Introduction to Polymer Chemistry

Classification of Polymers

Polymers are classified in several ways:

• By Source (Origin)

• By Structure

• By Mode of polymerization

• By Molecular forces

• By Type of monomers

• By Biodegradability

1. Classification Based on Source / Origin

a) Natural Polymers

Definition: Polymers obtained from natural sources (plants/animals).

• i. Plant polymers → obtained from plants.

o Cotton (cellulose from cotton plant)

o Linen (from flax plant)

o Natural rubber (from latex of bark of rubber trees)

• ii. Animal polymers → obtained from animal sources.

o Wool (from sheep hair)

o Silk (from silkworm)

b) Synthetic Polymers

Definition: Man-made polymers prepared artificially by polymerization of one monomer (homopolymer)

or copolymerization of two/more monomers (copolymer).

• Examples: Nylon, Terylene (polyester), Neoprene.

• Subtypes:

1. Fibres → e.g., Nylon, Terylene.

2. Synthetic rubbers → e.g., Neoprene, Buna-S.

3. Plastics → e.g., PVC, Polythene.

c) Semisynthetic Polymers

Definition: Polymers derived from natural polymers but chemically modified. Also called Regenerated
fibres.

• Examples:

o Cellulose acetate rayon

o Cellulose nitrate

o Viscose rayon

o Cuprammonium rayon

• Uses:

o Non-inflammable photographic films

o Cinema films

o Varnishes

2. Classification Based on Structure

Based on the way monomers are linked (chain configuration).

a) Linear (Straight Chain) Polymers

Definition: Polymers where monomers join in a straight, linear arrangement.

• Formed from bifunctional monomers or alkenes.

• Chains are closely packed → high density, strong.

• Examples: PVC, High Density Polythene (HDPE).

b) Branched Chain Polymers

Definition: Polymers where the main chain has side branches.

• Formed from monomers having 3 functional groups or already having side chains.

• Packing is irregular → less dense, weaker.

• Example: Low Density Polythene (LDPE).

c) Cross-linked (Network) Polymers

Definition: Polymers where linear chains are interconnected by cross-links → forming a rigid 3D network.
 • Formed from polyfunctional monomers.

• Properties: hard, brittle, highly rigid.

• Examples: Bakelite, Melamine.

3. Classification of Polymers on the Basis of Mode of Polymerization

Polymerization – Definition:
The fundamental process where low molecular mass compounds (monomers) are converted into high
molecular mass compounds (polymers) by linking repeating structural units via covalent bonds.

Modes of Polymerization (3 types):

1. Addition Polymerization (Chain growth polymerization)

2. Condensation Polymerization (Step growth polymerization)

3. Ring Opening Polymerization

a) Addition Polymerization (Chain Growth Polymerization)

Definition:
Formation of polymers by addition of monomers without elimination of small molecules.

• Repeating unit has same elemental composition as monomer.

• Typically occurs in compounds with double bonds.

• Also called Vinyl polymerization (most monomers belong to vinyl group).

Examples:

• Vinyl chloride (CH2 =CHCl) → PVC

• Acrylonitrile (CH2 =CHCN) → Polyacrylonitrile

• Ethylene → Polyethylene

Key Features:
 • Produces high molecular mass polymer directly (no formation of low-mass intermediates).

• Proceeds mainly via Free Radical Mechanism (chain reaction).

Free Radical Mechanism Steps:

1. Chain Initiation:

o The chain reaction is initiated by a free radical.

o An Initiator (catalyst) such as benzoyl peroxide, acetyl peroxide, tert-butyl peroxide

generates a free radical.

o Initiator radical (R·) adds to olefin’s (vinyl monomer) double bond, forming a new radical
containing both R and the monomer unit.

2. Chain Propagation:

o New radical reacts with another monomer → larger radical.

o Repeats rapidly → long chain radical of very high molecular mass.

3. Chain Termination:

o Growth stops when radicals combine (or by other processes). One mode of termination is by
combination of two growing chain radicals.

b) Condensation Polymerization (Step Growth Polymerization)

Definition:
Formation of polymers from polyfunctional monomers with elimination of small molecules (e.g., H₂O, HCl,
CH₃OH, NH₃).

Mechanism:

• The chain growth occurs by a series of condensation steps.

