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Introduction

n
ISSUES TO ADDRESS...
What are the basic
Classification?
Monomers and chemical groups?
Nomenclature?
Polymerization methods?
Molecular Weight and Degree of Polymerization?
Molecular Structures?
Crystallinity?
Microstructural features?
Polymer
Students should:

Be able to understand the concept of polymerisation
Be able to differentiate/ distinguish between thermoplastic,
thermoset and elastomer
Be able to describe the two basic methods of polymerization of
thermoplastic and thermoset materials

Understand the difference between a homopolymer, copolymer,
alloy, and blend
Be able to name the polymer
Understand how molecular weight can affect the properties of the
material




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

Polymers - long chain molecules of high
molecular weight


n State Use
1-4 gas burned for energy
5-11 liquid gasoline
9-16 med. visc.
liquid
kerosene
16-25 hi visc. liq. oil, grease
25-50 solid paraffin wax
1000-
3000
tough plastic PE bottles, containers
Hydrocarbons
at Room Temperature

Gas
Methane
Ethane
Propane
Butane

Plastic Liquid


Waxy
20 to 40
Carbons
5 to 19
Carbons
40 or more
Carbons
Polymer, Macromolecule and Polymerization
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 polymerization.

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

BASIC POLYMER CHEMISTRY
HYDROCARBONS & POLYMERS
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.

Melting Point

As the length of hydrocarbons get longer, the
Melting Point grows Higher. Why?
-300
-200
-100
0
100
200
300
400
500
600
0 5 10 15 20 25 30 35 40 45
T
e
m
p
u
r
a
t
u
r
e

(

C
)


Number of Carbons
Melting and Boiling Temperatures of Alkanes
Boiling Point (C)
Melting Point(C)
What other material properties
change?
Viscosity

Hardness

Toughness

Flammability

Bonding
Covalent

Ionic (NaCl)

Polar (H
2
O)

Van der Waals
Polymers
As Broad as in Daily Life: synthetic polymers
polystyrene cis-polyisoprene poly(vinyl pyrrolidone)
polycarbonate
poly(vinyl chloride)
Low-Density Polyethylene (LDPE)
Chain Length: 1000 - 2000
High-Density Polyethylene (HDPE)
Chain Length: 10,000 100,000
Ultra-high-molecular-weight
polyethylene (UHMWPE)
Helmet
Gears
Joint
Replacement
Chain Length: 2-6 million
PVC (polyvinyl chloride)
Chain Length: 4,000 5,000
More Polar Stronger Bonding
Polyethylene Terephthalate (PETE)
Polyester
Chain Length: 4,000 8,000
Ester
Nylon

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.
Polymers in
Biology
DNA
Sugar
Starch
Proteins
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



Kevlar
Strong Network of Covalent Bonds
And Polar Hydrogen Bonds
1.1 CLASIFICATION
Classification of polymers

Polymers can be assigned to three groups based on their:
Response towards heat or processing
characteristics.
Polymerization mechanism.

Response towards heat
Polymers can de divided into two major groups based on
their thermal processing behaviour:
Thermoplastics
Thermosets


Synthetic Polymers
(Based on Properties)
Thermoplastics
Elastomers Thermosets
e.g.
polystyrene
(amorphous)
,
Polyethylene
(crystalline),
etc.
e.g.
phenol
resin,
epoxy
resin, etc.
Thermoplastic
Elastomers (TPE)
Vulcanized
Elastomers
e.g.
polystyrene-b-
poly
butadiene-b-
polystyrene
(Kraton

)
e.g.
styrene-
butadiene
rubber
(SBR)
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.


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. Cant be thermally
processed.
E.g. Epoxy, phenol-formaldehyde resins, and
unsaturated polyesters.
Applications suitable materials for composite,
coatings, adhesive.

Synthetic Polymers
(Based on First Order Structures)
Homopolymers Copolymers Polymer Blends and IPNs
-A-A-A-A-A-A-A-A-
polyA + polyB
Statistical
Copolymers
-B-B-A-B-A-A-B-
Alternating
Copolymers
-A-B-A-B-A-B-A-B-
Graft
Copolymers
-A-A-A-A-A-A-A-A-
B
B
B
Block
Copolymers
-A-A-A-A-B-B-B-B-
-A-A-A-B-B-B-A-A-A-
B
B
B
Homopolymer: Formal definition: a polymer derived from one species of monomer.
Structure-based definition: a polymer whose structure can be represented by
multiple repetition of single type of repeat unit which may contain one or more
species of monomer units (structural units).
Copolymer: Formal definition: a polymer derived from more than one species of
monomer. Structure-based definition: a polymer whose molecule contains two or
more different types of repeat unit (polymers such as PET, Nylon are usually
considered as homopolymers.)
Polymer Blends and IPNs: Linked together through secondary (physical) forces.
IPNs: interpenetration polymer networks.
Cascade
polymers-
dendrimers
???
Copolymers
two or more monomers
polymerized together
random A and B randomly vary
in chain
alternating A and B alternate in
polymer chain
block large blocks of A alternate
with large blocks of B
graft chains of B grafted on to A
backbone

