Polymers

Polymers
Polymer - a large molecule consisting of (at
least five) repeated chemical units (`mers')
joined together, like beads on a string.
Polymers usually contain many more than five
monomers, and some may contain hundreds
or thousands of monomers in each chain.
Polymers may be natural, such as cellulose or
DNA, or synthetic, such as nylon or
polyethylene.

Hydro-Carbon Molecules

 . Polymer chains containing carbon and hydrogen atoms only

are held together by weak van der Waals forces

low melting points

low mechanical strength

If polymer chains are held together by

the mechanical strength of the polymers would be stronger

If cross-linkages are present between polymer chains
the polymers would be mechanically
stronger,
more elastic or more rigid
depending on the extent of
crosslinkages in the polymer

(i)
stronger van der Waals forces (PP,PTFE)
(ii) dipole dipole interaction (PVC,PET),
(iii) hydrogen bonds (Nylon)

Hydro-Carbon Molecules

Isomerism

 Two types of isomerism are possible:

stereoisomerism and geometrical isomerism

Common Polymers

Polymerization

Polymerization

Common Polymers

Polymerization

Condensation Polymerization
Condensation polymerization is a chemical process in which monomer molecules are
joined together to form a polymer with elimination of small molecules such as water,
ammonia and hydrogen chloride

In condensation polymerization,

each monomer molecule must

bifunctional

have at least two functional groups

Examples of naturally occurring condensation polymers are:

Proteins
Polysaccharides
DNA
Examples of synthetic condensation polymers are:

Nylon (a polyamide)

Kevlar (a polyamide)

Dacron (a polyester)

Urea-methanal

Nylon

A group of condensation polymers formed by

the condensation polymerization between a diamine and a

dicarboxylic acid
In the polymerization, Amide linkages are formed. Nylon is a Polyamide
One of the most important nylon is nylon-6,6
made from the condensation polymerization between
hexane-1,6-diamine and hexanedioic acid

The condensation polymerization begins with the formation of a dimer, and

a water molecule is eliminated

 Molecular structure
Physical properties of polymers depend
not only on their molecular weight/shape,
but also on the difference in the chain
structure
Four main structures
Linear polymers
Branched polymers
Crosslinked polymers
Network polymers

Types of Polymer

Copolymer

Graft copolymers.
One mer forms
backbone, another
mer is attached to
backbone and is a
sidechain (it is
grafted to the
other polymer)

Block copolymers. Domains of pure mers

Adapted from Fig.

4.9, Callister &
Rethwisch 3e.

Copolymers
two or more monomers
polymerized together
random A and B randomly
positioned along chain
alternating A and B alternate
in polymer chain
block large blocks of A units
alternate with large blocks of B
units
graft chains of B units grafted
onto A backbone
A

random

alternating

block

graft
24

Copolymers
Polymers often have two different monomers along the
chain they are called copolymers.

With three different units, we get a terpolymer. This gives us

an enormous design space

 Oligomer: Short polymer chain

Polymer Structure
Elastomers (rubbers)
Polymers with irregular structure, weak intermolecular attractive forces and
flexible chains.
Can undergo local mobility, but gross mobility of chains is restricted.
Characterized by high extensibility, low initial modulus in tension but they stifen
when strecthed.

stretch

leave

ENTROPY WORK!

Polymer Structure
Plastics
Fall between the elastomers and fibers. However there is no exact boundary
Harder to stretch than elastomers (Because of crystalline regions?). But preserve
their shape when stretched unlike elastomers (Strain induced crystallization, stiff
chains)
They are pliable, that is, they can be shaped and molded easily
Thermoplastics: Melt when heated and can be melted again after cooling
Thermosets: Undergoes crosslinking when heated, so does not melt again,
decomposes if heated further
Flexible plastics: Plastics above their Tg. Flexible, soft
Rigid plastics: Plastics below their glass transition temperature (Tg). Brittle, hard

What are Tg, crosslinking and melting for polymers ?

Polymer Structure
Glass transition temperature (Tg)
Different polymers have different segments on their backbones. The ease of movement of
these segments (portions of the chain) depends on the structure, physical environment of the
chain etc. of the segment.

Any movement of these segments require energy which is kinetic in this case, right? Then each
different polymer would have different energy requirement for the movement of these segments
(different polymer = different structure, different physical environment of the chain etc).
Below glass transition temperature, these segments do not have sufficient energy to move. So,
if you apply some stress, say if you try to bend a polymer which is below its Tg then the segments
wont be able to move into new positions to relieve the stress which you have placed on them;
which will make the polymer brittle. Above Tg they would, so they would be flexible.