 • Hence called Step Growth Polymerization.

• Continues until high molecular mass polymer forms.

• Repeating unit do not have same elemental composition as monomer.

Example:

• Terylene (Polyester) formation:

o Ethylene glycol (–OH) + Terephthalic acid (–COOH) → ester linkage + water eliminated.

c) Ring Opening Polymerization

Definition:
Polymerization in which cyclic compounds polymerize via opening of ring structure.

Features:

• Catalysed by strong acid or base.

• Cyclic compounds like lactams, cyclic ethers, lactones polymerize by ring opening polymerization.

• Example: ε-caprolactam → Nylon-6.

• Repeating unit has same elemental composition as monomer (like addition polymerization).

• Difference from addition polymerization:

o Addition polymerization = often very rapid.

o Ring opening polymerization = proceeds stepwise, by addition of single monomer units to

the growing chain molecules, not large units.

• Thus, resembles step growth polymerization (like condensation).

4. Classification of Polymers on the Basis of Intermolecular Forces

The mechanical properties of polymers such as tensile strength, toughness, and elasticity vary widely
depending upon intermolecular forces.
a) Elastomers

Definition:
Elastic polymers (elastomers) can be stretched under external force and return to their original shape when
the force is removed.

Reason for elasticity:

• Very weak van der Waals forces allow the polymer to be stretched.

• A few cross-links between chains help the polymer to regain its original shape after stretching.

Examples:

• Vulcanized rubber

• Buna-S

• Buna-N

• Neoprene

Key Properties:

• Soft & stretchable

• Elastic (rubber-like)

• Low tensile strength

b) Fibres

Definition:
Polymeric solids that can be drawn into long, thin threads are called fibres.

Reason for strength:

• Strong intermolecular forces (hydrogen bonding + dipole-dipole interactions).

• Hence, fibres are crystalline in nature.

Property:

• High tensile strength → strong resistance to breaking under tension.

Examples:

• Polyamides → Nylon-6,6

• Polyesters → Terylene

Key Properties:

• Crystalline in nature

• Hard & brittle compared to elastomers

• High tensile strength

c) Thermoplastic Polymers

Plasticity is a property of being easily shaped or moulded.

Definition:
Polymers that soften on heating and harden on cooling, and this cycle can be repeated multiple times.

Reason:

• Possess moderately strong intermolecular forces → intermediate strength (between elastomers

and fibres).

Examples:

• Polythene

• Polystyrene

• Polyvinyl

Key Properties:

• Flexible & mouldable

• Can be remoulded many times

• Recyclable

d) Thermosetting Polymers

Definition:
Rigid polymers that can be moulded on heating, but once hardened they become infusible and cannot be
softened/remoulded.

Reason:

• Due to extensive cross-linking by covalent bonds during the hardening (setting) process while hot.

• This makes them permanently hard and heat-resistant.

Examples:

• Bakelite

• Urea-formaldehyde resin

Key Properties:

• Hard, brittle & highly cross-linked

• Heat resistant

• Non-recyclable (cannot be remoulded)

 Type Forces Properties Examples

Weak VdW + few Rubber, Buna-S, Buna-N,

Elastomers Stretchable, elastic
crosslinks Neoprene

Strong H-bonds & High tensile strength,

Fibres Nylon-6,6, Terylene
dipole crystalline

Soften & harden Polythene, Polystyrene,

Thermoplastics Moderate
repeatedly, recyclable PVC

Strong covalent Hard, infusible, non- Bakelite, Urea-

Thermosetting
crosslinks recyclable formaldehyde resin

5. Classification of Polymers on the Basis of Type of Monomers

a) Homopolymers

• Definition: Polymers that contain only one type of repeating unit.

• Formation: Usually formed from a single monomer.

o Note: In some cases, the repeating unit can be formed by condensation of two distinct
monomers.

• Examples:

o Polythene

o Polypropene

o Nylon-6

o Polyacrylonitrile

o Nylon-6,6

b) Copolymers

• Definition: Polymers that contain two or more types of repeating units.

• Formation: Produced by polymerization of two or more different monomers in the presence of

each other.

• Structure: Different monomer units are randomly sequenced in the polymer chain.

