
 This has resulted in:
o Increased scale of production
o Use of multicomponent and multiphase materials.

Types of polymer blends:

1. Miscible polymer blend:
• Homogenous
• It is a single –phase structure, i.e. they are usually clear.
• It exhibits a single glass transition temperature (Tg) intermediate between those of the individual
components.
• Example PS/PPO (Poly Styrene and Poly Phenylene Oxide)
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2. Immiscible polymer blend:

• Heterogeneous
• They are usually opaque.
• It exhibits separate glass transition temperature (Tg’s) characteristic of each component.
• Example PA/PPO, PA/PP (Poly Amide/ Poly Propylene), PA/ABS (Acrylonitrile Butadiene styrene)

3. Partially Miscible blend: Blends that is miscible in a certain range of composition and temperature, but
immiscible in others. Example: PC/ABS (Poly Carbonate/ Acrylonitrile Butadiene Styrene)

Advantages of blending:
1. Production of desired materials which are low in cost.
2. It improves Solvent and Chemical Resistance.
3. It improves Flame Resistance.
4. Plastic wastes are recycled.
5. Blending reduces the material cost.

Questions:-
Q1.Write a note on:- Polymer blend
Q2. What are organometallic compound? Give its classification.
What is the difference between Polymer Blend and Composite?
S. No. Property Polymer Composite Polymer Blend
1. Definition Polymer composite is a compound made Polymer blend is a combination of two
up of two or more elements resulting a or more polymers, which are physically
multiphase, multicomponent system mixed to obtain a single phase.
2. General Polymer composites consist of polymer Polymer blends consist of two or more
Composition component and non-polymer component polymers
3. Nature of Polymer composites have chemical and Polymer blends usually do not form
Bonding physical bonds between polymer and strong chemical bonds between
non-polymer. polymers.
For Fibreglass, in which small glass fibre poly(styrene) (PS)–poly(phenylene
Example: are embedded within a polymeric oxide) (PPO) and poly(styrene-
material (normally an epoxy or acrylonitrile) (SAN)–poly (methyl
polyester). methacrylate) (PMMA) are miscible
The glass fibre is relatively strong and blends, while poly(propylene) (PP)– PS
stiff (but also brittle), whereas the and poly(propylene)–poly(ethylene) (PE)
polymer is ductile (but also weak and are immiscible blends.
flexible).

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ORGANOMETALLIC COMPOUNDS
The compounds in which the carbon atom is directly linked to metal atom are known as organometallic
compounds.

CM
Covalent bond
Where M = any metal like Mg, Li, Na, Ca, Al etc.

Classification of organometallic compounds:

ORGANOMETALLIC COMPOUNDS

Based on groups attached to On the basis of type of C-M bond

Metal Ionic Organometallic Comp.

Covalent OMC
Simple OM Mixed OMC
Symmetrical Electron deficient OMC

Unsymmetrical Organometallics involving π bonds

Based on groups attached to metal atom:

1. Simple organometallic compounds: Metal atom is bonded to only carbon and hydrogen atoms. E.g.
(C2H5)4Pb. They are of two types:
a) Symmetrical: Metal atom is bonded to same type of groups. E.g. (C 2H5)2Hg.
b) Unsymmetrical:Metal atom is bonded to different hydrocarbon radicals. E.g. C2H5Hg C4H9
2. Mixed organometallic compounds: In addition to carbon the metal atom is attached to other groups also.
E.g. C2H5MgBr
On the basis of type of C-M bond:

1. Ionic Organometallic Compound: Ionic bond between metal atom and carbon atom. E.g. Organo
sodium compounds (C6H5Na), Organo potassium compounds (C5H5K).

2. Covalent Organometallic Compounds or sigma bonded compounds: Covalent bond between carbon
and atom. E.g. Metal alkyl compounds – Pb(C2H5)4, Zn(C6H5)2

3. Electron defficient Organometallic Compounds: These include the compounds having bridge alkyl
groups. E.g. Dimeric boron hydride (B2H6), Dimeric trialkyl aluminium [Al2(CH3)6]

4. Organometallics involving π bonds: Have metal-ligand bonds between metal and π orbital of organic
ligands. E.g. Ferrocene - (C5H5)2Fe.

GENERAL SYNTHESIS:
1. Direct reaction of metal with alkyl/aryl halide in the presence of ether or THF.
M + RX RMX
2. Mg + CH3I  CH3MgI (in presence of ether)
3. Use of alkylating agents:
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The alkylation is generally done either in ether or hydrocarbon solvents.
PCl3 + 3 C6H5MgCl  P(C6H5)3 + 3MgCl2

(Lecture – 10)
GRIGNARD REAGENT

It is a type of organometallic compound formula RMgX where X is a halogen, and R is an alkyl or aryl (based
on a benzene ring) group. A typical Grignard reagent might be CH3MgBr.

