Timeline

Definition

 Plastic is broadly defined as

 Any inherently formless material that can be
molded or modeled under heat or pressure
 As early as…
 Go back as far as the Old Testament
 References of:
 Fillers
 Adhesives
 Coatings
 Good Ol’ Enoch Noyes
 1760
 Opened business with the use of natural
polymers
 Made combs out of organic proteins
(Keratin and Albuminiod) derived from
animal horns, hoofs, an tortoise shells
 In the beginning…
 Greek word plastikos
 First natural plastics
 Tortoise shell
 Tree resins
 Shellac
 Insect secretion
 Natural Rubber
 Natural rubber: mainly
polyisopropene

n
isoprene polyisoprene
 Tends to be sticky when
hot, brittle when warm
 Does not reform when
stretched
 Natural Rubber
 Natural rubber: mainly Charles Goodyear, 1839
polyisopropene Oven cleaning

Sulfur
crosslinking

n
isoprene polyisoprene S
 Tends to be sticky when S

hot, brittle when warm S S

S S

 Does not reform when

stretched
 Ebonite bracelet from 1880

1851: Hard Rubber— 20-30% Sulfur

 Christian Schoenbine
 Swiss Chemist
 1840’s
 Developed Cellulose nitrate
 Mix of cotton (wife’s apron), nitric acid, and
sulfuric acid

Early Films
Highly flammable and explosive
 Parkes Invents Celluloid
 The first man-made plastic was unveiled by
Alexander Parkes at the 1862 Great International
Exhibition in London.
 Parkesine- organic material derived from cellulose that
could be molded in heat and retain its shaped when
cooled
 Buttons
 Combs
 Pens
 Alexander Parkes- 1855
 Rights sold to Daniel Spill (1865)
 Patented
 Downfall- high cost of the raw materials needed
in its production.
 John Wesley Hyatt
 Billiard Co. in U.S.
 Needed substitute for ivory in making balls
 John Wesley Hyatt developed collodion CH3
H 2C
 Upon spilling a bottle of collodion in his workshop, he
discovered that the material congealed into a tough,
flexible film H 3C O
 Camphor and cellulose nitrate
 Occasional Explosion upon impact

C elluloid tics
m er ican t he Plas n
e d the A is t oday r por atio
Form ny which anese Co
a el
Comp n of the C
o
Divisi
 Bakelite
 Dr. Leo Baekeland
 First totally synthetic plastic (1907)
 Didn’t throw away his foul glassware
 Patented in 1909
 Thermoset resin
 Replaced rubber for insulation in
electrics
 Bakelite

H + +
:OH O :O OH OH OH OH OH2
:OH
H+

OH
OH OH OH O

OH OH OH

HO OH

HO
 Bakelite
 Phenol-formaldehyde
resins which he called
Bakelite.
 Polyvinyl Chloride (PVC)
 PVC was first created by
the German chemist
Eugen Baumann in 1872.
 Patented in 1913
 Waldo L. Semon,
invented a way to make
polyvinyl chloride (PVC)
useful
Polyvinyl Chloride (PVC)
Baumann's 1872 experiment

Cl Cl Cl Cl Cl Cl Cl
sunlight

sealed tube

•R
Cl
•

R R

•
Cl Cl Cl
Applications of PVC
Applications of PVC

O plasticizers

O
O

O
 Polymerization
 In 1920, German Hermann
Staudinger published theories
on polyaddition
 Nine year later published the
polymerization of polystyrene.

Ph Ph Ph
+

Ph Ph Ph Ph Ph

1%
 Polystyrene
 Dow Chemical
brought polystyrene
to the U.S. in 1937

Toy shark, in
 Merrifield resins Polystyrene, with
moving jaw, Made
in USA around
1950
 Styrofoam
 Foam egg cartons, burger containers, coffee
cups , "peanuts" used in packing and the
lightweight foam pieces that cushion new
appliances and electronics.
 Gas is blown in during the polymerization-- 95 %
of styrofoam is air (try dissolving in acetone)
 CFC’s were used until the 80’s: phased out and
replaced with pentane or CO2

Polystyrene up close
 Dr. Wallace H. Carothers
 1930’s research on
polymer chains at
DuPont Chemical
Department
 Invented Neoprene
and Nylon
Nylons
 Condensates of aliphatic diacids with
aliphatic diamines
 Introduced in the 1939 Worlds Fair
 “Nylonmania” interrupted during WWII,
but resumed after the war (the infamous
Nylon riots of 1946)

Nylon 66
co-crystalline
O
+ NH 2
HO H 2N
OH
O
- H 2O

O O
H H
N N etc.
N N
H H
O O

Fibers are spun (showerhead)

 Synthetic Rubbers

Neoprene: The first Synthetic Rubber

Cl
Cl Cl •

Cl etc
Cl •
R• R
R
benzoyl peroxide
inititates free radical Gasoline pump hoses,
polymerization
Hoses for automobile engines

Styrene/Butadiene copolymer (SBR) is the most important synthetic rubber,

and was the first and most widely produced rubber of WWII
 Plexiglass: anionic
polymerization

Polymethylmethacrylate:

Me CO 2Me
Me CO 2Me
Me CO 2Me CO 2Me
MeO 2C Me
Me

cat Nu – Nu

Windshields, plastic coatings, hard and soft contact lenses

 Ok, but how can I make a leisure suit

 Polyesters

O OMe OH

MeO O HO

O O
O O

O O
O O

O O Dacron
 Teflon

 Teflon
 Polytetrafluoroethylene
(PTFE)
 Dupont Chemical
Department
 First used for artillery
shell covers
F F

F F
 World War II
 Polyethylene (1933)
 Imperial Chemical Industries in England
 E.W. Fawcett & R.O. Gibson
 First used for underwater cable coatings and
insulation for radar

Low density polyethylene

1939

High density polyethylene

Ziegler-Natta catalysts
 Polyethylene
 1943 Karl Ziegler changed
polymerization of
polyethylene
 Use of catalysts
 Now is most widely
produced and perhaps most
versatile plastic
 Polypropylene
 Guilio Natta continued Ziegler’s work
 Created polypropylene in 1957
 Substituted for polyethylene where high
temperatures were involved
 Ex. Dishwasher safe dishes

Car’s front bumper

made of polypropylene
in 1978
Stereochemistry and Polymer Properties

isotactic

syndiotactic

atactic

Isotactic: fabrics for carpets, automobile parts, battery casings,

medicine bottles
Syndiotactic: new applications are emerging
Atactic: soft, and not very useful
 Relevant Additional Links
 History of Plastic and Leo Bakeland
 inventors.about.com/library/inventors/blplastic.htm

 History of Plastics
 www.lle.mdx.ac.uk/site/docs/dt/Historyofplastics.html

 About Plastics
 www.americanplasticscouncil.org/benefits/about_plastics/history.html