• Examples:

o Buna-S

o Buna-N
6. Classification of Polymers on the Basis of Biodegradability

1. Non-biodegradable Polymers

• Definition: Synthetic polymers that are not decomposed by microorganisms.

• Feature: Persist in environment for very long → cause pollution hazards.

• Examples: Polythene, PVC, Polystyrene.

2. Biodegradable Polymers

• Definition: Polymers that are broken down by microbes into harmless products.

• Feature: Eco-friendly; most natural fibres are biodegradable.

• Examples: Cotton, Wool, Silk (natural); PHBV, Nylon-2-Nylon-6 (synthetic).

Some Important Polymers

1. Rubber
Rubber = Elastomers

• Elastomers are popularly called rubbers.

• Examples: balloons, shoe soles, tyres, surgeon’s gloves, garden hose, etc.

Natural Rubber
 • Monomer: Isoprene (2-methyl-1,3-butadiene).

• Type: High molecular mass linear polymer of isoprene.

• Molecular mass: 130,000 u → 340,000 u.

o Corresponds to 2000–5000 monomer units.

Properties of Natural Rubber

1. Cis-configuration of C=C double bond in polyisoprene molecule.

2. Chains are held by weak van der Waals forces → gives coiled structure.

3. Can be stretched like a spring → exhibits elasticity.

Vulcanization of Rubber

• Definition: Process of introducing cross-links in elastomers.

• Invented by: Charles Goodyear (1839).

• Purpose: Improves physical properties like:

o Tensile strength, stiffness, elasticity, toughness.

• Most common method: Sulfur vulcanization.

o Sulfur forms cross-links between polyisoprene chains → enhances properties.

How Vulcanization is Done (did u know)

• Raw rubber heated with sulfur powder + accelerators (e.g., ZBX = zinc butyl xanthate).

• Temperature: ~150 °C.

• Effect of sulfur amount:

o Small % → improves strength and elasticity.

o Large % (40–45%) → gives hard, non-elastic material called ebonite.

 possible 3D structure of vulcanized rubber

Cross-linking -

• One or more sulfur atoms link two polyisoprene chains.

• Cross-linking occurs by opening of double bonds.

• Produces three-dimensional vulcanized rubber.

2. Polythene
• Simplest & most widely used thermoplastic hydrocarbon polymer.

• Structure: Repeating unit → [–CH₂–CH₂–]ₙ

• IUPAC name: Polyethene

• Two main types:

1. Low Density Polyethylene (LDP)

2. High Density Polyethylene (HDP)

1. Low Density Polyethylene (LDP)

• Preparation:

o Polymerization of ethene at high pressure (1000–2000 atm) & temp (350–570 K).

o In presence of traces of O₂ / peroxide (initiator).

o Mechanism: Free radical addition + H-atom abstraction → causes branching.

o Branching → chains loosely held → low density polymer.

 • Properties:

o Flexible but tough

o Chemically inert & moisture resistant

o Poor electrical conductor

o Melting point: ~110 °C

• Uses:

o Pipes (agriculture, irrigation, domestic water lines)

o Insulation: electric + submarine cables

o Producing extruded films, sheets

o Packaging of squeeze bottles and containers

2. High Density Polyethylene (HDP)

• Preparation:

o Polymerization of ethene at 333–343 K, 6–7 atm.

o Catalyst: Ziegler–Natta (TiCl₄ + Al(C₂H₅)₃).

o Results in linear polymer → close packing → high density.

• Properties:

o Crystalline nature

o Melting point: 144–150 °C

o High tensile strength & stiffer than LDP

o Chemically more resistant than LDP

• Uses:

o Household: toys, buckets, dustbins, bottles, pipes

o Prepare laboratory wares

o Articles needing strength + stiffness

3. Teflon
• Monomer

Tetrafluoroethylene, CF₂=CF₂ (gas at room temperature).

• Properties:

o Tough and durable.

o Chemically inert.

o Resistant to heat and attack by corrosive reagents (alkalis, acids, organic solvents).

o Strong C–F bond makes it highly stable.

• Uses:

o Non-stick cookware coating.

o Oil seals and gaskets.

4. Polyacrylonitrile
• Definition: Polyacrylonitrile is a synthetic polymer that resembles wool and is commonly used as a
substitute for natural wool.