A B

random
block
graft

alternating
Homopolymer of PP
-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-
H H H H H H H H H H H H H H H
H cH3 H cH3 H cH3 H cH3 H cH3 H cH3 H cH3 H
-c-c-c-c-c-c-c-c-c-c-c-c-c-c-c-
H H H H H H H H H H H H H H H
H cH3 H cH3 H cH3 H H H H H H H H H
Copolymer of PP
PP-PP-PP-PP-PP-PE-PE-PE-PE-PE
Block Copolymer of PP
Random Copolymer of PP
PP-PE-PP-PP-PP-PE-PE-PP-PE-PE
EXAMPLE : POLYPROPYLENE (PP)
Thermoset vs. Thermoplastic
Thermoplastics can be repeatedly
reheated and molded into shapes on
cooling

Thermosetting plastics when reheated
decompose

1.2 POLYMERIZATION
a. Addition Polymerization;
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

Covalent chain configurations and strength:
Direction of increasing strength
Adapted from Fig. 14.7, Callister 6e.
Polymer Microstructure
Van der Waals, H
More rigid
Main Categories of Polymers:
Plastics:
Thermoplastics can be remelted:
Engineered Thermoplastics
Commodity Thermoplastics
Thermosetting Plastics can not be remelted
Engineered Thermosets
Commodity Thermosets
Elastomers:
Thermosets and thermoplastic!!

Commodity Thermoplastics
Commodity: Polyethylene (PE), Polystyrene (PS),
Polypropylene (PP), Polyvinyl Chloride (PVC or
vinyl) 80% of all thermoplastics!!
Also, Styrene Acrylonitrile (SAN) the copolymer
we tested in lab
Flows at elevated temperatures.
Has a glass transition temperature.
Long polymer chains
Can be remelted and recycled.
Engineering Thermoplastics
Engineering Plastics: Polycarbonate (PC),
Acrylonitrile-butadiene-styrene (ABS),
Polyamide (Nylons, PA)
Engineered plastics account for about 10%
of all plastic usage.
Generally have higher tensile strength and
elongation than commodity plastics
Elastomers
Butyl, natural rubber (polyisoprene),
EPDM, neoprene, nitrile, etc..
Characterized by high deformation
(extremely flexible) generally greater than
100%.
Almost all are thermosetting with
exception of TPEs
Vulcanization

Thermoset
Materials
Cross-linked
Phenol-formaldehyde
Unsaturated polyesters
Epoxide resins
Amino-formaldehydes
Natural rubber
Synthetic rubbers
Thermoplastic elastomers
Urea-formaldehydes
Materials
Thermosets (PF, UF, MF)
Bakelite radio 1930 Picnic set (UF) 1940s
Adhesives and impregnating resins
Electrical fittings
Tableware/picnicware
Kettle/iron/soucepan handles
Decorative laminates for work surfaces
Parts for domestic appliences
Thermoset
Materials
Thermosets (GRP, Epoxy resin)
Blondecell
Risho
Marine mouldings
Aircraft components
Sports equipment
Racing car components
Adhesives
Electrical insulators
+
Thermoset
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 :
Acoording to name of functional group in the polymer backbone

Polyamide, Polyester

1.3 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


Nomenclature
1.3.1 Vinyl polymers

A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid),
Poly(-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)
Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)
CH
2
CH
Polystyrene Poly(acrylic acid)
Poly(-methylstyrene) Poly(1-pentene)
CH
2
C
CH
3
CH
2
CH
CO
2
H
CH
2
CH
CH
2
CH
2
CH
3
B. Diene monomers
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)

CH
2
CH CHCH
2
CH
2
CH
HC CH
2
1,2-addition 1,4-addition
1.3.1 Vinyl polymers
1.3.2 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)
Additives
Polymers
Materials
Additives
Fillers
Plasticizers
Stabilizers
Flame retardants
Colorants
Lubricants
Antistatic agents
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
RECYCLING
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.
Since they dont 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.
The decks, fence, stepping stones, house shingles, and the
sweat shirt, were all made from recycled plastic.
RECAP
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 isnt 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 Waals
forces.)

The two main polymerization methods or reactions used to create
polymer chains are:

ADDITION and CONDENSATION
REACTIONS

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