Preparation of a Grignard reagent:

1. Prepared by the action of organic halide and Mg metal in presence of ether or tetra hydro furan.
RX + Mg ether RMgX
ArX + Mg ether ArMgX
The reaction is carried out in presence of diethyl ether or tetra hydro furan to avoid the presence of
moisture, as Grignard Reagent reacts with water to form alkane.

2. Metal exchange reactions.

RC≡CH + C2H5MgBr RC≡CMgBr + C2H6

Applications of Grignard reagent

1. Formation of alkanes:

a) With water: C2H5MgBr + H2O C2H6 + Mg(OH)Br

ethyl magnesium bromide ethane

b) With alcohol: C2H5MgBr+C2H5OH C2H6 + Mg(OC2H5)Br

c) With Ammonia: CH3MgBr + HNH2 CH4 + MgBr(NH2)

2. Formation of amides: Reaction of G.R. with chloramine

CH3MgX + ClNH2 CH3NH2 + ClMgX

Chloramine methanamine

3. Formation of carboxylic acid: Grignard reagent and CO2

4. Formation of primary, secondary and tertiary alcohols:

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 ENGINEERING CHEMISTRY (BAS102/BAS202)

Questions:-

Q1. Write a short note on application of Grignard reagent?

Q2. What are Grignard reagents? How are they prepared?

Lithium Aluminium Hydride (LAH)

Preparation: LAH is prepared by slowly adding a calculated amount of anhydrous Aluminium chloride to a
paste of Lithium hydride in dry ether or THF (Tetra Hydro Furan).

4LiH + AlCl3 ------- LiAlH4 + 3LiCl

Lithium Hydride Aluminium Chloride Lithium Aluminium Hydride Lithium Chloride

1. Precipitated lithium chloride and the unreacted lithium hydride are removed by filtration.
2. The filtrate is evaporated in the absence of air and CO2 when LAH is obtained as grey solid.

Properties:
1. It is soluble in ether, THF and dioxin.
2. It is spontaneously inflammable and reacts violently with water and alcohol with the evolution of
hydrogen.

Uses:
1. The reagent may be used to reduce aldehydes, ketones, acids and their derivates, epoxides etc. to
alcohols.
2. The reagents can also reduce nitriles, aliphatic nitro compounds, anilides, azides and isocyanates to
amines.

Reactions: RCHO + LAH --- RCH2OH

Li[AlH 4] + 4 H 2O → LiOH + Al(OH) 3 + 4 H.

This reaction provides a useful method to generate hydrogen in the laboratory.

Applications of LiAlH4

1. LiAlH4 reduces aldehydes or ketones to the corresponding primary or secondary alcohols.

Acetaldehyde, for example, is reduced to ethyl alcohol, while acetone is reduced to isopropyl alcohol.

2. Lithium aluminium hydride is used to reduce carboxylic acids, esters, and acid halides to their
corresponding primary alcohols.
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3. Lithium aluminium hydride, LiAlH4, reduces the amides to amines. This method is particularly useful for
obtaining secondary amines.
Diethylamine, for example, can be synthesized from acetyl chloride.
4. LiAlH4 reduces the nitriles to primary amines.
For example, LiAlH4 reduces acetonitrile to ethyl amine.
5. The oxiranes (epoxides) are converted to alcohol by lithium aluminium hydride. The mechanism involves a
hydride attack on the epoxide’s less hindered side.
For example, 2-methyloxirane primarily yields 2-propanol.

6. Lithium aluminium hydride is used to convert haloalkanes and haloarenes to their corresponding
hydrocarbons.

Question: Predict the final product obtained when LiAlH4 reacts with [2022-23(II)]

(i) LiAlH4, ether

1. CH3. (CH2)4.CHO ------------------------ CH3 – (CH2)4 – CH2OH
Hexanaldehyde (ii) H3O+ Hexanol

(i) LiAlH4, ether

2. CH3 – CH = CH – CHO ------------------- CH3 – CH = CH – CH2OH
Crotonaldehyde (ii)H3O+ Crotyl alcohol

(i) LiAlH4, ether

3. C6H5 – CH = CH – CHO ------------------ C6H5 – CH2 – CH2 – CH2OH
Cinnamaldehyde (ii) H3O+ 3-phenyl propanol-1

(i) LiAlH4, ether

4. CH3 – CH2 – CO – CH3 ---------------------- CH3 – CH2 – CH(OH) – CH3
Methyl Ethyl Acetone (ii) H3O+ Butan – 2 ol

(i) LiAlH4, ether

5. CH3 – CO – CH2 – COO – C2H5 ------------------ CH3 – CH(OH) – CH2 – CH2OH
Ethyl acetoacetate (ii) H3O+ Butan – 1, 3 diol