• Monomer: Acrylonitrile (CH₂=CH–CN).

• Preparation

o Formed by addition polymerization of acrylonitrile.

o Polymerization initiated by peroxide initiator.

• Uses:

o Resembles wool and used as substitute for wool

o Used in making Orlon and Acrilan (synthetic fibers).

5. Polyamide Polymers (Nylons)

• Definition:
Polyamide polymers are generally known as nylons.

o They are synthetic linear polyamides obtained by:

▪ Condensation polymerization between dicarboxylic acids and diamines

▪ Self-condensation of an amino acid

▪ Ring-opening polymerization of lactams

o They contain the –CO–NH– group as inter-unit linkages.

o Two important polyamide polymers: Nylon 6,6 and Nylon 6

a) Nylon 6,6

• Monomers:

o Adipic acid

o Hexamethylenediamine

• Preparation:

o Mixing monomers → forms nylon salt

o Condensation polymerization under high temperature and pressure → Nylon 6,6

o The name “6,6” = number of carbon atoms in each monomer

• Properties:

o High molecular mass (12,000–50,000 u)

o Linear condensation polymer

o High tensile strength

o Does not soak in water

• Uses:

o Sheets

o Bristles for brushes

o Surgical sutures

o Textile fabrics

b) Nylon 6

• Monomer:

o ε-Caprolactam (contains 6 carbon atoms)

• Preparation:

o Heated with water at high temperature → ring-opening polymerization → Nylon 6

 • Properties:

o High tensile strength

o Lustrous fibres

• Uses:

o Tyre cords

o Fabrics

o Ropes

Important Notes

• Lactam: Cyclic amide formed when an amino group and carboxyl group in the same molecule react
intramolecularly.

• Lactone: Cyclic ester formed when a hydroxyl group and carboxyl group in the same molecule react
intramolecularly.

6. Polyester
• Definition:

o Polyester polymers have ester linkage joining the repeating units.

o The most important commercial polyester fibre is Terylene (Dacron).

a) Terylene (Dacron)

• Monomers:

o Ethylene glycol

o Terephthalic acid

• Preparation:

o Obtained by condensation polymerization of

ethylene glycol and terephthalic acid

o Requires catalyst and high temperature

• Properties:

o High melting point (265 °C)

o Resistant to chemicals and water

 • Uses:

o Making wrinkle-free fabrics by blending with:

▪ Cotton → Terycot

▪ Wool → Terywool

o Used as glass reinforcing material in safety helmets

b) Polyethylene Terephthalate (PET)

• Type: Thermoplastic polyester

• Trade name: PET

• Uses: Bottles, jars, packaging containers

c) Polycarbonates

• Type: Polyester polymers (with carbonate linkages)

• Properties:

o High melting

o Thermosetting resins

• Uses: Safety equipment, engineering plastics

7. Phenol – formaldehyde and related polymers

a) Bakelite

• Type: Thermosetting polymer (oldest synthetic polymer)

• Monomers:

o Phenol

o Formaldehyde

• Preparation:

1. Phenol + formaldehyde → react in presence of acid or base catalyst

2. Forms a thermosetting/moulding powder called Novolac (in 2 stages)

3. In the third stage, Novolac is shaped in moulds and heated at:

- Temperature: 138 °C – 176 °C

- High pressure
 4. Crosslinking occurs → rigid polymer Bakelite is formed

• Properties:

o Insoluble and infusible

o High tensile strength

o Rigid polymeric material

o Can substitute for glass

• Uses:

o Telephone instruments

o Kitchenware

o Electric insulators

b) Melamine–Formaldehyde Polymer

• Type: Thermosetting plastic

• Monomers:

o Melamine

o Formaldehyde

• Preparation:

o Melamine + formaldehyde → condensation polymerisation → crosslinked melamine

formaldehyde

• Properties:

o Resistant to heat and moisture

• Uses:

o Decorative table tops (Formica)

o Plastic dinnerware

Formation of cross linked melamine formaldehyde resin

 Preparation of Bakelite

8. Buna-S Rubber (SBR – Styrene-Butadiene Rubber)

• Type: Elastomer (synthetic rubber)

