Lecture on Basics of Polymer Science &

its Chronological Development

Course Instructor:
Vimal Katiyar, Department of Chemical Engineering
Polymer Science & Technology (CL-623)
 Introduction
Polymer: (poly)+(mer)

Monomer (elementary repeat unit)

❑ Number of small molecules capable of polymerizing

❑ Mass of one polymer chain (M)=NₓMmon

(No of elementary repeat unit)

monomer O
dimer O + O O O

trimer O O + O O O O
tetramer
O O + O O O
oligomer m m+1
polymer O O + O O O
n n+1
Polymer Science & Technology (CL-623)
Basic Definitions and Nomenclature

❖ Skeletal Structure
❑ Linear skeletal:- Chain with two ends
❑ non-linear skeletal
▪ Short Branch skeletal Large branch skeletal

▪ Network skeletal
▪ Ring
▪ Star-branched
▪ H-branched
▪ Comb
▪ Ladder
▪ Dendrimer
Polymer Science & Technology (CL-623)
❖ Density: Depends on packing of polymer chains
❖ Strength
❑ Linear PE has higher MP about 20 than that of branched PE
❑ Unlike linear or branched polymers Network does not melt
upon heating and will not dissolve
❑ It may swell in compatible solvents properties can be change
by tailoring crosslink density.
❑ Crosslinked polymer characterized by their crosslink density
or degree of crosslinking related to (no. of junction points
per unit volume)

Polymer Science & Technology (CL-623)

Polymers Based on sequence of Monomers
❖ Homopolymer A A A A A A A A
❖ Heteropolymer: Copolymer, terpolymer,...
❖ Copolymer:
❑ Polymer derived from more than one monomer
❑ Polymers whose molecules contains two or more different type of repeat
units.
▪ Simplest copolymers: A and B repeat unit.

❑ Statistical copolymers: copolymers in which the sequential distribution of

the repeat units obey known statistical law (Markovion)
❑ Random copolymers: Here distribution of repeat units is truly random.
A A B B B A B B A A
❑ Alternating copolymers
A B A B A B A B

▪ RC and AC generally have properties intermediate to those of the corresponding

homopolymers.

Polymer Science & Technology (CL-623)

❖ Block polymers: where repeat units exist only in long sequences (linear
polymers) or blocks of same type.
A A A A A B B B B B

Block A Block B

❖Graft polymers: Branched polymers in which the branches have a different

chemical structure to that of the main chain. B B B B B B
B

A A A A A A A A A A
❑ BC and GC generally show properties characteristics of B

B B B B B B
each of the constituent homopolymer.
Principles of nomenclature for copolymers
Type of copolymers Examples of nomenclature
❑ Unspecified Poly(A-co-B)
❑ Statistical Poly(A-stat-B)
❑ Random Poly(A-ran-B)
❑ Alternating Poly(A-alt-B)
❑ Block PolyA-block-polyB
❑ Graft* PolyA-graft-polyB
Polymer Science & Technology (CL-623)
 Classification of Polymers
(Based on molecular structure of the polymers )

Polymers

Thermoplastics Elastomers Themosets

Rigid material and are

Crystalline Amorphous network polymers in which
order (highly coiled) (Crosslinked rubbery chain motion is greatly
Molecular
polymers (rubbery network) restricted by DC
Arrangements
can be stretched easily to * Degrade rather melting
high extensions(3 x to 10 x to
Can be melt upon the their original dimensions)
application of heat
Can be processed
Do not crystallize easily
upon cooling
And rapidly converts their
Appear simultaneously in
original dimensions when
both Crys. & Amorphous
applied stress is released.
Sharp &

Force of intermolecular attraction and

Polymer Science & Technology (CL-623)
Advances in Polymer Sci. and Tech..

❖In the beginning…

❑ First natural plastics
▪ Tortoise shell
▪ Tree resins
▪ Insect secretion
❑ 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

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..