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 ENGINEERING CHEMISTRY (BAS102/BAS202)
(i) LiAlH4, ether
6. CH3 – COCl ------------------------------- CH3 – CH2OH
Acetyl Chloride (ii) H3O+ Ethanol

(i) LiAlH4, ether

7. (CH3 – CO)2O ------------------------ 2CH3 – CH2OH
Acetic anhydride (ii) H3O+ Ethanol

(i) LiAlH4, ether

8. CH3. CHO ------------------------ CH3– CH2OH
Acetaldehyde (ii) H3O+ Ethanol

(i) LiAlH4, ether

9. CH3 – C  N ------------------------ CH3 – CH2 – NH2
Methyl Cyanide (ii) H3O+ Ethyl Amine

10. (i) LiAlH4, ether

CH3 – COOH ---------------------- CH3 – CH2  OH
Acetic Acid (ii) H3O+ Ethanol

11. (i) LiAlH4, ether

CH3 – N3 ---------------------- CH3 – NH2
Methyl Azide (ii) H3O+ Methyl Amine

12. (i) LiAlH4, ether

CH3 – CH – CH2O ---------------------- CH3 – CH(OH)  CH3
2-methyloxirane (ii) H3O+ Propan– 2– ol OR 2-Propanol

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 ENGINEERING CHEMISTRY (BAS102/BAS202)
(Lecture – 11)
Q. Outline the process of vulcanization of rubber. Describe the preparation, important properties
and uses of Butyl rubber OR Kevlar. [2022-23(I)]

Ans.: Natural Rubber (2011):

There are many rubber products which we come across in our daily life.

Some common rubber-based objects that we use in our day-to-day lives include rubber gloves, rubber
bands, and rubber footwear.
Rubber items have the ability to recover their shapes after being stretched or distorted, which is the reason
why rubber can be classified as an elastomer.
Rubber is an elastic substance which can be obtained both naturally (natural rubber) or artificially (they can
also be synthesized chemically in laboratories; synthetic rubber-like butyl rubber, neoprene, etc.)

Types of rubber
There are two primary types of rubber, namely natural rubber and synthetic rubber.

Natural rubber
These are the elastomers which are obtained naturally.
Natural rubber is made up of solid particles suspended in a milky white liquid (called latex) that drips from
the bark of certain tropical and subtropical trees (Hevea brasiliensis).

This latex rubber is mainly found in countries like Brazil, India (Kerala, Tamil nadu, Karnataka, Assam,
Meghalaya, Tripura), Indonesia, Malaysia, and Sri Lanka.
It is made by the polymerization of isoprene (2 methyl-1, 3-butadiene) which has a chemical formula
(C5H8) n and it is known as cis- 1, 4- polyisoprene.

Drawbacks of Natural Rubber (2005, 2006, 2011, 12)

1. Its usage temperature range is very limited. It becomes soft and sticky in hot summer while hard
and brittle in cold weather.
2. It is weak due to low tensile strength.
3. It is easily attacked by oxidizing agents (HNO3, Conc H2SO4, O3, H2O2 etc.
4. Due to its oxidation in air it is not durable.
5. It is soluble in polar organic solvents. It undergoes swelling and gradual disintegration.
6. It possess tackiness, that means under pressure two fresh raw rubber surface coalesce (संगठित होना)
together to form a single piece.
7. When stretched to a great extent , it suffers from permanent deformation.

To enhance all these properties, sulphur is added to the rubber and it is heated at a temperature
ranging from 373 K to 415 K. This process is known as vulcanization. The sulphur acts as a cross-linking
agent and after vulcanization, rubber gets cross-linked and becomes hard.

Vulcanization (2001, 05, 06, 2007, 2011, 2021-22 2022-23(1):

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 ENGINEERING CHEMISTRY (BAS102/BAS202)
It consists of heating the raw rubber with at 100 – 140C with sulphur. The sulphur combines chemically at
the double bonds of different rubber springs and provides cross linking between the chains. This cross linking
prevents intermolecular movement of rubber springs.
The amount of sulphur added determines the extent of stiffness of vulcanized rubber.

Advantages of vulcanization: (2001, 2007)

1. The tensile strength of vulcanized rubber is very good, about 10 times the tensile strength of raw
rubber.
2. It has excellent resilience property i.e., after removal of external force, it regains original shape.
3. It has broader useful temperature range (40C to 100C).
4. It has better resistance to moisture, oxidation and abrasion.
5. It is resistant to organic solvents (CCl4, Benzene, petrol etc), but swells in them.
6. It has slight tackiness.

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