Polymers

Polymers: What are they?

Different Types
Uses and Applications
Chemical Make-up
Polymers - What are they?

Polymers are a special kind of

macromolecule
The word polymer comes from the Greek
words “poly,” meaning “many”, and
“meres,” meaning “parts” or “repeating
units”
A Polymer consists of a large chain of
repeating molecules (monomers) that are
attached in an end to end fashion
Description of Polymers

Imagine a string of beads

Each bead is identical (for example, red
sphere)
• Represents the “mer”
The string can contain 100’s of beads
• Represents the “poly” characteristic
The string in between the beads represents
the chemical bond between monomers
Length of Polymers

Polymer chains are HUGE!

Polymers typically consist of between
20,000 and 40,000 individual monomers
If each bead on the string of beads were one
inch apart, one polymer molecule could be as
long as 10 football fields!!!
This chain length is what gives the
polymer most of its desirable
characteristics
Description of Polymers

Polymer chains are flexible, and usually

“clump” together into a smaller shape
This enables the individual chains to
interact and become entangled
This helps to give a polymer its strength
and flexibility
Types of Polymers

There are two main types of polymers

Natural
• (cotton, silk, wood, leather…)

Synthetic
• (plastics, nylon, latex…)
Synthetic Polymers

There are two basic types of synthetic

polymers
Thermoplastics (plastics, Styrofoam)
• These can be softened by heating and hardened by
cooling - easily recycled
• Can easily be cast into various shapes
Thermosets (epoxy’s, adhesives)
• These harden after being heated
• Can easily be cast into different shapes
• Cannot be reformed
Types of Polymers -
Copolymers

Most polymer chains are made up of one

type of monomer (for example, red
beads)
However, some polymers are made up of
different types of monomers (for example,
blue and red beads) - these are called
copolymers
Copolymers

There are four main types of copolymers

The different monomers can be arranged
either in an alternating or random fashion
Alternating
...-red-blue-red-blue-red-blue-red-blue-red-…
Random
…-blue-red-red-blue-red-blue-blue-red-blue-…
Copolymers

There are also block copolymers and graft

co-polymers
Block
…-R-R-R-R-R-R-B-B-B-B-B-B-R-R-R-R-R-R-…
Graft
…-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-…
|
B-B-B-B-B-B-B-B-B-…
Polymers - Pros and Cons

A polymer has many very advantageous

properties. Polymers are:
Lightweight
Strong and durable
Cheap
Easy to manufacture
Unfortunately, polymers do not easily
biodegrade and end up producing large
amounts of waste
Uses of Polymers

Polymers are incorporated into nearly

every aspect of daily life
Entertainment
Sports
Clothes
Hobbies/Toys
Household products
Automotive
Polymer Chemistry

A polymer chain is built on a Carbon

backbone
A monomer unit consists of a small
carbon chain attached to a specific type of
functional group
The functional group is what gives each
polymer chain its individual characteristics
Polymer Chemistry

As previously stated, polymer chains

interact with one another, becoming
entangled
Polymer chains also form cross-links with
adjacent chains, which allows the polymer
to hold its shape and gives added
strength
Summary

Polymers are made up of large chains of

repeating units, called monomers
Individual chains interact to form a
stronger overall substance through
entanglements and cross-links
Polymers are incorporated into almost
every aspect of daily life
Polymers are lightweight, strong, and
inexpensive
The Structure and Properties of
Polymers
Also known as

Bonding +
Properties
What is a polymer?