Always keep this in mind: Tg IS A PROPERTY RELATED WITH THE AMORPHOUS REGIONS OF THE
POLYMER, NOT CRYSTALLINE!
So it should now be obvious that elastomers are elastomers above their Tg. Below, they are not
elastomers, they are glassy, because they are not flexible anymore (Remember my experiment
with rubber glove and liquid nitrogen during the lecture).

Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be melted (tires,
rubber bands)
Thermoplastic: Meltable plastic
Elastomers: Polymers that stretch and then return to their
original form: often thermoset polymers
Thermoplastic elastomers: Elastic polymers that can be melted
(soles of tennis shoes)

Polymer Families
Polyolefins: made from olefin (alkene) monomers
Polyesters, Amides, Urethanes, etc.: monomers linked by ester,
amide, urethane or other functional groups
Natural Polymers: Polysaccharides, DNA, proteins

PLASTICIZERS
Most polymers of high molecular weight are quite rigid.
These polymers can be softened and made flexible by
adding plasticizers, usually dialkyl phthalate esters,
such as dibutyl phthalate, a high boiling liquid.
O
C
C
O

O CH2CH2CH2CH3
O CH2CH2CH2CH3

dibutyl phthalate

The plasticizer separates the individual polymer chains

from one another. It acts as a lubricant which reduces
the attractions between the polymer chains.

SOME COMMON ADDITION POLYMERS

example

monomer

polymer

polyethylene

CH2

CH2

polypropylene

CH2 CH

CH2

CH3

CH2

CH2 CH
CH3

polystyrene

CH2 CH

CH2 CH

polyvinyl chloride

CH2 CH

CH2 CH

(PVC)

Cl

Cl

uses
most common polymer
bags, wire insulation,
squeeze bottles

fibers, bottles,
indoor-outdoor carpet
styrofoam,
inexpensive molded
objects: household items,
toys
synthetic leather, clear
bottles, floor coverings,
water pipe

Teflon

CF2 CF2

CF2 CF2

non-stick surfaces,
chemically resistant items

polyacrylonitrile
(Orlon, Acrilan)

CH2 CH

CH2 CH

fiber used in sweaters,

blankets, carpets

C N

C N

COMMON ADDITION POLYMERS (cont)

example
poly(methyl
methacrylate)

monomer

CH3
CH2

poly(vinyl acetate)

CH3
CH2

CH2

(PVA)

CH

CH2 CH

O C CH3

O C CH3
O

O
CH3

natural rubber
CH2

C CH CH2

CH3

CH2 C CH CH2

Cl

neoprene rubber
CH2

unbreakable glass,
latex paint

CO2CH3

CO2CH3

(Lucite, Plexiglass)

uses

polymer

C CH CH2

Cl

adhesives,
latex paints,
textile coatings
chewing gum
the polymer is crosslinked with sulfur
(vulcanization)

cross-linked with ZnO,

resistant to gasoline
and oil

CH2 C CH CH2

Addition Polymerization

Examples of addition polymers:

Polyethene (PE)
Polypropene (PP)
Polystyrene (PS)
Polyvinyl chloride (PVC) p.81
Polytetrafluoroethene (PTFE) p.81
Polymethyl methacrylate (PMMA) p.96

1. Polyethene (PE)

Ethene is the monomer that is used to synthesize polyethene

Depending on the manufacturing conditions, two kinds of
polyethene can be made
low density polyethene (LDPE)
high density polyethene (HDPE)

Molecular mass between 50 000 and

3 000 000
Light, flexible
Low melting point
Used to make soft items (e.g. wash bottles, plastic bags and
food wraps)

Low Density Polyethene (LDPE)

Molecular mass between 50 000 and 3 000 000

Light, flexible
Low melting point
low density PE, good flexibility, good tenacity, less rigid than HDPE
Applications garbage bags, flexible pipes, toys,

High Density Polyethene (HDPE)

Molecular mass up to 3 000 000

Tougher
Higher melting point
High density PE,
Moderately rigid, good impact resistance, excellent resistance, to almost all
chemicals, sensitive to UVs; vast
Applications engine oil bottles, garbage containers, buckets and large tanks,
handling containers, pipes, to make soft items (e.g. wash bottles, plastic bags
and food wraps)
Used to make more rigid items
(e.g. milk bottles and water buckets)

