Basic Sciences

Petroleum Chemistry program Level 3

Lecture 1: Polymer Chemistry & Technology (CHE312)

Ass. Prof. : Omayma Fawzy Date : 19 / 02 / 2024

1
CHE312- Polymer Chemistry & Technology

2nd semester, 2023-2024

Instructor: Dr. Omayma Fawzy

(Associate Prof. of Organic Chemistry)
Office Room: B 305

Office Hours: Sunday 08:00 AM – 10:00 AM

Wednesday 9:00 AM – 11:00 AM

Tel & WhatsApp: 01007876873

2
 Course contents
Lecture 1: Definition of polymers + Nomenclature + Properties + Classification

Lecture 2: Mechanism of polymerization reactions (Free radical + Ionic)

Lecture 3: Ionic mechanism of polymerization

Lecture 4: Factors affecting polymerization reaction + Tacticity of polymers + Copolymerization reactions

Lecture 5: Polycondensation reactions

Lecture 6: Methods of preparation of polymers

Lecture 7: Fiber forming polymers and introduction to biopolymers + Polymer additives

Lecture 8: Polymers Degradation (Thermal oxidative – Photo-oxidation – Mechanical )

Lecture 9: Vulcanization of Rubber + Plastisization of Plastics + Testing and analysis of polymers

Lecture 10: Advanced polymer processing + Applications of polymers

3
Resources

4
Course aims:
1. Develop a solid understanding of polymer nomenclature, classification, and the relationship between
polymer structure and properties.

2. Explain the mechanisms of polymerization reactions, including free radical and ionic polymerization, and

their significance in polymer synthesis.

3. Explore the factors influencing polymerization reactions and their impact on polymer properties and
performance.
4. Understand the concept of tacticity in polymers and its influence on their physical and chemical properties.
5. Familiarize students with polycondensation reactions and their role in the synthesis of condensation
polymers.
6. Introduce various methods of polymer preparation and their applications in different industries.

7. Examine the unique characteristics and applications of fiber-forming polymers and biopolymers.

8. Discuss the degradation mechanisms of polymers, including thermal oxidative and photo-oxidation

degradation, and their consequences.

9. Understand the processes of rubber vulcanization and plasticization of plastics and their effects on material

properties.

10. Provide knowledge and skills in testing, analysis, and evaluation of polymers, as well as advanced polymer

processing techniques and their applications.

 Definition of Polymers
 The terms polymer and monomer were derived from the Greek roots poly (many),
mono (one) and meros (part). Mono mer Poly mer
One part many repeat unit (building blocks)

Polymers are large molecules made up of repeating units called monomers. They can have diverse structures
and properties and are used in a wide range of applications across various industries.

Repeat unit Repeat unit Repeat unit

H H H H H H H H H H H H H H H H H H

C C C C C C C C C C C C C C C C C C

H Cl H Cl H Cl H CH3 H CH3 H CH3

H H H H H H

Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)

7
Carbon chain backbone
 Polymer science is a relatively new branch of science. It deals with the chemical,
physical, and mechanical properties and applications of macromolecules.

Importance of Polymeric Macromolecules: (Why we study polymer science???!!!!!!)

In an organic sense, polymers contribute to many important biological processes and are

essential structural materials. For instance, proteins are polymers of 20 different types of

amino acids and are essential for cell and tissue growth, while nucleic acids (polymers of

complex molecules called ‘nucleotides’) carry genetic information within our cells.

Meanwhile, the solid parts of plants are also made up of polymers, like cellulose and

resins.
For chemists and manufacturers like us, the near-infinite possibilities that arise from the

ability to polymerize materials are what makes polymers so useful to industry and commerce.

Polymers can be synthesized to exhibit varying levels of hardness, flexibility, and

biodegradability, to name but a few. Polymers help us to save energy, with lighter vehicles

and insulated buildings; package consumable goods; reduce land use and fertilizers, thanks to

synthetic fibers; preserve other materials using coatings; and save lives by way of countless

medical applications
Writing Formulas for Polymeric Macromolecules

For polyethylene:

 Polyethylene is the simplest polymer.

 It is demonstrated by the following equation:
 Acrylonitrile

Polystyrene Poly Acrylonitrile

Nomenclature of polymers

In source-based nomenclature of homopolymers, the polymers are named by writing the

prefix ‘poly’, followed by the name of the actual or apparent monomer by

IUPAC rules for the nomenclature of organic chemistry.