❖Natural rubber: n
mainly polyisoprene isoprene polyisoprene

❑ Tends to be sticky when hot, brittle when warm

❑ Does not reform when stretched

❑ 1851: Hard Rubber— 20-30% Sulfur

Greatly enhances its elasticity and toughness

Sulfur ❖Charles Goodyear, 1839

crosslinking

S
S

S S
His “sulfurized” rubber, later known
S S
as “vulcanized” rubber, is still widely used today

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..
❖ Cellulose nitrate
❑ Semi-synthetic plastic
❑ Demonstrated in Great International Exhibition in
London, England as Parkesine, (cellulose nitrate
and a solvent).
❑ Could be heated, formed, and it retained its shape
when cooled.
❑ Can be molded or carved into products such as
buttons, combs, picture frames and knife handles.
❑ This was never commercialized due its relatively
high cost compared to vulcanized rubber.
❑ Mix of cotton (wife’s apron), nitric acid, and
sulfuric acid
Examples:Buttons, Combs, Pens Alexander Parkes, 1862
Polymer Science & Technology (CL-623)
Advances in Polymer Sci. and Tech..

❑ Blended nitrocellulose with camphor (sap from the

laurel tree)
❑ Produce a durable, colorful, and moldable
thermoplastic known as celluloid.
John Wesley Hyatt
❑ Celluloid was the first commercially
celluloid in 1868
successful semi-synthetic plastic.
*Billiard balls
*Shirt collars
*Eyeglass frames
*Pen housings

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..
Bakelite (1907)
❖ Dr. Leo Baekeland (Belgian born chemist)
❑ First totally synthetic plastic
❑ Didn’t throw away his foul glassware

Catalyst: hexamethylenetetramine
❖Patented in 1909: Right to Kodak Co. (Camera)
❑ Thermoset resin, replaced rubber for insulation in electrics
❑ Properties: electrically resistant, chemically stable, heat resistant, rigid,
moisture and weather resistant.
❑ Hyatt-Burroughs Billiard Ball Company replaced celluloid by Bakelite for
their billiard balls due to its superior performance.
Polymer Science & Technology (CL-623)
Advances in Polymer Sci. and Tech..
❖Polyvinyl Chloride (PVC)
▪ Invented by the German chemist Eugen Baumann.
▪ Waldo L. Semon, invented a way to make polyvinyl chloride
(PVC) useful by adding Plasticizer
▪ PVC formulations can be either rigid or flexible depending their
plasticizer concentration.
▪ Initial application for PVC included foul weather gear and
electrical wire insulation.

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..
❖Baumann's 1872 experiment O

Cl Cl Cl Cl Cl Cl O
Cl sunlight O
sealed tube O

•R • Cl Plasticizers

•
R R
Cl Cl Cl

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..
Polystyrene
❑ Scientist from the BASF Corporation developed a
commercial process for the manufacture of PS IN 1930.

Ph Ph Ph
+

Ph Ph Ph Ph Ph

1%

1939: Wood TV 1948: Phenolic 1970: HIPS TV

Cabinet TV Cabinet Cabinet
Polymer Science & Technology (CL-623)
Advances in Polymer Sci. and Tech..

❑ Toy shark, in Polystyrene, with moving jaw, Made in USA around

1950
❑ Dow Chemical brought polystyrene to the U.S. in 1937
❑ 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

Polymer Science & Technology (CL-623)

Nylon

❖ 1930’s research on polymer chains at DuPont Chemical Department Invented

Neoprene and Nylon
❖ Dr. Wallace H. Carothers, pulled the first long, strong, flexible strands of a synthetic
polymer fiber out of a test tube & introduced commercially in 1938.
❑ This artificial fiber had properties similar and in many ways superior to
natural fibers.
❑ The material, poly(hexamethylene adipamide), is more commonly known as
“nylon 66”. One of the earliest uses of nylon 66 fiber: tooth brush bristles.
❖ During World War II, nylon was used for many applications
❑ cargo parachutes,
❑ tire cord for bombers,
❑ glider tow ropes,
❑ flak jackets, mosquito netting,
❑ Jungle clothing

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..

❑ Condensates of aliphatic diacids with

aliphatic diamines
O
+ NH2
HO H 2N
OH
O
- H 2O

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

co-crystalline Nylon 66

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..

❖ Synthetic Rubbers
Neoprene: The first Synthetic Rubber
Cl
Cl Cl •

Cl etc
Cl •
R• R
R
benzoyl peroxide
inititates free radical
polymerization

❖Applications:
▪ Gasoline pump hoses,
▪ Hoses for automobile engines

Polymer Science & Technology (CL-623)

Advances in Polymer Sci. and Tech..