Low Density Polyethene and High

Density Polyethene
LDPE : HDPE : -

Highly branched polymer chains

Linear polymer chains with very little branching

The branches prevent the polymer chains from getting close to each other

low packing efficiency

Structure
of LDPE

 creates a significant proportion of

structure
low density

crystalline

amorphous regions in the

amorphous

Structure
of LDPE

HDPE :
contains long polymer chains with very

the polymer chains can pack closely

crystalline
structure

higher density

little branching
together into a largely

Low Density Polyethene and High

Density Polyethene
Crystalline
structure

Structure of HDPE

Low Density Polyethene and

High Density Polyethene

Compared with LDPE, HDPE

is harder and stiffer
has a higher melting point
has greater tensile strength
has strong resistance to chemical
has low permeability to gases

attack

Some products made of polyethene

2. Polypropylene (PP)

propene can be polymerized to

isotactic polypropene (ionic mechanism)

All methyl groups are arranged on the same(iso) side of the polymer chain. It has close
packing with high-density, rigid, tough, high m.p.

Semi-crystalline thermoplastic, Lightest plastic

More rigid than HDPE
used for moulded furniture
High mechanical strength and strong resistance to abrasion - used for making
crates,
kitchenware and food containers
Spun into fibres for making ropes and carpets

especially useful for making

athletic wear

they do not absorb water from sweating as cotton does.

Ideal for garden furnitures (PP + talc), pumps and agitators of laundry machines,
interior of dishwashers, ventilators, car bumpers...
Food containers that go from the microwave to the refrigerator
Transparent films of bi-oriented PP are used for the packaging of products (ex.
cigarettes, records, books)

Uses of PP

Packaging film

much
stronger than
wrapping film
for food (PE)

Max T: 275F/135C
Min T: 32F 0C
Melting P: 338F 170C
Tensile Strength: 4,500 psi
Hardness: R95
UV Resistance: Poor
Excellent resistance to dilute and concentrated Acids, Alcohols, Bases and Mineral
Oils
Good resistance to Aldehydes, Esters, Aliphatic Hydrocarbons, Ketones and
Vegetable Oils
Limited resistance (for short term use only) to Aromatic and Halogenated
Hydrocarbons and Oxidizing Agents

3. Polystyrene (PS)

Styrene is made from the reaction of benzene with ethene

followed by dehydrogenation
The styrene produced is polymerized by a free radical mechanism into
polystyrene

at 85 100C

using dibenzoyl peroxide as the initiator

3. Polystyrene (PS)
PS is more rigid than HDPE due to the induced dipole-induced dipole
interaction between benzene rings of adjacent polymer chains.

Polystyrene is amorphous, transparent, brittle and chemically inert

used to make toys, specimen containers and cassette cases

By heating polystyrene with a foaming agent (e.g. pentane + steam),

expanded polystyrene can be made

Expanded polystyrene is
an extremely light, white solid foam

mainly used to make light-weight

ceiling tiles in buildings, and
food boxes and shock absorbers for
packaging, disposable glasses
and utensils, packaging materials, toys, disposable razors

4. Polyvinyl Chloride (PVC)

PVC is produced by addition polymerization of the choroethene(vinyl chloride)

monomers

in the presence of a peroxide catalyst

(e.g. hydrogen peroxide at about
60C)

amorphous thermoplastic
Most fire resistant of
commodity polymers
Presence of the polar C Cl bond

considerable dipole-dipole
interactions exist between the
polymer chains

makes PVC a fairly strong material

PVC is hard and brittle

used to make pipes and bottles
When plasticizers are added the effectiveness of the dipole- dipole interactions is
reduced

PVC becomes more flexible

Used to make shower curtains, raincoats and artificial leather, insulating coating of
electrical wires , Applications of rigid PVC: piping, gutters, external coatings
of houses, vertical blinds, credit cards, transparent bottles, Applications of flexible PVC:
cable sleeving, flooring, leather , limitations, film for packaging, garden hoses, transparent

5. Polytetrafluoroethylene (PTFE)

PTFE is produced through addition polymerization of the tetrafluoroethene

monomers under high pressure and in the presence of a catalyst
Commonly known as Teflon or Fluon.

semi-crystalline thermoplastic- Outstanding thermal and chemical resistance Poor creep behavior, low coefficient of friction, expensive
Fluorine is larger than hydrogen
the molecular mass of PTFE is greater than that of PE
leads to greater van der Waals forces between the polymer chains
PTFE has a relatively high melting point and is chemically inert
Its non-stick properties make it
an ideal material for the
coating of frying pans
As the insulating coating of electrical wires
As sealing tapes for plumbing joints -For making valves and
bearings

6. Polymethyl Methacrylate (PMMA)

More commonly known as Plexiglass - amorphous thermoplastic - Fragile, very
resistant to UV, poor chemical resistance, especially to organic products

PMMA is formed by the free radical addition polymerization of methyl methacrylate

in the presence of an organic peroxide at about 60C

PMMA is a dense, transparent and tough solid

makes it a good material for making
safety goggles, advertising sign
boards and vehicle light protectors
Unlike PP, it is easily scratched - Clear, colorless polymer used extensively for optical
applications light wells, port-holes and plane cockpits, lenses of cameras, rear and position
lights of cars, watch glass, signs, etc.