Polyvinyl alcohol Polyvinyl chloride

Copolymers are named by writing the prefix ‘poly’ followed by the names of the monomer

units. An infix called a connective, is placed between the names of the monomers or blocks,

respectively, to indicate the arrangement of units within the chains.

Polyisoprene-graft-maleic anhydride
 Properties of macromolecules

1. Physical Properties:

1. Density: Polymers can have varying densities, ranging from low-density polymers (such as

polyethylene) to high-density polymers (such as polypropylene). Density affects the weight

and floating of the material.

2. Melting Point: Polymers have different melting points, which determine their thermal

processing capabilities. Some polymers have low melting points and can be easily molded,

while others have high melting points and require more energy for processing.
3. Glass Transition Temperature (Tg): It is the temperature at which an amorphous

polymer transitions from a rigid, glassy state to a more flexible, rubbery state. Tg affects

the material's stiffness and ability to withstand deformation.

4. Solubility: Polymers can be soluble or insoluble in various solvents. Solubility depends on

the polymer's molecular structure and the polarity of the solvent. Some polymers dissolve

completely, while others swell or remain insoluble.

2. Chemical Properties:
3. Chemical Resistance: Polymers can exhibit resistance or susceptibility to chemical
substances. Some polymers are resistant to acids, bases, solvents, or other chemicals, while
others may degrade or react with specific substances.

2. Oxidation Resistance: Polymers can have different levels of resistance to oxidation caused
by exposure to oxygen, UV radiation, or other oxidizing agents. Oxidation can degrade the
polymer and affect its properties over time.

3. Chemical Reactivity: Polymers can undergo chemical reactions, such as cross-linking,

or degradation, which can alter their structure and properties. These reactions can be initiated by
heat, radiation, or chemical agents.
3. Mechanical Properties:

4. Tensile Strength: It is the maximum stress a polymer can withstand before breaking

under tension. Tensile strength determines the material's resistance to stretching or pulling

forces.

2. Flexibility and Elasticity: Polymers can exhibit flexibility and elasticity, allowing them to

undergo deformation and return to their original shape. This property is important for

applications requiring resilience and durability.

3. Hardness: Polymers can have different levels of hardness, ranging from soft and rubbery

to rigid and tough. Hardness affects scratch resistance, impact resistance, and the material's

ability to withstand wear and tear.

4. Fracture Toughness: It is a measure of a polymer's ability to resist crack propagation.

Polymers with high fracture toughness are less prone to brittle fracture and have better

resistance to crack propagation.

 Classification of Macromolecules

1. According to the origin:

Natural polymers – Synthetic polymers – Semi-synthetic polymers

1. Natural Polymers:
Natural polymers are derived from natural sources and are typically found in living organisms.
They are often biodegradable and renewable. Examples of natural polymers include:

a. Proteins: Proteins are natural polymers composed of amino acids.

b. Polysaccharides: Polysaccharides are polymers composed of sugar units.

c. Nucleic Acids: Nucleic acids, such as DNA and RNA, are natural polymers that carry genetic

information and play a vital role in protein synthesis and heredity.

d. Natural Rubber: Natural rubber is a polymer derived from the milky latex sap of certain

plants, such as the rubber tree. It exhibits excellent elasticity and is used in

various applications.
2. Synthetic Polymers:
Synthetic polymers are human-made polymers created through chemical reactions. They are
derived from non-natural sources, such as petrochemicals. Examples of synthetic polymers
include:

c. Synthetic Rubber: Synthetic rubber polymers, such as styrene-butadiene rubber (SBR) and

neoprene, are created from petroleum-based monomers and are designed to mimic the

properties of natural rubber.

d. Polystyrene: Polystyrene is a synthetic polymer derived from the monomer styrene. It is

widely used in packaging, insulation, and disposable products.

3. Semi-synthetic Polymers:

Semi-synthetic polymers are derived from natural polymers through chemical modifications

or processing. These polymers retain some of the properties of natural polymers while

incorporating synthetic modifications. Examples of semi-synthetic polymers include:

a. Cellulose Derivatives: Cellulose, a natural polysaccharide, can be chemically modified to

produce derivatives such as cellulose acetate and cellulose nitrate. These derivatives have

different properties and are used in applications like films, coatings, and fibers.
b. Rayon: Rayon is a semi-synthetic polymer derived from cellulose. It is produced through a

process where cellulose fibers are dissolved, regenerated, and spun into fibers. Rayon is used

in textiles and other applications.

c. Modified Natural Rubber: Natural rubber can be chemically modified to improve its

properties, such as increasing its strength or resistance to heat and chemicals.

