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, Speciality 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 derwaals 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? (UPTU 2002)
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: (UPTU 2008, 2009, 2010, 2011, 2012)

Thermoplastic resins (or) Polymers Thermosetting resins

(1) Formed by additional polymerization Formed by condensation polymerization.
(2) Chains are linked by weak Vander Waal’s forces. Have three dimensional network structure.
(3) On heating they soften and on cooling become On heating become stiff & hard.
hard.
(4) They can be remoulded. They cannot be remoulded.
(5) Can be reused. 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- PCV Ex- Bakelite

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:

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:
 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:

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

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(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:

Mechanism of reaction for the preparation of stereoregular polypropylene using Zeigler Natta Catalyst
(UPTU 2009)

(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:

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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:
• 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
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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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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

(Lecture – 5)
CONDUCTING POLYMERS: 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
• Permeable
• Non- toxic
• Bio-compatible
• Controlled rate of degradation

FACTORS AFFECTING BIODEGRADATION:

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• Size and shape: Polymers should not be very large and too branched.
• Crystallinity: Polymers should be semicrysatalline. The percentage if crystallinity should be less.
• Hydrophillic: Polymers should be water soluble.
• 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 ST: The long polymer molecules are reduced to shorter and shorter lengths and Undergo oxidation.
The molecules become hydrophilic (water attracting) and small.
STEP 2ND: Biodegradation occurs in the presence of moisture and micro-organisms. The polymer is
completely broken down in to the residual products.
STEP 3RD: 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.
• 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
Questions:-
Q1. What are biodegradable polymer? Discuss their application.

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

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

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
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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:
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.

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(Lecture – 8)
COMPOSITES:
Composite material is a material made up of two or more phases (matrix phase and dispersed phase) and
Properties of composites are different from those of any of the phases.

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.

Classification based on Reinforcement

Composite

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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 Blend is defined as a 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)
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

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, PA/ABS

3. Homologous polymer blend: Mixture of same polymers with different molecular weight distribution.

4. Isomorphic polymer blend: Polymer blends of two or more different semi-crystalline polymers.

5. Compatible polymer blend: Blends that is miscible in a certain range of composition and temperature, but
immiscible in others. Example: PC/ABS

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.
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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 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 G.R. 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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Questions:-

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

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

(Lecture – 11)

Co-ordination Polymerisation or Ziegler-Natta Catalytic Polymerization

Ziegler-Natta catalyst: Made of transition metal halides with organometallic reagent- TiCl3 + Al(C2H5)

Importance of Ziegler Natta catalysis:

To prepare linear unbranched polyethylene.
To prepare isotactic polypropylene.

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Questions:-
Q1. Discuss the mechanism of preparation of polypropylene using a combination of an
organometallic compound and transition metal halide or Zeigler Natta catalyst. What are the
advantages of this process over free radical polymerization?

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