Objects made of PMMA: safety goggles and vehicle light protectors

7. Polyethylenetherepthalate PET or Terylene

The ester linkages are polar.

Polymer chains are held together by
strong dipole-dipole interaction
strong
tough
smooth
resistant to water and chemicals
semi-crystalline thermoplastics
Clothes made of 100% polyester
resistant to chemicals
Non-toxic
easily washed
PET is commonly used for making food containers and bottles.,
OHP sheets

PolyOxymethylene (Acetal or POM)

Crystalline Yes, very flexible - semi-crystalline thermoset - High rate of crystallinity

Hygroscopic Yes (O)
Glass Transition Low (-100 F)
Flammability Yes (only C and O bonds)
Low to Medium Cost
Good Chemical Resistance
High Strength
Excellent Fatigue
Good Creep Resistance
Excellent mechanical properties, less sensitive to water than nylons, excellent wear
resistance
Dimensional Stability at High Temperature

Uses - Gears,
Clips, and Zippers

Bearings, Faucet Components, Fuel Pump Components, Refrigerator

Polycarbonates (PC)

Crystalline No, too rigid - amorphous thermoplastic

Hygroscopic Yes (O) - Transparent, rigid and highly resistant to impact
Glass Transition High (300 F)
Flammability No (High number of double carbon bonds will extinguish soot)
Polycarbonates are amorphous linear polyesters with excellent moldability.
Good impact strength, temperature resistance.
Transparent (aka Plexiglas)
Tensile strength similar to ABS and nylon except impact strength can be 10X
greater! ButCosts more and susceptible to environmental stress cracking.
Uses - Helmets (football and hard hats), face shield, power tool housings, cell
phones, automotive dashboards, window cranks, small gears, etc. helmets,
visors, motorcycle and boat windshields, police shields, windows of counters in
banks, sterilizable dishes and machines, luminaries

Nylon/Poly Amide
Polyamides (nylon) are polymers formed as a condensation product of an acid
and amine. They all contain the characteristic amide group: CO-NH.
Properties- semi-crystalline thermoplastics
High Strength among the highest of all engineering plastics
Good candidate for structural parts
Good Heat Resistance (continuous use up to 260 F, bonded to rubber in molds
up to 350 F) - good impact resistance can be improved by the addition of rubber
Good Chemical Resistance
Excellent Wear Resistance
Good Fatigue Resistance - excellent friction properties
Uses - Structural parts!! (i.e. replacement for cast aluminum 380 series),
Electrical Connectors, Gears, Bearings, Cables, Ties, Rope
Fishing Line , Automotive Valve Covers/Oil Pans, Sports/Exercise Equipment,
Tools. Tennis rackets, components of cameras and numerous industrial
machines (pumps, printers, valves, ball bearing cages, etc.), speedometer gears,

Polymethylmethacrylate (Acrylic) (PMMA)

Crystalline No, too rigid (dual methyl groups)

Hygroscopic Yes (O)
Glass Transition High (220 F)
Flammability Yes (only C-H and C=O bonds)
Low Cost
Good Chemical Resistance
Hardness
Good Creep Resistance
Transparency
Best Polymer for Weatherability
Uses - Sheet, Windows, Displays, Signs, Surgical Instruments.

Acrylonitrile Butadiene Styrene (ABS)

This is an ethenic engineering plastic
i.e. basic monomer structure as ethylene just
modifying polystyrene by:
Adding plasticizer and copolymers of styrene butadiene and
styrene acrylonitrile to produce a polystyrene terpolymer of
acrylonitrile, butadiene and styrene (ABS).
Properties
Low to Medium Cost
Good Impact Strength
Good Chemical Resistance
High Gloss Surface Finish
Good Flexural Properties
Uses - Appliance Housings, Canoes, Typewriter Keys, Pipes & Pipe Fittings, Telephone
Housings, Household goods, tools, packaging (excluding foods), interior elements for
cars, tubes and junctions

Acrylonitrile Butadiene Styrene (ABS)

ABS combines the strength and rigidity of acrylonitrile and styrene polymers with the
toughness of polybutadiene rubber. While the cost of producing ABS is roughly twice
the cost of producing polystyrene, it is considered superior for its hardness, gloss,
toughness, and electrical insulation properties.