 2. Classification of polymers according to the nature of the preparation reaction:

Addition polymers – Condensation polymers

1. Addition Polymers:

Addition polymers are formed through an addition or chain-growth polymerization process. In

this process, monomers with unsaturated double bonds (such as ethylene or vinyl monomers)

undergo repeated addition reactions to form a polymer chain. Addition polymers typically do

not involve the elimination of any byproducts during polymerization. Examples of addition

polymers include polyethylene, polypropylene, and polyvinyl chloride (PVC).

2. Condensation Polymers:

Condensation polymers are formed through a condensation or step-growth polymerization

process. In this process, two different monomers react, typically with the elimination of a

small molecule like water or alcohol. The monomers join together to form a polymer chain,

and the polymerization continues as more monomers are added. Examples of condensation

polymers include nylon, polyester, and polyurethane.

3. Chemical Classification

It is based on the chemical constitution of the polymeric chains.

Carbon-chain polymers – Hetero-Chain polymers – Organo-Metallic-Chain polymers

1. Carbon-chain polymers

In this case, the backbone chains are composed only of carbon atoms e.g. Polyethylene,

Polystyrene
2. Hetero-chain polymers

In this case, the backbone chains contain in addition to carbon atoms, atoms of other

elements such as Oxygen, Nitrogen, Sulfur, Phosphorous e.g. Polyamides,

Polyesters

3. Organo-metallic-chain polymers

In which the backbone chains contain atoms of Si or Ti e.g. Glass Hemoglobin

4. Classification according to the shape of the polymeric chains:

Linear polymers - Branched polymers – Cross-linked polymers (3D)

1. Linear Polymers:
Linear polymers have a straight chain structure. The polymer chains are composed of
monomer units that are linked end-to-end, without significant cross-linking or branching.
Examples include polyethylene, and polypropylene.
2. Branched Polymers:
Branched polymers have a main chain with side branches or smaller chains branching off from
it. The branching can occur randomly or at regular intervals. Branched polymers often exhibit
different physical properties compared to linear polymers, such as lower density and improved
melt flow. Examples include low-density polyethylene (LDPE) and polyethylene with long-
chain branching (LCB).
3. Crosslinked or Network Polymers:
Crosslinked or network polymers have a three-dimensional network structure due to the
presence of covalent bonds between polymer chains. This crosslinking provides increased
strength, rigidity, and dimensional stability. Crosslinked polymers are often insoluble and
infusible. Examples include vulcanized rubber, epoxy resins, and crosslinked polyethylene
(PEX).
 5. Classification according to the effect of heat:

Thermoplastic polymers – Thermosetting polymers

1. Thermoplastics:
Thermoplastics are polymers that soften and become more malleable when heated, and they
can be melted and re-molded multiple times without undergoing significant chemical
change. When cooled, they solidify and retain their new shape. This behavior is reversible,
allowing for recycling and reshaping. Examples of thermoplastics include polyethylene,
polypropylene, polystyrene, and polyvinyl chloride (PVC).
2. Thermosetting Polymers:

Thermosetting polymers, also known as thermosets, undergo a chemical reaction when

heated, resulting in a crosslinked three-dimensional network structure. Once set, thermosets

cannot be re-melted or re-molded. They retain their shape and properties even at high

temperatures and are generally more rigid and heat-resistant than thermoplastics. Common

examples of thermosetting polymers include epoxy resins, phenolic resins, and polyurethane.
 6. Classification according to Physico-Mechanical properties:

Elastomers – Plastomers – Fibers

1. Elastomers:
Elastomers are polymers that exhibit a high degree of elasticity, which allows them to
undergo significant deformation under stress and return to their original shape when the
stress is released. Elastomers typically have a flexible, amorphous structure and can be
stretched to several times their original length without permanent deformation.
2. Plastomers:
Plastomers are a class of polymers that exhibit properties intermediate between elastomers
and plastics. They have relatively low crystallinity and are more flexible and less rigid
compared to typical plastics. Plastomers have a combination of elastomeric and plastic
properties, such as good elasticity, processability, and heat sealability.

3. Fibers
These polymers are characterized by high elastic modulus and a small range of elastic
deformation. The effect of temperature on the mechanical properties is very limited. This is
due to strong cohesive forces between neighboring chains.
37