Polymer Science and Engineering

"I am inclined to think that the

development of polymerization
is perhaps the biggest thing that
chemistry has done, where it has
had the biggest effect on
everyday life
Lord Todd,1980

Ethylene
CH = CH
2

Polyethylene
Magic ?

[-CH -CH -]n

2
2

A Useful Classification

USE

NATURAL

SYNTHETIC

Fibers

Adhesives

Wool, Silk,
Cellulose
Natural Rubber,
Elastin
Gutta Percha,
DNA,
Polypeptides
Wood,
Bone,
Teeth
Barnacles!

Paints

Shellac

Nylon, PET,
Lycra
SBR, Silicones,
Polybutadiene
Polyethylene,
Polypropylene,
Polystyrene
Polyester/Glass,
Carbon Fiber/Epoxy
Formica
Elmers Glue-All
Super-Glue
Acrylics

Elastomers
Plastics
Composites

Historical Background
NATURAL POLYMERS

- used throughout recorded

history

SYNTHETIC POLYMERS

- initially chemically modified

natural polymers

RUBBERS OR ELASTOMERS

- unique materials, both

natural and synthetic

Historical Background
1845
1848
1862

1870s
1884

SCHOENBEIM

- nitration reactions

MENARD

- collodion films ;nitrated

cellulose

PARKES

- "Parkesine" ; added
camphor (and other stuff)
- plasticizers

HYATT

- billiard balls !!

CHARDONNET

- extrusion

1890s

CROSS, BEVAN,
& BEADLE

1905

BAEKELAND

- Bakelite, the first thermoset

STAUDINGER

- the macromolecular hypothesis

1920
> 1920

NEW THERMOPLASTICS

- regenerated cellulose
rayon,cellophane

- (more on these later)

Natural Polymers
NATURAL POLYMERS - - used throughout recorded history

A natural fiber
on the hoof
Silk

Better hope your garden never looks like this

Cotton

Nitrated Cellulose

OH

HO

O
O
CH2
OH

Cellulose

Schoenbeim

Explosive Stuff!
O
N

C
O

Glycerol
CH2OHCHOHCH2OH

C
O

O
N

N
O

Nitroglycerin

Some Basic Chemistry:

Atoms and Bonding
H

Covalent
H

Na

Cl

Ionic

Cl

Molecule

Na

Does not form NaCl molecule!

Metallic

Some Basic Chemistry:

Single and Double Bonds

HC H

H
H

H H

CH4

HC C H
H H

C2H6

H H
CC

H H

C2H4

Some Basic Chemistry:

Functional Groups
CH2=CH2
Ethylene
O

RCOR
Ester
O
=

RNH2 + RCOH
Amine Carboxylic Acid

ROH + RCOH
Alcohol Carboxylic Acid

RCNHR
Amide

Functional Groups are small groups of atoms held together in a specific

arrangement by covalent bonds. They are responsible for the principle chemical
properties of the molecule in which they are found.

Condensation Reactions
O

Reversible
Reaction!

CH3 - C - OH + CH3 - CH2 - OH

Acetic Acid

Ethyl Alcohol
or Ethanol

Ester linkage

CH3 - C - O - CH2 - CH3 + H2O

Ethyl Acetate

If you dont
know what this
is you should
be castigated
unmercifully

Why do Molecules React ?

Acetic Acid

O
CH3 - C - OH

kersplat!

HO - CH2 - CH3
Ethyl Alcohol
or Ethanol

Why do Molecules React ?

O
H:O - CH2 - CH3

CH3 - C:OH

HO. + .H
O
CH3 - C. + .O - CH2 - CH3

HO:H ~ H2O
O
CH3 - C:O - CH2 - CH3

This isnt what really happens, but shows you

how the valency electrons get rearranged

Making a Polymer
O
CH3 - C - OH + CH3 - CH2 - OH
Acetic Acid

Ethyl Alcohol
or Ethanol

Reversible
Reaction!

Ester linkage

CH3 - C - O - CH2 - CH3 + H2O

Ethyl Acetate

If we heat acetic acid and ethanol up to just over 1000C,

to get the reaction going and drive off water, why dont
we form polymer?

Explosive Stuff!
O
N

C
O

Glycerol
CH2OHCHOHCH2OH

C
O

O
N

N
O

Nitroglycerin

Guncotton
and
Collodion

Guncotton and
Collodion

P a r k e s and P a r k e s i n e
He wasnt this
miserable.

The Crystal Palace

Hyatt and the Elephants

Celluloid
What a sales pitch

C h a r d o n n e t and Mother-in-Law Silk

Regenerated Cellulose
Cellophane and Rayon

OH
HO

O
O
CH 2OH

NaOH
OH
HO

O
O
CH 2ONa

CS2
OH
HO

O
O
CH 2OCSNa
H+

S
OH

HO

O
O
CH2OH

More
Cellophane

Rayon

B a e k e l a n d and Bakelite
The first true synthetic plastic

Bakelite - Material of a Thousand Uses

Clear Bakelite items

A Bakelite camera

Clock made of a phenolic resin

and celluloid

A Bakelite radio

A Bakelite telephone

A Bakelite microphone

Network Formation
The hydrogens in the ortho and para positions to
the OH group, which by convention are not
usually shown but here are indicated by a *, can
react with fomaldehyde to form (initially)
oligomers.

OH

OH
CH2

CH2
OH
CH2

OH
CH2

OH

OH

+ CH 2O

OH
CH2

CH2

CH2
OH

OH

A Condensation Reaction!
OH

OH

H
OH

H
H

O
H

Network Formation
Continued reaction
builds up a densely
cross-linked network.
This is Bakelite, a
thermosetting
polymer. Once the
reaction is complete,
the material cannot
be reheated and
reformed. So, what do
you think the
definition of a
thermoplastic is?

OH
CH 2

OH
CH2

OH
CH 2

OH

CH 2

CH2

OH

HO

CH 2

CH 2

CH 2
O

CH 2

OH
O

CH 2

H 2C

CH 2

CH 2

H2 C

HO

OH
CH 2

HO

HO
CH 2
HO

O
CH 2

CH 2
HO

OH

CH 2

CH 2

NEXT;
S t a u d i n g e r and the
Macromolecular
Hypothesis