PolyImide(PI) -

R
Norton

Thermosetting polyimides

It has thermal stability, fire resistant polymers

good chemical resistance,

excellent mechanical properties, and

characteristic orange/yellow color.

Polyimides compounded with graphiteor glass fiber reinforcements have

flexural strengths

Thermoset polyimides exhibit very low creep and hightensile strength.

Molded polyimide parts and laminates have very good heat resistance.

Normal operating temperatures for such parts and laminates range from
cryogenic to those exceeding 500 F (260 C).

Polyimides are also inherently resistant to flame combustion and do not

usually need to be mixed with flame retardants.

Applications - lightweight, flexible, resistant to heat and chemicals. Therefore,

they are used in the electronics industry for flexible cables, as an insulating film
on magnet wire and for medical tubing. For example, in a laptop computer, the cable
that connects the main logic board to the display, Bearings, Aerospace Applications

PI

PolyAmideImide(PAI) - Torlon
High strength Plastic - long-term strength and stiffness up to 275C
Outstanding wear resistance
Superior toughness from cryogenic up to 275C
It has outstanding resistance to wear, creep, and chemicals
Resistant to strong acids and most organics
Inherent flame resistance

Applications
Aircraft hardware and fasteners, Mechanical and structural components
Transmission and powertrain components, Coatings, composites, additives,
Electric motor components, Semiconductor fabrication and testing, Oil and gas
exploration and recovery equipment, Bearing retainers, Gears, Bushings, Seals and
Thrust washers -Parts for combustion and jet engines, bearings, pressure disks as well
as components for mechanical, electrical and electronics application.

Poly Ether Ether Ketone (PEEK)

This thermoplastic features the following properties: mechanical
strength, stiffness, hardness, high durability at high temperatures, good
resistance to chemicals and a consistent low flammability as well as a
small smoke emission during the process of burning. PEEK normally is
semi-crystalline, light-amber-colored and intransparent.

Applications
Flexible circuit boards (plastic films), fabrics and single fibres, injectionmoulded machine parts, components for high-radiation-application and
the space flight sector.

Poly-Phenylene-Oxide (PPO)
PPOs are a family of amorphous, intransparent, light-grey-colored
thermoplastics. They feature an outstanding stability at high
temperatures and therefore can be applied within a wide temperature
range. Some more characteristics are extraordinary hydrolytic stability
and excellent dielectric properties within a wide range of frequencies
and temperatures.

Applications
Electric parts and components for TVs, washing maschines and
dishwashers, automobile parts, integral foamed plastics

Poly-Phenylene-sulfide (PPS)

PPS is a highly crystalline, linear structured thermoplastic composed of

alternating sulfur atoms and phenylene rings in a para substitution pattern.
This means that the polymer contains sulfur-linkings between the benzene
cycles of the backbone, the highly stable chemical bonds of its molecular structure
conferring a remarkable degree of stability towards both thermal degradation and
chemical reactivity.
Branched types of this polymer can be transformed into a thermoset material by
using thermic methods. Glas fibre enhanced PPS feature permanent high
temperature resistance .

Applications - Hydraulic components, runs, electronic and automobile parts

CODE SYSTEM FOR PLASTIC MATERIALS

These codes allow consumers to separate plastics for recycling.

1
2
3

PETE

polyethylene
terephthalate

soft drink bottles

HDPE

high-density
polyethylene

milk and beverage

containers, products
in squeeze bottles

polyvinyl
chloride

bottles with cleaning

agents in them, some
shampoo bottles

LDPE

low-density
polyethylene

thin plastic bags,

plastic wrap

PLASTIC MATERIALS CODE SYSTEM (cont)

PP

polypropylene

heavy-duty,
microwavable containers
used in the kitchen

PS

polystyrene

foam beverage cups,

envelope windows

Other

All other resins,

multilayered materials,
containers made of
other materials

ketchup bottles,
snack containers,
mixtures where
the top differs from
the bottom

The codes are frequently stamped on the bottom of containers.

Urea Formaldehyde
Amino plastics are hard, scratch and stain resistant, moldable, thermally resistant, and
come in a variety of transluscent and opaque colours. While they are fairly strong, they are
not unbreakable. They are resistant to solvents such as cleaning fluids, gasoline, and
oils. Aminos will not burn or soften, even in open flame.

Applications - Amino resins are used in molding powders. Molded products of amino
plastics include switch cover plates, buttons, electric mixer housings, radio cabinets, coffee
makers, and door knobs. Aminos are also extremely useful as adhesives, especially in the
woods industry, and as laminated lay-ups for kitchen counters. Finally, aminos are also
employed as surface coatings on paper and fabri

Phenol formaldehyde