❖ PMMA anionic polymerization (1937)

❑ PMMA is a very hard material and have superior optical properties

❑ Transparent than glass

❑ Used as Hard and soft contact lenses

❑ Thermoformed aircraft canopies.

❑ Automotive tail light lenses due to its, where it is still used today.

PMMA is also used as acrylic fibers, paints and coatings, and as a

marble replacement for kitchen countertops.

Polymer Science & Technology (CL-623)
Advances in Polymer Sci. and Tech..
❖ Polyethylene Terephthalate (PET), 1941
❑ Extremely versatile thermoplastic
❑ Made by the condensation reaction of ethylene glycol
and terephthalic acid.
❑ Initially used for the production of synthetic textile
fiber, know today as Dacron®.
❑ Biaxially oriented PET film, known as Mylar®
❑ However, largest use for PET is -“stretch blow
molded” transparent, lightweight, have good barrier
properties, and shatter resistant beverage bottles.
❑ PET is recyclable.
❑ Recycled PET bottles are reprocessed to form PET textile fiber for
clothing.
Polymer Science & Technology (CL-623)
 O OMe OH

MeO O HO

O O
O O

O O
O O

O O

❖ Polytetrafluoroethylene (PTFE)
❑ Dupont Chemical Department F F
❑ First used for artillery shell covers
F F

Polymer Science & Technology (CL-623)

Polytetrafluoroethylene (PTFE), 1938.
❑ DuPont scientist Dr. Roy Plunkett, accidentally discovers
polytetrafluoroethylene (PTFE).
❑ An inherently slippery and remarkably chemically resistant
plastic. Most slippery substance on earth.
❑ Commercial introduction of DuPont’s Teflon® - 1946.
❑ Teflon® is most widely known for its widespread use
in nonstick cookware
❑ Cable insulation.
❑ Teflon® sheet is used as an insulator and lubricant between the copper
skin and the stainless steel skeleton of the Statue of Liberty.
❑ The roof of the Pontiac Silverdome is made of a Teflon® coated woven
glass fiber fabric.

Polymer Science & Technology (CL-623)

❖Polyethylene (1933)
❑ Imperial Chemical Industries in England
❑ E.W. Fawcett & R.O. Gibson
❑ First used for underwater cable coatings and
insulation for radar

Karl Ziegler changed Low density polyethylene

1939
polymerization of
polyethylene
Use of catalysts Polyethylene
Now is most widely
produced and perhaps
most versatile plastic High density polyethylene
Ziegler-Natta catalysts

Polymer Science & Technology (CL-623)

❖Ultra High Molecular Weight Polyethylene
(UHMWPE) UHMWPE
acetabular
❑ One of the most interesting medical applications for
UHMWPE is the “artificial hip”.
❑ Each prosthesis is made up of two parts: the acetabular
component (socket portion) that replaces the acetabulum,
and the femoral component (stem portion) that replaces the
femoral head.
❑ The femoral component is made of titanium, while the
acetabular component is made of a metal shell with a
plastic inner socket liner. UHMWPE acts like a bearing. It is
extremely tough, abrasion resistant and has a very low
coefficient of friction. Titanium
stem
❑ This is a very good example of how plastics and metals work
together to enhance our quality of life.

Polymer Science & Technology (CL-623)

❖Polyacrylonitrile butadiene styrene ABS (1951)
❑ “Blend” of SAN & butadiene rubber
❑ Butadiene act as an impact modifier.
❑ if the SAN is chemically grafted onto the butadiene rubber
“terpolymer”-provide outstanding Impact strength.
❖Applications
❑ football helmets, which are now made from polycarbonate.
❑ Today, ABS is most widely used for consumer electronics
and business machine housings.