• A long molecule made

up from lots of small
molecules called
• monomers.
 All the same monomer
• Monomers all same
type (A)
• A+A+A+A
• -A-A-A-A-
• eg poly(ethene)
polychloroethene
PVC
Different monomers
• Monomers of two
different types A + B
• A+B+A+B
•  -A-B-A-B-
• eg polyamides
• polyesters
 Addition polymerisation
• Monomers contain C=C bonds
• Double bond opens to (link) bond to next
monomer molecule
• Chain forms when same basic unit is
repeated over and over.
• Modern polymers also developed based on
alkynes R-C C - R’
 Copolymerisation
• when more than one monomer is used.
• An irregular chain structure will result eg
propene/ethene/propene/propene/ethene
• Why might polymers designers want to
design a polymer in this way?
• (Hint) Intermolecular bonds!
 Elastomers, plastics & fibres
• Find a definition and
suggest your own
example of each of
these.
 What decides the properties of a
polymer?
• Stronger attractive forces between chains =
stronger, less flexible polymer.
• Chains able to slide past each other = flexible
polymer .
• In poly(ethene) attractive forces are weak
instantaneous dipole - induced dipole, will it be
flexible or not?
• Nylon has strong hydrogen bonds, why does this
make it a strong fibre?
 Getting ideas straight
• Look at page 110 -111 of Chemical Ideas.
• Take turns in explaining to a partner how
the following molecular structures affect the
overall properties of polymers :-
• chain length, different side groups, chain
branching, stereoregularity, chain
flexibility, cross linking.
 Thermoplastics (80%)

• No cross links between chains.

• Weak attractive forces between chains broken by
warming.
• Change shape - can be remoulded.
• Weak forces reform in new shape when cold.
 Thermosets

• Extensive cross-linking formed by

covalent bonds.
• Bonds prevent chains moving relative to
each other.
• What will the properties of this type of
plastic be like?
Longer chains make stronger
polymers.
• Critical length needed before
strength increases.
• Hydrocarbon polymers average
of 100 repeating units
necessary but only 40 for
nylons.
• Tensile strength measures the
forces needed to snap a
polymer.
• More tangles + more
touching!!!
 Crystalline polymers
• Areas in polymer where
chains packed in regular way.
• Both amorphous and
crystalline areas in same
polymer.
• Crystalline - regular chain
structure - no bulky side
groups.
• More crystalline polymer -
stronger and less flexible.
 Cold-drawing

• When a polymer is stretched a ‘neck’ forms.

• What happens to the chains in the ‘neck’?
• Cold drawing is used to increase a polymers’
strength. Why then do the handles of plastic carrier
bags snap if you fill them full of tins of beans?
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 Synthetic and Biological Polymers

Polymers: Macromolecules formed by the covalent

attachment of a set of small molecules termed monomers.

Polymers are classified as:

(1) Man-made or synthetic polymers that are
synthesized in the laboratory;
(2) Biological polymer that are found in nature.

Synthetic polymers: nylon, poly-ethylene, poly-styrene

Biological polymers: DNA, proteins, carbohydrates

31
Hydrocarbons
ex: Alkanes
 1 – Meth-
 2 – Eth-
 3 – Prop-
 4 – But-
 5 – Pent-
 6 – Hex-
 7 – Hept-
 8 – Oct-
 9 – Non-
 10 – Dec-
 11 – Undec-
 12 – Dodec-
 Hydrocarbons
at Room Temperature
 Gas  Liquid  Waxy  Plastic
 Methane 20 to 40 40 or more
 Ethane 5 to 19 Carbons Carbons
 Propane Carbons
 Butane
Melting Point
 As the length of hydrocarbons get longer, the
Melting Point grows Higher. Why?

Melting and Boiling Temperatures of Alkanes

1.2

1
Tempurature (˚C)

0.8
Series3 Series2

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
Number of Carbons
What other material properties
change?
 Viscosity

 Hardness

 Toughness

 Flammability
Bonding

 Covalent

 Ionic (NaCl)

 Polar (H2O)

 Van der Waals

 Methods for making polymers

Addition polymerization and condensation polymerization

Addition polymerization: monomers react to form a

polymer without net loss of atoms.

Most common form: free radical chain reaction of

ethylenes

n monomers one polymer molecule

37
Example of addition polymers

38
Free-Radical AdditionPolymerization of
Ethylene
H2C CH2

200 °C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 ..
RO
.. • Mechanism
H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 Likewise...

