Dr Wan Zaireen Nisa Yahya

POLYMER PROCESS ENGINEERING Email: zaireen.yahya@utp.edu.my

Office: 05-3687584 ( 04-03-24)

CDB4423
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 CDB 4423
POLYMER PROCESS
ENGINEERING
Chapter 1: Introduction

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 Basic Polymer Chemistry
Classification of Polymers
CONTENTS Polymer nomenclature
Polymer properties and additives
Polymer degradation

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LESSON OUTCOME
At the end of this lecture, students should be able to;
•Understand the concept of polymerisation
•Differentiate/ distinguish between thermoplastic, thermoset and elastomer
•Describe the two basic methods of polymerization of thermoplastic and
thermoset materials
•Understand the difference between a homopolymer, copolymer, alloy, and
blend
•Name the polymer
•Understand how molecular weight can affect the properties of the material

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BASIC POLYMER n

CHEMISTRY

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Definition
Polymers, Macromolecules, Polymerisation

In strict term, a polymer is a substance composed of molecules which have long sequences of one or
more species of atoms or groups of atoms linked to each other by primary, usually covalent bonds.

Macromolecules are formed by linking together monomer molecules through chemical reactions, the
process by which this is achieved being known as polymerisation.

Although the words polymer and macromolecule are usually interchangeably, the latter strictly defines
the molecules of which the former is composed.

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1.0 BASIC POLYMER CHEMISTRY
• Plastics vs Polymers
• Polymer = long chain molecule (poly + mer; Greek)
• Thermoset vs Thermoplastic
• Commodity vs Engineering plastics
• (Nearly) all are petrochemical based

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Polymers - long chain molecules of high molecular weight

Number of carbon, n State Use

1-4 Gas Burned for energy
5-11 Liquid Gasoline
9-16 Medium viscosity liquid Kerosene
16-25 High viscosity liquid Oil, grease
25-50 Solid Parafin wax
1000-3000 Tough plastic PE bottles, containers

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 Hydrocarbons at Room Temperature

 Gas  Liquid  Waxy  Plastic

 Methane 20 to 40
5 to 19 40 or more Carbons
 Ethane Carbons
Carbons
 Propane
 Butane

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 BASIC POLYMER CHEMISTRY

• HYDROCARBONS & POLYMERS

– Based on the carbon atom

– Form 4 bonds with other atoms (valence)

– Joins to itself to form long chains & other shapes

– Polymerization results from this:

• Ethylene -> polyethylene

• Propylene -> polypropylene

• Styrene -> polystyrene

• Vinyl chloride -> polyvinyl chloride

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 BASIC POLYMER CHEMISTRY

• HYDROCARBONS & POLYMERS

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 What Makes Polymers Unique?

• Really big molecules (macromolecules) like polymers have very different

properties than small molecules
• Chain entanglement: Long polymer chains get entangled with each other.

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Melting Point

 As the length of hydrocarbons get longer, the Melting Point grows Higher.
Why?

Melting and Boiling Temperatures of Alkanes

600

500

400
Boiling Point (˚C)
Tempurature (˚C)

300

200
Melting Point(˚C)

100

-100

-200

-300
0 5 10 15 20 25 30 35 40 45
Number of Carbons
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What other material properties change?

 Viscosity

 Hardness

 Toughness

 Flammability

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Bonding

 Covalent

 Ionic (NaCl)

 Polar (H2O)

 Van der Waals

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 Polymers
• As Broad as in Daily Life: synthetic polymers

Polystyrene, PS cis-polyisoprene, rubber poly(vinyl pyrrolidone), PVP

poly(vinyl chloride), PVC

Polycarbonate, PC 16
Chain Length: 1000 - 2000

Low-Density Polyethylene (LDPE)

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Chain Length: 10,000 – 100,000

High-Density Polyethylene (HDPE)

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Chain Length: 2-6 million

Ultra-high-molecular-weight polyethylene
(UHMWPE)
Joint Replacement

Helmet

Gears
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 Chain Length: 4,000 – 5,000

PVC – (polyvinyl chloride)

More Polar  Stronger Bonding

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Chain Length: 4,000 – 8,000

Polyethylene Terephthalate (PETE)

“Polyester”

Ester

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Nylon

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 Cotton

Long Strands of Cellulose

+ Hydrogen Bonds
Cellulose is the most common organic material on earth!
It is also a primary constituent of wood and paper.

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Polymers in Starch
Biology
DNA

Sugar Proteins

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Polymer (Thermoset) :
• reinforced with fibres to form
composite materials (use in
aerospace and automotive industries)

• structural adhesive e.g for joining

composite
- surface coating
- electrical and furniture
industries

• crack sealing and repair

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 Kevlar

Strong Network of Covalent Bonds

And Polar Hydrogen Bonds

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 POLYMER By response towards heat
By polymerisation mechanism
CLASSIFICATION By chain structure

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CLASSIFICATION OF POLYMERS
Polymers can be assigned to three groups based on their:

1. Response towards heat or processing characteristics.

2. Polymerization mechanism.

3. Classification by Chain structure (molecular architecture)

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Polymer Classification

Polymers

Thermoplastics Elastomers Thermosets

Crystalline Amorphous

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Polymer Classification:
1. By processing characteristics

❖ Response towards heat or processing characteristics.