SAN: polystyrene-acrylonitrile copolymer

Polymer Science & Technology (CL-623)
Glass Fiber Reinforced Plastic (1953)

❑ General Motors introduced-Chevrolet Corvette in

❑ Glass fiber reinforced plastic as a body material
❑ Car was available in white body and red
❑ Interior 1953, and sold for $3,498

2003 50th Anniversary Corvette

Polymer Science & Technology (CL-623)
Polycarbonate (1953)
❑ Hermann Schnell from Bayer A.G. & Daniel Fox from GE-discovered PC
❑ Optically transparent engineering thermoplastic
❑ Unique combination having:
▪ Stiffness and toughness, heat resistance and electrical insulating
properties
❑ Application
▪ Automotive headlights,
▪ Tool housings,
▪ Helmets and computer enclosures
▪ All CD’s, CD-ROM’s and DVD’s

Polymer Science & Technology (CL-623)

Polypropylene (1957)
❖Guilio Natta continued Ziegler’s work
❑ Created polypropylene in 1957
❑ Substituted for polyethylene where high temperatures were involved
❑ Ex. Dishwasher safe dishes
❑ Long chain stereo-regular polypropylene molecule.
❑ Very good balance of properties include stiffness, toughness, chemical
resistance, and translucent optics.
❑ Strong ability to form copolymers with most widely used thermoplastics.

Car’s front bumper (1978)

Polymer Science & Technology (CL-623)
 Plastic made MOON possible
❑ July 20, 1969 –greatest technological achievement
❑ when Neil Armstrong set foot on the moon
❑ Plastics played an important roll.
❑ Apollo A7L space suits were a multi-layer plastic structure comprised of

▪ Nylon fabric,

▪ Neoprene coated nylon fabric,

▪ Dacron® (PET) fabric,

▪ Aluminized Mylar® (PET) film,

▪ Kapton® (PI) film, and Teflon® (PTFE) coated fabric.

▪ “fish bowl” helmet - polycarbonate.

▪ Space suits of today make even more extensive use of plastics.

Polymer Science & Technology (CL-623)

Kevlar® (1960’s)
▪ Five times stronger than steel (on a strength per
weight basis)
▪ Kevlar® is a condensation polymers.
▪ Bulletproof vests are made;
▪ In fact, Kevlar® has dozens of important applications, Stephanie Kwolek
including

Radial tire cord,

Brake pads,
Racing boat sails,
Aircraft components,
Suspension bridge
cables.

Polymer Science & Technology (CL-623)

Kevlar® contd..
❖ Thermal Stability

❖ Stress-strain relation

Polymer Science & Technology (CL-623)

Polyurethane
❑ Polyurethane- Formed by reacting a polyol (an alcohol
with more than two reactive hydroxyl groups per
molecule) with a diisocyanate or a polymeric isocyanate
❑ In the presence of suitable catalysts and additives.
❑ It can be molded, extruded, or cast,
❑ Available as foams, coatings, specialty adhesives and
sealants.
❑ The first artificial replacement heart, the Jarvic-7, was
produced from a flexible and fatigue resistant
polyurethane.
❑ The toughness and abrasion resistance of polyurethane
make it an ideal material for applications such as in-line
skate wheels

Polymer Science & Technology (CL-623)

❖ Plastics for telephone housings since the turn of the last century.
❑ Thermosetting phenolic thicknesses up to 13 mm.
❑ Injection molded ABS phones were introduced
in the 1950’s. thicknesses of about 3 mm.
❑ ABS has a very high gloss, good impact resistance, and could
be molded in a variety of different colors.
❑ Polycarbonate & ABS blend (PC/ABS). The compact and
lightweight phones of today have wall thicknesses in the range
of 1 mm.
❑ Telephones are a good example of how plastic products evolve
over time.
❑ Creative product designers make use of new plastic materials
and new plastic processing technologies as they become
available in order to improve product performance
Polymer Science & Technology (CL-623)
The Nobel Prize-Field of Polymers macromolecules

❖ Hermann Staudinger for his many discoveries in the field of macromolecular

chemistry (1953)

❖ Karl Ziegler and Giulio Natta for their discoveries related to polymer
chemistry and new polymerization technologies (1963)

❖ Paul J. Flory for fundamental achievements, both theoretical and

experimental, in the physical chemistry of macromolecules (1974)

❖ P.G. de Gennes for creating the reptation model of polymer dynamics used
to predict polymer properties and viscosity (1991)

❖ Alan J. Heeger, Alan G. MacDiarmid and H. Shirakawa for the discovery and
development of inherently conductive polymers. (2000).
❖ Atom Transfer Radical Polymerization-2005

Polymer Science & Technology (CL-623)