•H2C=CHCl polyvinyl chloride

•H2C=CHC6H5 polystyrene

•F2C=CF2 Teflon
Important
constitutions
for synthetic
polymers

49
Supramolecular
structure of
polymers

50
Structural
properties of
linear
polymers:
conformationa
l flexibility
and strength

51
Molecular Structure
of Polymers
 Linear
 High Density Polyethylene (HDPE), PVC, Nylon,
Cotton
 Branched
 Low Density
Polyethylene (LDPE)
 Cross-linked
 Rubber
 Network
 Kevlar, Epoxy
Chain Length: 1000 - 2000

Low-Density Polyethylene (LDPE)

 Chain Length: 4,000 – 5,000

PVC – (polyvinyl chloride)

More Polar  Stronger Bonding

Chain Length: 10,000 – 100,000

High-Density Polyethylene (HDPE)

Chain Length: 2-6 million

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

Helmet

Gears
Rubber Tree

 Sap:
 Sticky
 Viscous
 Gooey

 Goodyear
 Experiment
 Luck
 Profit ($0)
Vulcanization
 Condensation polymerization

Condensation polymerization: the polymer grows from

monomers by splitting off a small molecule such as
water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

59
Chain Length: 4,000 – 8,000

Polyethylene Terephthalate (PETE)

“Polyester”

Ester
 Kevlar

Strong Network of Covalent Bonds

And Polar Hydrogen Bonds
Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Q uic kTim e™ and a
Ph ot o - JPEG d ec om pr ess or
ar e nee ded t o s ee t h is pic t ur e .

They're nylons, Benjamin.

adipic acid
+
NH2
H2N

hexamethylene diamine

nylon
62
Nylon
 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

64
 Biopolymers

Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)

Sugar polymers (Carbohydrates)

Genetic information for the cell: DNA

Structural strength and catalysis: Proteins

Energy source: Carbohydrates

65
 Proteins: amino acid monomers

The basic structure of an amino acid monomer

HO NH2
H
O R

The difference between amino acids is the R group

 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 Starch
Biology
DNA

Sugar Proteins
69
 Proteins: condensation polymers

Formed by condensation polymerization of amino acids

Monomers: 20 essential amino acids

NH2 General structure of an amino acid
H R
CO2H
R is the only variable group

Glycine (R = H) + Glycine First step toward poly(glycine)

70
Representation of the
constitution of a protein

71
Three D representation of the structure of a protein

72
DNA
 Thymine (T)
The monomers:

Adenine (A)
Cytosine (C)

Guanine (G)

Phosphate-
Sugar (backbone) of
DNA
74
Phosphate-
sugar
backbone
holds the DNA
macromolecule
together

75
One strand
unwinds to
duplicate its
complement via a
polymerization of
the monomers
C, G, A and T

76
Carbohydrates
78
Endless Possibilities

 New
Functional
Groups

 Different
Polymer
Backbones
Conclusions:
 Polymers make up all sorts of materials that
are all around us!
 They can have a huge range or material
properties based on their:
 Functional Groups
 Structure
 Backbone
 Keep thinking about how chemical
interactions on the nano-scale correspond to
material properties on the macro-scale
Links
 http://en.wikipedia.org/wiki/Plastic_recycling
 http://en.wikipedia.org/wiki/Alkane
 http://en.wikipedia.org/wiki/Higher_alkanes
 http://en.wikipedia.org/wiki/Ultra-high-molecular-weight_polyethylene
 http://en.wikipedia.org/wiki/Polycondensation
 http://www.chemistryland.com/ElementarySchool/BuildingBlocks/BuildingOrg
anic.htm
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm
 http://www.bbc.co.uk/schools/gcsebitesize/science/21c/materials/molecstru
ctpropertiesrev3.shtml
 http://en.wikipedia.org/wiki/Van_der_Waals_force
 http://en.wikipedia.org/wiki/Vulcanization
 http://www.scribd.com/doc/26766586/08-Polymers-Why-is-Rubber-Elastic
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm