Historical Perspective on the

Use of Polymers
CHE 653

Polymer Use Ancient Civilizations

Polymers have
been utilized
throughout ancient
history
Most ancient
civilizations utilized
polymers in one way
or another
Egyptian
Hindu
Mesoamerican

Polymers fit for the Pharaoh

Polymers and resins
found many uses in
ancient Egypt
Mummification was
performed using either
resin or bitumen
Resin is from trees
(pistacio)
Bitumen petroleum
based

The term Mummy is

derived from the Persian
word for pitch
Resins were also used
in the manufacture of
perfumes

Shellac Ancient Hindu Resin

Shellac is a natural
resin that comes
from Laccifer Lacca
Lac is the resinous
substance secreted
to form the cocoon
This sticklac is the
raw material for
shellac
Originally prized for
its red color (Lac
Dye) ~250AD
First use as a
coating in ~1590

Mesoamerican uses for Rubber

Sap from certain
trees could be mixed
with other plants to
produce a solid
material.
Water proof
Elastic

Use dates from

~1600BC
Olmecs
Aztecs
Maya

Making the Ball

Starting latex came
from Castilla Elastica
cis 1,4-polyisoprene
Water
Emulsifiers
Proteins

Mixed with juice

from a Morning Glory
Turns into a solid
rubber mass in ~10
minutes
Must be shaped
quickly

Rediscovery of Rubber
This feat wouldnt
be repeated until
1839
Charles Goodyear
discovers the
vulcanization of
rubber with sulfur
Doesnt patent it
until 1844
Simplest definition
is heating of natural
rubber with sulfur
under pressure

Commercialized Rubber
Castilla Elastica not
viable for commercial
rubber production
Modern natural
rubber derives from
Hevea Brasiliensis
While derived from
Brasil, most natural
rubber comes from
SE Asia
Latex contains cis1,4-polyisoprene

Gutta Percha: the Other Natural Rubber

Another version of
natural rubber is
derived from
Palaquium gutta
Not elastic like the
Mesoamerica latex
Could be heat
cycled
Softens around
100C
trans-1,4polyisoprene

Review: 3000 BC to 1844

Polymer use has
been tied to human
history
Resins were used in
Pharaonic Egypt
Continued use
through history

Elastomers used in
Ancient Mesoamerica
First example of
Polymer Processing
Techniques lost
until 1839

The Arrival of Celluloid

In 1846, Christian
Schonberg creates Gun
Cotton, the first
nitrocellulose
Georges Audemars
develops cellulose nitrate
fibers (rayon) in 1855
Parkesine is developed by
Alexander Parkes in ~1862
John Wesley Hyatt refines
the process and moves it to
an industrial scale to create
Celluloid in 1863
Required the use of a good
solvent (Camphor)

The Arrival Injection Molding

John Wesley Hyatt is also
credited with creating the first
Injection Molding System in
1868 (patent in 1872)
Operates as a simple
plunger system
First used as a replacement
for ivory to create billiard
balls as part of a contest
Doesnt change until 1946
when James Hendry builds
the first screw injection
molding machine
Used in Photographic Film
(1888) and later in Motion
Picture Film

Bakelite and the Rise of Art Deco

Leo Baekeland
discovers the phenol
formaldehyde resin
based polymers in
1907
Becomes very
popular after WWI for
use in the home
Rise of Art Deco,
with rounded edges
and streamlining,
help bakelite become
a material of choice

Discovery of Macromolecules
Hermann Staudinger proposes that
rubber and polymers are long chains of
short repeating molecular units (1920)
Prevailing thought at the time is that the
high measured molecular weights of
these molecules was due to an
aggregation phenomenon
Experimental evidence comes in the
1930s
membrane osmometry
viscosity
x-ray diffraction

Receives the 1953 Nobel Prize in

Chemistry for his discoveries in the field
of macromolecular chemistry.

Introduction of Condensation Polymers

Wallace Carothers
develops the first
synthetic Rubber
(Neoprene) in 1929
Sets the stage for
the concept of
condensation vs.
addition polymers
Goes on to develop
many of DuPonts
namesake brands
including the nylon
series (1934)
Died in 1937

Other significant Milestones

1926 Plastisizing and Moulding of
PVC by Waldo Semon (BF Goodrich)
Discovered twice in the 1800s
1838 Henri Victor Regnault
1872 by Eugen Baumann

Seen as white flake in vinyl chloride gas

that was left in the sun
Patented in 1913 by Friedrich Heinrich
August Klatte
Originally investigated as a replacement for
natural rubber
First used in shock absorber seals and
fabric coatings
Success came when used to insulate
wiring on military ships in WW2
First used as a piping material in the 1950s
which now accounts for the half the PVC
manufactured today.

Other significant Milestones

1938 TEFLON by Roy Plunkett
First synthesized by freezing and
compressing Freon gases
Initially formed a white, waxy solid using the
iron from the container as a catalyst

Patented in 1941
Teflon trademarked in 1945
Used early on to coat valves and seals
for uranium processing at Oak Ridge
National Lab for the Manhattan Project
First applied to a pan in 1954 by Marc
Grgoire and sold under the brand name
Tefal (he originally used it to coat fishing
line)
Used in NASA space suits starting with
the Apollo missions

Other significant Milestones

1943 Silly Putty by James Wright
(General Electric)
Combined Boric acid with Silicone oil
Looking for synthetic rubber
Earl Warwick and Rob Roy McGregor
(DowCorning) also claim credit

1949 Ruth Fallgatter and Peter Hodgson

Block Shop toy store
Sell Bouncing Putty for $2

Hodgson comes up with the name Silly

Putty in 1950
Responsible for the first TV ads
targeted at children in 1957
Marks the beginning of silicone based
rubbers and sealants

Other significant Milestones

1953/1954 Polyethylene/polypropylene
Karl Ziegler & Giulio Natta (Nobel Prize
1963)
First synthesized in 1898 by Hans von
Pechmann
Reacted diazomethane under heat and pressure
Results in a white, waxy material

First synthesized commercially in 1933 by Eric

Fawcett and Reginald Gibson (ICI)
Reacted ethylene with benzaldehyde and trace amounts
of oxygen under heat and pressure
Again results in a white, waxy material

Developed a catalyst that could operate at lower

temperatures and pressures and provide
stereoselectivity
Titanium Halides
Organometallic aluminum (triethyaluminum)

Off spec material originally used in the

hula hoop (1957)
Used as a replacement for glass in baby
bottles (1959)

Other significant Milestones

Polymer Related Nobel Prizes
1953 Hermann Staudinger: for his discoveries in the field
of macromolecular chemistry
1963 Karl Ziegler and Giulio Natta: for their discoveries in
the field of the chemistry and technology of high polymers
1974 Paul J. Flory: "for his fundamental achievements,
both theoretical and experimental, in the physical chemistry
of the macromolecules
1991 Pierre-Gilles de Gennes:"for discovering that
methods developed for studying order phenomena in
simple systems can be generalized to more complex forms
of matter, in particular to liquid crystals and polymers"
2000 Alan J. Heeger, Alan G. Macdiarmid, Hideki
Shirakawa: "for the discovery and development of
conductive polymers"