❖ Can be divided into two major groups based on their thermal
processing behaviour:
 Thermoplastics
 Thermosets

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Classification of polymers (cont.)

Response towards heat (cont.)

Thermoplastics

Can be heat-softened in order to process into a desired form.

Can be melt-processed by a variety of methods including extrusion and molding.
Waste thermoplastics can be recovered and refabricated by heat and pressure.
E.g, Polystyrene, polyethylene, polypropylene, PVC
Applications – film for packaging, photographic and magnetic tape, beverage
and trash containers, automotive parts and upholstery.

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Classification of polymers (cont.)

Response towards heat (cont.)

Thermosets

Individual chains have been chemically linked by covalent bond during

polymerization or fabrication

These cross-linked networks resist heat softening, creep, and solvent attack. Can’t
be thermally processed.
E.g. Epoxy, phenol-formaldehyde resins, and unsaturated polyesters.
Applications – suitable materials for composite, coatings, adhesive.

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 Thermoset vs. Thermoplastic
 Thermoplastics can be repeatedly reheated and molded into
shapes on cooling

 Thermosetting plastics when reheated decompose

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Polymer Classification: By polymerisation mechanism

a. Addition Polymerisation
 Most packaging plastics
 Needs the correct conditions of temperature & pressure
 Catalysts & promoters aid the process

b. Condensation Polymerization
 PET & polyamide (nylon)
 Joins 2 reactive monomers and releases water

c. Rearrangement
 monomers link together without losing any atoms, but rearrange themselves

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  Source name
NOMENCLATURE  IUPAC name

OF POLYMER  Functional group name

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NOMENCLATURE
A. Types of Nomenclature
a. Source name : to be based on names of corresponding monomer
Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)
b. IUPAC name : to be based on CRU, systematic name
Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene)
c. Functional group name : according to name of functional group in the polymer backbone
Polyamide, Polyester

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NOMENCLATURE
d. Trade name : The commercial names by manufacturer Teflon, Nylon

e. Abbreviation name : PVC, PET

f. Complex and Network polymer : Phenol-formaldehyde polymer

g. Vinyl polymer : Polyolefin

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Vinyl polymers

A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid), Poly(α-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene), Poly(1-methyl-1-phenylethylene),
Poly(1-propylethylene)

Polystyrene Poly(acrylic acid)

CH 2CH CH 2CH
CO 2H

Poly(α-methylstyrene) Poly(1-pentene)
CH 3
CH 2C
CH2CH
CH2CH2CH3
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 Vinyl polymers

B. Diene monomers
CH2CH CH2CH CHCH2

HC CH2

1,2-addition 1,4-addition

Source name : 1,2-Poly(1,3-butadiene) 1,4-Poly(1,3-butadiene)

IUPAC name : Poly(1-vinylethylene) Poly(1-butene-1,4-diyl)

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1.2.2 Vinyl copolymer

Systematic
Poly[styrene-co-(methyl methacrylate)]
Poly[styrene-alt-(methyl methacrylate)]
Polystyrene-block-poly(methyl methacrylate)
Polystyrene-graft-poly(methyl methacrylate)

Concise
Copoly(styrene/methyl methacrylate)
Alt-copoly(styrene/methyl methacrylate)
Block-copoly(styrene/methyl methacrylate)
Graft-copoly(styrene/methyl methacrylate)

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 POLYMER  General properties

PROPERTIES  Additives

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 Polymers
Materials
Properties
• Lightness
• High strength-to weight ratio
• High strength composites
• Low thermal conductivity
• Low electrical conductivity
• Resistance to chemicals
• Variety of colours and transparencies
• Low cost
• Recyclability
• Flammability
• Static electrification
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Polymer vs. other materials:

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 Polymer additives

Materials
Additives
• Fillers
• Plasticizers
• Stabilizers
• Flame retardants
• Colorants
• Lubricants
• Antistatic agents

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 POLYMER  Recycling
DEGRADATION

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The favorite properties of plastics are that they are inert and won't react with what is stored in
them. They also are durable and won't easily decay, dissolve, or break apart. These are great
qualities for things you keep, but when you throw them away, they won't decompose.

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Since they don’t decompose, the answer is to recycle the plastics so they can be
remade into something else. Here we see a bunch of CDs getting recycled.

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The decks, fence, stepping stones, house shingles, and the sweat shirt, were all
made from recycled plastic.

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RECYCLING

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 SUMMARY
✓ Thermoplastic molecules are long strands or chains of atoms.
✓ Smaller atoms or groups of atoms (mers) are linked together to form the long chains so that they are
many units long. (many ‘mers’ – polymer)
✓ This long length to diameter or high aspect ratio gives polymeric materials very distinctive properties
like high strength with very light weight.
✓ The reason for these properties is that the polymer chains are held together due to ENTANGLEMENT.
The chains have a hard time sliding past each other like tangled hair.
✓ The polymer chains do not share chemical bonds with each other. If they did, they would be
crosslinked and would not melt when reheated.
✓ Entanglement isn’t the only thing that holds the molecules together, there are charges on the
molecules that attract the other molecules (polar forces), and weak attractive forces between the
molecules (secondary forces sometimes called Van der Waal’s forces.)
✓ The two main polymerization methods or reactions used to create polymer chains are:
▪ ADDITION and CONDENSATION REACTIONS
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THANK YOU

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