• Monomers:

o Styrene

o Butadiene

• Preparation:

o Copolymerisation of 75 parts butadiene and 25 parts styrene

o Polymerisation carried out by addition reaction using sodium

o Vulcanised with sulfur

• Properties:

o Superior to natural rubber in mechanical strength

o High abrasion resistance

• Uses:

o Widely used in tyre industry

 Formation of SBR (Buna - S)

9. Neoprene
• Type: Synthetic rubber

• Monomer: Chloroprene (2-chloro-1,3-butadiene)

• Preparation:

o Polymerisation of chloroprene occurs rapidly in presence of oxygen

o Vulcanisation is carried out in presence of magnesium oxide

• Properties:

o Resistant to petroleum, vegetable oils, light, and heat

• Uses:

o Hose pipes for transport of gasoline

o Gaskets

o Insulator cables

o Jackets

o Belts for power transmission and conveying

Neoprene and vulcanization

10. Viscose Rayon
• Type: Semisynthetic fibre (regenerated cellulose)

• Composition:

o Derived from cellulose (linear polymer of glucose units).

o General formula:

o Often represented as Cell–OH in reactions.

• Preparation Process:

1. Raw material: Cellulose (wood pulp).

2. Treated with concentrated NaOH → forms alkali cellulose (fluffy).

3. Alkali cellulose treated with carbon disulphide (CS₂) → gives cellulose xanthate.

4. Cellulose xanthate mixed with dilute NaOH → forms viscose solution.

5. Viscose solution extruded through spinnerets of spinning machine into an acid bath → regenerated
cellulose fibres (viscose rayon) precipitate.

Formation of viscose rayon

Molecular Mass and Degree of Polymerization of Polymers

• Polymer molecular mass:

o Polymers are mixtures of molecules with different molecular masses.

o Molecular mass of a polymer is the average mass of its constituent molecules.

• Degree of Polymerization (DP):

o Number of monomer units in a polymer molecule.

 o Molecular mass of polymer depends on DP:

Mpolymer = DP × Mmonomer unit

• Mechanical properties vs molecular mass:

o Low molecular mass: brittle, low mechanical strength.

o Very high molecular mass: tough, unmanageable.

o Optimal range: polymer must exceed critical molecular mass to show desired properties.

• Critical Degree of Polymerization:

o Minimum DP required for a polymer to exhibit properties needed for a specific application.

o For polymers with hydrogen bonding: lower critical DP.

o For polymers with weak intermolecular forces: higher critical DP.

• Polymerization control:

o Must be carefully controlled to avoid too low or too high molecular mass.

Problem 15.2: The critical degree of polymerization is low for nylon 6, but high for polythene. Explain.

Solution:

• Nylon 6 is a polyamide with strong intermolecular hydrogen bonding.

• Polythene chains interact through weak van der Waals forces.

• Stronger intermolecular forces in nylon 6 mean it achieves the required mechanical properties at a
lower degree of polymerization.

• In contrast, polythene requires a higher DP to reach the same level of properties.

Biodegradable Polymers

1. Introduction

• Conventional synthetic polymers cause environmental pollution due to their resistance to

microbial degradation.

• Natural wastes degrade via microbes to form humus, but most plastics persist for long periods,
creating pollution.

• Solution: Development of biodegradable synthetic polymers that mimic functional groups in

biopolymers (like proteins).

• Key classes: Aliphatic polyesters and polyamides with a high proportion of polar linkages.
2. Important Biodegradable Polymers -

A. PHBV

• Full name: Poly β-hydroxybutyrate-co-β-hydroxyvalerate.

• Type: Aliphatic polyester.

• Composition: Copolymer of

o β-hydroxybutyric acid (3-hydroxybutanoic acid)

o β-hydroxyvaleric acid (3-hydroxypentanoic acid)

• Structure: Hydroxyl group of one monomer forms ester linkage with the carboxyl group of the
other.

• Degradation: Readily degraded by microbes in the environment.

B. Nylon 2–Nylon 6

• Type: Polyamide copolymer.

• Composition: Copolymer of

o Glycine

o ε-Amino caproic acid

• Property: Biodegradable.

Commercially Important Polymers

Apart from the polymers already discussed in this chapter, many more polymers are used extensively.
Structures and applications of some of them are given in the Table-